JP2002529352A - Metal oxide particles - Google Patents

Abstract

(57) Summary Manganese oxide particles and lithium manganese oxide particles having an average particle size of about 500 nm or less have been produced. These particles have a high degree of homogeneity, including a very narrow particle size distribution. A method for producing a metal oxide by performing a reaction using an aerosol containing a metal precursor has been described. In particular, these particles were prepared by laser pyrolysis. Lithium manganese oxide particles can be prepared by heat treating manganese oxide nanoparticles. Alternatively, lithium manganese oxide particles can be produced directly by laser pyrolysis. The lithium manganese oxide particles are useful as an active material in the anode of a lithium-based battery. An improved battery is obtained by using uniform nanoscale lithium manganese oxide particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to metal oxides. More particularly, the present invention relates to nanoscale metal oxide particles such as manganese oxide particles and lithium manganese oxide particles produced by laser pyrolysis. The invention further relates to a method for producing metal oxide powder using laser pyrolysis and aerosol. Furthermore, the present invention provides
The present invention relates to a method for producing ternary particles, especially crystalline nanoparticles, by laser pyrolysis.

[0002] Advances in the background various fields of the invention, the demand for many types of new material has been created. In particular, a variety of chemical powders are used in many different processing-related fields, such as the manufacture of batteries. In particular, including small structures or high surface area materials,
There is considerable interest in the application of ultrafine or nanoscale powders, which is particularly useful for a variety of applications. This demand for ultrafine chemical powders has led to the development of sophisticated technologies, such as laser pyrolysis, for the production of these powders.

[0003] The miniaturization of electronic components is achieved by using small telephones, pagers (storage devices, pages).
Has resulted in widespread growth in the use of portable electronic devices such as video cameras, facsimile machines, portable stereo sound equipment, personal organizers and personal computers. The growing use of portable electronic devices has led to an ever-increasing demand for improved power supplies for such devices. Suitable batteries include primary batteries, ie, batteries designed for use in a single charge cycle, and secondary batteries, ie, batteries designed to be rechargeable. Some batteries, which are originally designed as primary batteries, can be recharged to some extent.

[0004] Lithium-based batteries are the subject of significant development efforts and are sold commercially. Lithium-based batteries generally use an electrolyte containing lithium ions. Cathodes for these batteries are lithium metal or alloy (
(Lithium battery) or a composition containing lithium between layers (lithium ion battery). A recommended electroactive material for incorporation into the anode is a composition containing lithium between the layers. This composition containing lithium between the layers for use in the anode is usually chalcogenides, such as metal oxides that can incorporate lithium ions in their lattice.

[0005] Manganese can exist in various oxidation states. Correspondingly, it is known that manganese oxides having various stoichiometric compositions exist. Further, manganese oxides having a particular stoichiometric composition can have various crystal lattices,
Or it may be amorphous. Thus, manganese oxide exhibits an extremely abundant phase diagram.

[0006] Manganese oxide and lithium manganese oxide having various stoichiometric compositions have attracted attention as promising materials used in anodes for lithium-based batteries. In particular,
Suitable manganese oxides can incorporate lithium ions between layers of the crystal structure to form lithium manganese oxide. Lithium manganese oxide is useful for manufacturing a lithium secondary battery. Due to this interest in lithium manganese oxide,
Several methods for producing lithium manganese oxide powder have been developed.

[0007] In summary first aspect of the invention, the present invention has an average particle size of less than about 500 nm, amorphous manganese oxide, crystalline MnO, crystalline Mn ₅ O ₈ and crystalline Mn ₂ O ₃ A manganese oxide having a structure selected from the group consisting of:

In another aspect, the invention is a method comprising reacting an aerosol in a reaction chamber to prepare a metal oxide, wherein the aerosol comprises a metal precursor. And the metal oxide particles have an average particle size of about 500 nm or less.

[0009] In a further aspect, the present invention provides a method for forming a stoichiometric composition of manganese oxide particles, comprising heating manganese oxide particles in an oxidizing atmosphere at a temperature of about 600 ° C. or less. How to change.

In another aspect, the invention relates to a battery having a cathode comprising manganese oxide particles, wherein the manganese oxide particles have an average particle size of about 250 nm or less.

Further, the present invention is a method comprising preparing a powder of composite metal oxide particles having an average particle size of about 1 micron or less, comprising reacting an aerosol, wherein the aerosol is And a method for producing composite metal oxide particles comprising a first metal compound precursor and a second metal compound precursor.

[0012] In a further aspect, the invention is a method of producing a lithium metal oxide comprising pyrolyzing a reactant stream in a reaction chamber, wherein the reactant stream comprises a lithium precursor, a non-lithium precursor. It comprises a lithium metal precursor, an oxidizing agent and an infrared absorber, the pyrolysis of which relates to a method driven by heat absorbed from a light beam.

In another aspect, the invention is directed to an aggregate of particles comprising lithium manganese oxide having an average particle size of about 250 nm or less, wherein the aggregate of particles comprises at least about 95% of the particles. A collection of particles having a particle size distribution such that percent has a diameter greater than about 40 percent of the average particle size and less than about 160 percent of the average particle size.

Still further, the present invention is a method of producing lithium manganese oxide particles comprising heating a mixture of manganese monoxide (MnO) particles and a lithium compound, wherein the manganese monoxide particles comprise about A process having an average particle size of 250 nm or less.

Further, the present invention is a method for producing lithium manganese oxide particles, comprising heating a mixture of manganese oxide particles and a lithium compound, wherein the manganese oxide particles have a particle size of about 250 nm or less. The average particle size of the resulting lithium manganese oxide particles is such that at least about 95 percent of the particles have a diameter greater than about 40 percent of the average particle diameter and less than about 160 percent of the average particle diameter. Having such a particle size distribution.

In a further aspect, the present invention provides a method wherein the particles of lithium manganese oxide comprise about 25
0 nm or less, wherein the lithium manganese oxide particles have a diameter such that at least about 95 percent of the particles are greater than about 40 percent of the average particle size and less than about 160 percent of the average particle size. A battery comprising lithium manganese oxide particles having a particle size distribution as described above.

In another aspect, the present invention is directed to a battery comprising lithium manganese oxide, wherein the battery has a 4 volt voltage curve having cycling stability within about 20 percent of its initial value after 25 cycles. Features.

Further, the present invention relates to a battery comprising lithium manganese oxide,
A battery having an initial capacity of Ah / g or more is characterized. Still further, the present invention provides an aggregate of particles comprising lithium manganese oxide, wherein the aggregate of particles has an average diameter of about 250 nm or less, and wherein the lithium manganese oxide comprises Li ₂ Mn ₄ O _9. About.

In a further aspect, the present invention is directed to an aggregate of particles comprising lithium manganese oxide, wherein the aggregate of particles has an average diameter of about 250 nm or less, and wherein the lithium manganese oxide has a mean diameter of 8. A collection of particles with lattice parameters along the axis of less than or equal to 23 Angstroms.

Still further, the present invention provides a method of producing crystalline ternary particles comprising reacting a reactant stream comprising a precursor comprising three atoms of the product ternary particles. Wherein the relative amounts of the three atoms in the reaction stream and the reaction conditions are selected to produce the crystalline ternary particles.

In another aspect, the invention is directed to a method of making crystalline lithium manganese oxide particles comprising reacting a reactant stream comprising a manganese precursor and a lithium precursor, the method comprising: Are driven by energy from electromagnetic radiation.

[0022] In a further aspect, the invention is an aggregate of particles comprising a crystalline multi-component metal oxide having an average particle size of about 500 nm or less, wherein the lithium manganese oxide particles have an average particle size of about 500 nm or less. At least about 95 percent relates to a collection of particles having a particle size distribution such that they have a diameter that is greater than about 40 percent of the average particle size and less than about 160 percent of the average particle size.

DETAILED DESCRIPTION OF THE RECOMMENDED EMBODIMENT Several methods for making metal oxide nanoparticles are described. These methods are provided for producing metal oxide particles, such as manganese oxide nanoparticles having a wide range of properties. Aerosol-based methods are described that can utilize low cost precursors to produce nanoparticles at high production rates. Desirable aggregates of metal particles have a submicron average particle size and a very narrow particle size distribution. Laser pyrolysis, used in combination with additional processing or alone, is a versatile method for the production of a wide range of manganese oxides. The aerosol-based method described herein is used for the production of many other metal oxide nanoparticles.

In particular, several alternative methods have been found for the preparation of nanoscale crystalline ternary particles. Crystalline ternary particles have three types of atoms located at particular lattice sites in one crystal structure. Ternary particles of lithium metal oxides, such as lithium manganese oxide, are of particular interest because they are useful in battery applications.

In the first method, it has been found that nanoscale manganese oxide provides a suitable starting material for the preparation of nanoscale lithium manganese oxide. In particular, by thermal processing using nanoscale manganese oxide starting materials, lithium manganese oxide having a spinel crystal structure and an average particle size of submicron can be prepared. The use of this nanoscale starting material makes it possible to use very mild temperatures in its processing. The resulting nanoscale lithium manganese oxide spinel provides an excellent material for the preparation of lithium-based batteries.

Alternatively, lithium manganese oxide nanoparticles can be prepared by laser pyrolysis. Amorphous lithium manganese oxide produced by laser pyrolysis can be heated under mild conditions to slowly heat-treat the particles to produce a spinel crystal structure. Further, crystalline lithium manganese oxide nanoparticles can be directly produced by laser pyrolysis. The lithium manganese oxide powder produced by this laser pyrolysis is subjected to a heat treatment to change and / or improve the properties of the particles. Thus, useful alternatives for producing lithium manganese oxide nanoparticles have been found.

More specifically, in a first method, the lithium manganese oxide particles comprise:
It is prepared by heating a mixture of nanoscale manganese oxide particles and a lithium compound. During this heating step, lithium is incorporated into the manganese oxide lattice. The manganese oxide particles for thermal lithium uptake can have a variety of stoichiometric compositions and, surprisingly, also include MnO. This heating is performed under either an oxidizing atmosphere or an inert atmosphere. Due to the nanoscale properties of the manganese oxide starting material, its heating can be performed under surprisingly mild conditions. Under these mild conditions, lithium manganese oxide particles having a submicron average particle size are formed.

A recommended method for preparing nanoscale manganese oxide particles suitable for lithiation involves laser pyrolysis. In particular, laser pyrolysis is a great method for efficiently producing manganese oxide particles and other metal oxide powders having a narrow average particle size distribution.

A fundamentally important point for successful application of laser pyrolysis for the production of metal oxide nanoparticles is the generation of a reactant stream containing metal precursor compounds, radiation absorbers and secondary reactants. is there. This secondary reactant may be a source of oxygen. The reaction stream is pyrolyzed by a strong laser beam. As the reactant stream leaves the laser beam, the particles are rapidly cooled.

To carry out the laser pyrolysis, the reactants are supplied in the form of steam. Alternatively, one or more reactants are provided as an aerosol. The use of aerosols makes laser pyrolysis available to a wider range of metal precursors than those that are only suitable for vapor delivery. Thus, less expensive precursors can be used by the aerosol delivery method. By appropriately controlling the reaction conditions using an aerosol, nanoscale particles with a narrow particle size distribution can be obtained. The heat treatment of manganese oxide nanoparticles for preparing lithium manganese oxide nanocrystals and batteries prepared from these nanoparticles are described below.

As one alternative for producing lithium manganese oxide nanoparticles by thermal processing of manganese oxide particles, lithium manganese oxide particles having substantially submicron diameter are produced directly by laser pyrolysis. Laser pyrolysis for direct production of lithium / manganese composites desirably includes an aerosol-based reactant delivery device. As a result of thermal processing of the composite material particles, crystalline lithium manganese oxide particles having a spinel crystal structure are obtained. The direct preparation of nanoscale amorphous lithium manganese oxide by laser pyrolysis is described further below.

As a result of the laser pyrolysis experiments described in the examples below, amorphous lithium manganese oxide nanoparticles are obtained. In other experiments, the parameters of laser pyrolysis synthesis are adjusted to directly obtain crystalline lithium manganese oxide nanoparticles by laser pyrolysis. These are also described in the examples below. Phase diagrams of these materials to be manufactured can guide the selection of appropriate laser pyrolysis conditions. In addition, these parameters may be adjusted experimentally to reach conditions suitable for the production of the desired crystalline ternary particles. In particular, to produce spinel LiMn ₂ O ₄ , water-based aerosols require high chamber pressures, large oxygen flows,
With a low laser intensity, and with aerosols based on water and isopropyl alcohol, a relatively high laser intensity is desirable.

The preparation of substituted metal oxides Ti _1-X V _X O ₂ by laser pyrolysis is described in Musci et al., Cited herein by reference. , “Laser synth
esis of vanadium-titanium oxide data
lyste "(" Laser synthesis of vanadium-titanium oxide catalyst ") J. Ma
ter. Res. Vol. 7 (10): 2846-2852 (October
1992). In these substituted metal oxides, vanadium is
Substituting the lattice site for the titanium atom. The value of x can only increase by about 0.25 or less before another vanadium oxide phase forms. These substituted metal oxides are not crystalline ternary compounds because their metal atoms are not at their own lattice sites. In a crystalline ternary compound, each atom is located at a particular lattice site and forms a particular crystal structure. A similar substituted compound in which chromium in Cr ₂ O ₃ is replaced by titanium is disclosed in US Pat.
3,706 [Inventor: Schram et al., Entitled "Metal oxide powders or mixtures thereof and their use in catalytic dehydrogenation of hydrocarbons"].

As noted above, various forms of manganese oxide and lithium manganese oxide are capable of reversibly incorporating lithium atoms and / or ions between the layers. These manganese oxide and / or lithium manganese oxide nanoparticles can be incorporated into the positive electrode thin film with a binder such as a polymer. The thin film preferably includes additional electrically conductive particles held by a binder, along with the lithium manganese oxide particles. This anode thin film is used in a lithium battery or a lithium ion battery. The electrolyte for lithium and lithium ion batteries contains lithium ions.

A. Production of particles using laser pyrolysisLaser pyrolysis is used to produce nanoscale metal oxide particles, especially for further processing manganese oxide particles into lithium manganese oxide or lithium manganese oxide particles. It has been found to be a useful tool for direct manufacturing. Furthermore, particles produced by laser pyrolysis are a convenient material for further processing to broaden the path for producing the desired metal oxide particles. Thus, by using laser pyrolysis alone or in combination with additional processing, a wide variety of metal oxide particles can be produced.

Manganese oxide nanoparticles produced by laser pyrolysis are desirable starting materials for the lithium incorporation method described herein that involves mildly heating the manganese oxide nanoparticles and the lithium compound. In addition, lithium manganese oxide nanoparticles
It can be produced directly by laser pyrolysis, in which case heating is used to change and / or improve the properties of the resulting particles. The lithium manganese oxide nanoparticles prepared by the laser pyrolysis may be amorphous or crystalline.

The quality of the particles produced by laser pyrolysis depends on the reaction conditions. The reaction conditions for laser pyrolysis can be controlled relatively accurately to produce particles having the desired properties. Suitable reaction conditions for producing certain types of particles generally depend on the design of the particular device. The specific conditions for producing manganese oxide particles in two specific devices and the specific conditions for producing lithium manganese oxide in a first specific device having two different reactant delivery devices are described in the following examples. Illustrated in the example. Furthermore, there are some general correlations between the reaction conditions and the resulting particles.

As the laser output increases, the reaction temperature in the reaction zone increases, and the quench rate also increases. Rapid quenching rates tend to favor the creation of high energy phases that cannot be obtained by methods approaching thermal equilibrium. Similarly, increasing the pressure in the reaction chamber tends to create higher energy structures. Also, increasing the concentration of the reactant, which serves as an oxygen source in the reaction stream, favors the production of particles rich in oxygen.

The reactant gas flow rate and the velocity of the reactant gas flow (reactant gas flow rate)
stream) is inversely proportional to the particle size. That is, as the flow rate or velocity of the reactant gas increases, the particle size tends to become smaller. Furthermore, the kinetics of particle growth also significantly affects the size of the particles obtained. In other words, different forms of the product compound have a tendency to form particles of a different size than the other phases under relatively similar conditions. Laser power also affects particle size, and as laser power increases, lower melting materials tend to produce larger particles, and higher melting materials tend to produce smaller particles.

[0040] Laser pyrolysis is generally performed in a gas phase reaction. The use of exclusively gas phase reactions places some restrictions on the types of precursor compounds that can be used. Thus, several techniques have been developed to introduce an aerosol containing a reactant precursor into a laser pyrolysis chamber. Aerosol nebulizers are, roughly, as ultrasonic nebulizers that use ultrasonic transducers to prepare aerosols, or to prepare aerosols with one or more flowing fluids (liquids, liquids, etc.). Gases or supercritical fluids) are classified as mechanical atomizers that use energy from themselves. An improved aerosol delivery device for a reactant system is disclosed in co-pending U.S. patent application Ser. No. 09 / 188,092, incorporated by reference herein.
No. 670 [Inventor: Gardner et al., Name: “Reactant delivery device”, Filing date: 1
Nov. 9, 998].

Using an aerosol delivery device, a solid precursor compound can be delivered by dissolving the compound in a solvent. Alternatively, the powdered precursor compound is dispersed in a liquid / solvent for aerosol delivery. Liquid precursor compounds can be delivered as aerosols from pure liquids, as multi-component liquid dispersions, or, if desired, as liquid solutions. The aerosol reactant is used to obtain a significant amount of reactant flow. Solvents can be selected, if desired, to achieve the desired properties of the solution. Among the suitable solvents are water, methanol, ethanol, isopropyl alcohol, other organic solvents and mixtures thereof. The solvent should have the desired level of purity so that the resulting particles have the desired level of purity. For the production of a composite metal compound by laser pyrolysis, the solution may contain a plurality of metal compounds. As an alternative or in addition,
In addition to the metal precursor delivered as an aerosol, the metal precursor may be delivered to the reaction chamber in a vapor state.

When the aerosol precursor is prepared in the presence of a solvent, the solvent is rapidly evaporated by the laser beam in the reaction chamber so that the gas phase reaction proceeds. Thus, the basic characteristics of the laser pyrolysis reaction do not change. However, the reaction conditions are
Affected by the presence of the aerosol. The following examples illustrate the production of manganese oxide nanoparticles using a gas phase reaction precursor and an aerosol precursor using two different laser pyrolysis reaction chambers. The production of lithium manganese oxide nanoparticles by laser pyrolysis in one of these reaction chambers using an aerosol is also described in the examples. Thus, the parameters associated with aerosol reactant delivery are searched based on the description below.

[0043] Many suitable solid manganese precursor compounds are delivered as aerosols from solution. For example, manganese chloride (MnCl ₂ ) and hydrated manganese chloride (Mn)
Cl ₂ .H ₂ O) is soluble in water and alcohols and manganese nitrate [
Mn (NO ₃ ) ₂ ] is soluble in water and certain organic solvents. Also suitable for lithium aerosol delivery from solution include, for example, lithium chloride (LiCl), which is partially soluble in water, alcohols and some other organic solvents, and lithium nitrate, which is partially soluble in water and alcohol. (LiNO ₃ ). Additionally, suitable for vanadium precursors for aerosol delivery from solution include, for example, VOCl ₂ that is soluble in anhydrous alcohol.

Preferably, these compounds are dissolved in solution at a concentration of about 0.5 molar or more. Generally, the higher the concentration of the precursor in the solution, the higher the reactant flow rate through the reaction chamber. However, as this concentration increases, the solution becomes viscous and the aerosol may contain larger droplets than desired. Thus, the choice of the solution concentration can include a balance of factors in the selection of the desired solution concentration.

In preparing composite metal particles, the relative amount of metal precursor in the solution affects the relative amount of metal in the resulting particles. Thus, the desired composition of the product particles affects the choice of the relative amount of metal precursor to be delivered. While the desired stoichiometry may affect the relative amount of metal delivered to the reaction chamber, the relative amount of metal precursor may be different, as different or mixed phase materials may form. , May change part of the phase diagram sample. Due to the potential for the formation of mixed phase materials, the relative amounts of metals in the reactant stream do not translate directly into particles having the corresponding stoichiometric composition.

As pointed out above, the reaction conditions determine the type and properties of the particles produced by laser pyrolysis. Of course, in the production of composite metal oxide particles, the situation may even be more elusive as the corresponding complexity of the phase diagram is added. in this case,
There is an additional parameter, the amount of additional metal precursor that affects the resulting properties of the particle (s). Although the phase diagram may not be completely understood, and the non-equilibrium conditions in laser pyrolysis may give rise to additional uncertainties, we have found that in choosing the relative amounts of metal precursors, The known stoichiometric composition of the form can be a guide.

In the production of lithium manganese oxide, the composition of the metal precursor affects the crystallinity of the resulting nanoparticles. In particular, metal chloride precursors favor the production of amorphous particles, while metal nitrates favor the production of crystalline particles. Based on kinetic principles, a higher quench rate favors the formation of amorphous particles, while a slower quench rate favors the formation of crystalline particles. Faster quenching is achieved by increasing the speed of the reaction stream through the reaction zone.

[0048] Suitable manganese precursor compounds for gas delivery include, generally:
A manganese compound having a reasonable vapor pressure, i.e., a vapor pressure sufficient to obtain the desired amount of precursor vapor in the reaction stream. The vessel containing the liquid or solid precursor compound is a vessel that can be heated, if desired, to increase the vapor pressure of the manganese precursor. Suitable solid manganese precursors having sufficient vapor pressure for gas delivery include, for example, manganese carbonyl (Mn ₂ (CO 2
) ₁₀ ). FIG. 1 shows a container suitable for heating a solid precursor and delivering it to a laser pyrolyzer.

Referring to FIG. 1, a solid delivery device 50 for vapor delivery includes a container 52 and a lid 54. A gasket 56 is placed between the container 52 and the lid 54.
In one preferred embodiment, container 52 and lid 54 are made of stainless steel, and gasket 56 is made of copper. In this embodiment, the lid 54 and the gasket 56
It is bolted to the container 52. To accommodate the temperature and pressure exerted on the solid precursor device, other inert materials such as Pyrex ^R (Pyrex ^R) can be used. The container 52 is surrounded by a band heater 58, which is used to set the temperature of the delivery device 50 to a desired value. Suitable band heaters are available from Omega Engineering Inc. Stamford
, Conn. Available from The temperature of the band heater can be adjusted to obtain a desired vapor pressure of the precursor compound. An additional portion of the precursor delivery device may be heated after the precursor leaves the container 52 to maintain the precursor in a vapor state.

Preferably, a thermocouple 60 is inserted into the container 52 through the lid 54. Thermocouple 60 is inserted using Swagelok ^R fixture 62 or other suitable connecting hardware. The pipe 64 has an inlet for the carrier gas into the container 52. Piping 6
4 preferably includes a shut-off valve (shutoff valve) 66;
wagelok with ^R fixture 68 or other suitable connection device is inserted through the lid 54. Preferably, the discharge pipe 70 also includes a shut-off valve 72. The drain 70 preferably enters the container 52 through the lid 54 at the closed connection 74. Piping 64 and 70 are made of any suitable inert material, such as stainless steel. The solid precursor is placed directly into the container 52, or
Alternatively, it may be placed in the container 52 in a smaller open container.

Desirable reactants that serve as a source of oxygen are, for example, O ₂ , CO, CO ₂ , O _3, and mixtures thereof. The second reactant compound must not significantly react with the manganese precursor and / or lithium precursor before entering the reaction zone.
This is because the reaction usually produces large particles.

Laser pyrolysis is performed at various optical frequencies. The recommended light source operates in the infrared portion of the electromagnetic spectrum. A CO ₂ laser is a particularly recommended light source. Infrared absorbers to be included in the molecular stream are, for example, C ₂ H ₄ , NH ₃ , SF ₆ , SiH ₄ and O ₃ . O ₃ can act as both an infrared absorber and an oxygen source. Radiation absorbers, such as this infrared absorber, absorb energy from the radiation beam and distribute that energy to other reactants to drive pyrolysis.

[0053] Preferably, the energy absorbed from the light beam raises the temperature at an astonishing rate many times greater than the rate at which energy is produced by a strongly exothermic reaction under controlled conditions. This process generally involves non-equilibrium conditions, but the temperature can be approximately described based on the energy in the absorption region. This laser pyrolysis process is qualitatively different from the process in a combustion reactor driven by energy released by an exothermic reaction, where the energy source initiates a reaction. Laser pyrolysis requires the continuous delivery of laser energy to maintain its chemical reaction.

To reduce the amount of reactant and product molecules that come into contact with the reactant chamber members
, An inert shielding gas is used. Suitable shielding gases are, for example, Ar, He and N _Two It is.

Suitable laser pyrolysis devices generally include a reaction chamber that is isolated from the surrounding environment. A reactant inlet tube connected to the reactant supply generates a molecular flow through the reaction chamber. The path of the laser beam intersects the molecular flow at the reaction zone. After passing through the reaction zone, the reaction stream continues to an outlet, where it exits the reaction chamber and goes to a collector. Generally, the laser device is located outside the reaction chamber, and the light beam enters the reaction chamber through a suitable window.

Hereinafter, two further laser pyrolysis reaction chambers will be described. These laser pyrolysis reaction chambers can be adapted for delivery of gas phase reactants and / or aerosol reactants.

1. First Laser Pyrolysis Reaction Chamber Referring to FIG. 2, a specific embodiment 100 of the laser pyrolysis apparatus includes a reactant supply device 102, a reaction chamber 104, a collection device 106, a laser 108, and a shielding gas delivery device 110. Contains. In the apparatus of FIG. 2, two alternating reaction supply systems are used. The first type reactant delivery system is used exclusively for delivering gaseous reactants. A second type reactant delivery system is used to deliver one or more reactants as an aerosol.

Referring to FIG. 3, a first embodiment 112 of the reactant supply system 102 includes:
A source 120 of precursor compound is included. An optional second precursor source 121 is used for the production of composite / ternary particles. In the case of a liquid or solid precursor, a carrier gas from one or more carrier gas sources 122 may be used to facilitate delivery of the precursor as a vapor to the precursor source 120 and / or 12
Introduced in 1. Precursor source 120 and / or 121 may be a solid precursor delivery system 50 as shown in FIG. The carrier gas from this source 122 is preferably either an infrared absorber or an inert gas, and is preferably blown through the liquid precursor compound or fed into a solid precursor delivery system. . The inert gas used as the carrier gas can moderate the reaction conditions. The amount of precursor vapor in this reaction zone is roughly proportional to the flow rate of the carrier gas.

Alternatively, the carrier gas may be supplied directly from infrared source 124 or inert gas source 126 as appropriate. This second reactant is supplied from a reactant source 128 which is a gas cylinder or other suitable vessel. Precursor sources 120, 12
1 from the reactant source 128, the infrared absorber source 124 and the inert gas source 1
The gases from 26 are mixed by bringing these gases together in a single section of tubing 130. These gases flow together a sufficient distance from the reaction chamber 104 before entering the reaction chamber 104 so that the gases are well mixed.

The gases combined in tube 130 pass through duct 132 and enter a rectangular channel 134 that forms part of an injection nozzle for directing reactants toward the reaction chamber. A portion of the reactant supply device 112 is heated to prevent deposition of the precursor compound on the walls of the delivery device.

Referring to FIG. 4A, a second embodiment 150 of reactant delivery system 102 is used to deliver aerosol to duct 132. Duct 132 connects to a rectangular flow path 134 that forms part of an injection nozzle for directing reactants toward the reaction chamber. Reactant supply system 150 includes duct 132
And a delivery tube 152 connected to the delivery tube. Venturi tube 154 is connected to delivery tube 152 as an aerosol source. Venturi tube 154 is connected to gas supply tube 156 and liquid supply tube 158.

The gas supply pipe 156 is connected to the gas source 160. The gas source 160 may include a plurality of gas containers coupled to deliver a selected gas or mixture of gases to the gas supply tube 156. Gas supply pipe 15 from gas source 160
The gas flow to 6 is controlled by one or more valves 162. The liquid supply pipe 156 is connected to the liquid supply source 164. The delivery tube 152 is also connected to the storage container 16.
8 is connected to a drain pipe 166 flowing to the drain.

In operation, the gas flow through the Venturi tube 154 creates a suction that pulls liquid from the liquid supply tube 158 toward the Venturi tube. The gas-liquid mixture in Venturi tube 154 creates an aerosol when Venturi tube 154 is open toward delivery tube 152. The aerosol is drawn up to the duct 132 by the pressure difference in the system. Any aerosol that condenses in the delivery tube 152 is collected in a storage container 168 that is part of this closed system.

Referring to FIG. 4B, a third embodiment 170 of the reactant supply system 102 is used to supply an aerosol to the duct 132. The reactant supply system 170 includes an aerosol generator 172, a carrier gas / vapor supply tube 174, and a junction 176. Duct 132, aerosol generator 172 and supply pipe 17
4 come together in the interior volume 178 of the joint 176. The supply pipe 174 is oriented to flow carrier gas along the duct 132. The aerosol generator 172 has an opening to the duct 132 and the supply pipe 17.
It is mounted to occur inside the inner compartment 178 of the chamber between the outlets from 4.

The aerosol generator 172 can operate on a variety of principles. For example, the aerosol may be applied in an ultrasonic nozzle, in an electrostatic spray system, in a pressurized or single nozzle atomizer, in a whisk atomizer, or as a liquid passes through a small orifice. Can be produced with a gas atomizer that is forced at a pressure of and is sheared into small droplets by an impinging gas stream. Suitable ultrasonic nozzles may include a piezoelectric transducer. Ultrasonic nozzles including piezoelectric transducers and suitable broadband ultrasonic generators are available from Sono-Tek Corpo.
available from Ration, Milton, NY, as Model 8700-120. A suitable aerosol generator is described in commonly-owned U.S. patent application Ser. No. 09 / 188,670 (referenced to Gardner et al., Entitled "Reactant Delivery Device"). "). An additional aerosol generator may be attached to the junction 176 through another port 182 so that additional aerosol is generated in the inner compartment 178 and delivered to the reaction chamber.

The joint 176 includes a port 182 for providing access to the inner compartment 178 from outside the joint 176. Thus, the duct 132, the aerosol generator 172 and the supply pipe 174 are properly mounted. In one aspect, the joint 176 is a cube having six cylindrical ports 182, with one port 182 extending from each side of the joint 176. The joint 176 is made of stainless steel or other durable, corrosion resistant material. A window 181 is preferably attached to one of the ports 182 so that the inner compartment 178 can be visually observed. The port 182 extending from the bottom of the junction 176 desirably includes a drain 183 so that condensed aerosol not delivered through the duct 132 is removed from the junction 176.

The carrier gas / steam supply pipe 174 is connected to a gas source 184. The gas source 184 includes a plurality of gas containers, liquid reactant delivery devices, and / or solid reactant delivery devices that are connected to deliver a selected gas or gas mixture to the supply tube 174. Thus, the carrier gas / vapor supply tube 174 is used to deliver a variety of desired gases and / or vapors within the reaction stream, including, for example, laser absorbing gases, reactants, and / or inert gases. The flow of gas from the gas source 184 to the supply tube 174 is preferably regulated by one or more mass flow controllers 186. The liquid supply pipe 188 is connected to the aerosol generator 152. The liquid supply pipe 188 is connected to a liquid supply source 189.

For the production of lithium manganese oxide particles, liquid source 189 can hold a liquid comprising both a lithium precursor and a manganese precursor. Alternatively, for the production of lithium manganese oxide particles, liquid source 189 holds a liquid containing a manganese precursor, while the lithium precursor is supplied to vapor supply tube 174 and gas source (s). 184. Similarly, if desired, liquid source 189 holds a liquid comprising a lithium precursor, while manganese precursor is delivered by vapor supply tube 174 and gas source (s) 184. . Also, two separate aerosol generators 172 are used to generate aerosols in the junction zone 176, one of which produces an aerosol containing a manganese precursor, and a second device containing a lithium precursor. Produce aerosol.

In the embodiment shown in FIG. 4B, aerosol generator 172 generates an aerosol with momentum that is substantially perpendicular to the flow of carrier gas from tube 174 to duct 132. Thus, the carrier gas / vapor from the supply tube 174 directs the aerosol precursor generated by the aerosol generator in the direction of the duct 132. In operation, the carrier gas stream causes the aerosol delivered into the chamber 178 to pass through the duct 13.
Turn towards 2. In this way, the rate of delivery of the aerosol is substantially determined by the flow rate of the carrier gas.

In an alternative preferred embodiment, the aerosol generator is positioned at an angle upward with respect to the horizontal so that the component of the advancing momentum of the aerosol points in a direction along duct 132. In one preferred embodiment, the direct effluent from the aerosol generator is 45 ° relative to the standard direction defined by the opening to the duct 132, ie, the direction of flow from the supply line 174 to the duct 132. Placed at an angle of degrees.

Referring to FIG. 4C, another embodiment 191 of reactant supply device 102 is used to supply aerosol to duct 132. Reactant supply device 19
1 includes an outer nozzle 193 and an inner nozzle 195. Outer nozzle 1
93 has an upper channel 197 leading to a 5/8 inch by 1/4 inch rectangular outlet 199 at the top of the outer nozzle 193 as shown in the inset in FIG. 4C. The nozzle 193 includes a drain pipe 201 in the base plate 203. The drain pipe 201 is used for removing condensed aerosol from the outer nozzle 193. The inner nozzle 195 is clamped to the outer nozzle 193 by the fitting 205.

The inner nozzle 195 is connected to Spraying Systems (Wheaton
, IL) model number 17310-12-1x8jj. The inner nozzle is about 0.5 inch in diameter and 12.0 inches long. At the top of the nozzle is a twin orifice type internal mixing atomizer 207 (0.055 inch gas orifice and 0.005 inch liquid orifice). The liquid is supplied to the atomizer through tube 209 and the gas introduced into the reaction chamber is supplied to the atomizer through tube 211. The interaction of the gas with the liquid helps to create small droplets.

The outer nozzle 193 and the inner nozzle 195 are assembled concentrically.
The outer nozzle 193 shapes the aerosol generated by the inner nozzle 195 to have a flat rectangular cross section. The outer nozzle 193 further equalizes the velocity of the aerosol and helps to equalize the distribution of the aerosol along the cross section. The outer nozzle 193 can change configuration in different reaction chambers. The height of the outer nozzle 193 relative to the radiation / laser beam can adjust the spray characteristics so that particles of the desired properties are prepared. For the production of lithium manganese oxide by laser pyrolysis, the outer nozzle 193 is placed about 3 inches below the laser beam.

Referring to FIG. 2, the shielding gas delivery device 110 includes the inert gas duct 1
An inert gas source 190 connected to 92 is included. Inert gas duct 19
2 flows into the annular channel 194. Mass flow controller 196 controls the flow of inert gas into inert gas duct 192. If reactant delivery device 112 is used, inert gas source 126 may also function as an inert gas source for duct 192, if desired.

The reaction chamber 104 includes a main chamber 200. Reactant supply 102 is connected to main chamber 200 at injection nozzle 202. The reaction chamber 104 may be heated to maintain the precursor compound in a vapor state. The chamber is desirably heated to a surface temperature above the dew point of the mixture of reactants and inert components at the pressure within the apparatus. In many embodiments, the chamber is heated to about 120 ° C. if a solid precursor is used. Similarly, in many embodiments, the shielding argon gas is heated to about 150 ° C. if a solid precursor is used. This chamber is considered for condensation to ensure that no precursors deposit on the chamber.

At the end of the injection nozzle 202 is provided an annular opening 204 for the passage of a shielding inert gas and a reactant inlet 206 for forming a reactant passage for producing a reactant flow in the reaction chamber. ing. The reactant inlet 206 is preferably a slit as shown in the inset below FIG. The annular opening 204 is, for example, about 1.5 inches in diameter and about 1/8 to about 1/16 inch in width along the radial direction. The flow of shielding gas through the annular opening 204 helps prevent reactant gas and product particles from spreading throughout the reaction chamber 104.

Tubular sections 208, 210 are located on opposite sides of the injection nozzle 202. Tubular sections 208, 210 include ZnSe windows 212, 214, respectively. The diameter of the windows 212 and 214 is about 1
Inches. The windows 212, 214 are preferably cylindrical lenses (cyl)
Preferably, at the focal length, the focal length is equal to the distance between the center of the chamber and the surface of the lens so that the light beam is focused at a point just below the center of the nozzle opening. The windows 212, 214 are preferably provided with an anti-reflective coating. A suitable ZnSe lens is Laser Power
Available from Optics, San Diego, California.
The tubular sections 208, 210 allow the windows 212, 214 to be offset away from the main chamber such that the windows 212, 214 are less contaminated by reactants and / or products. ing. For example, window 2
12, 214 are offset from the end of the main chamber 200 by about 3 cm.

The windows 212, 214 are sealed with rubber O-rings to the tubular sections 208, 210 to prevent ambient air from flowing into the reaction chamber 104. To reduce contamination of the windows 212, 214, the tubular sections 208, 210
Tubular inlets 216, 218 are provided for the inflow of shielding gas into the air. The tubular inlets 216, 218 are connected to an inert gas source 190 or another inert gas source. In any case, it is desirable that the airflow to the air inlets 216 and 218 be controlled by the mass flow controller 220.

The light source 108 is arranged such that the generated light beam 222 enters the window 212 and exits the window 214. Windows 212, 214 define an optical path through main chamber 200 to intersect the reactant flow at reaction zone 224. After exiting window 214,
Light beam 222 strikes wattmeter 226, which also acts as a beam dump. Suitable power meters are available from Coherent Inc. , Santa
a Available from Clara, CA. Light source 108 may be a strong conventional light source, such as a laser or an arc lamp. The light source 108 is an infrared laser, in particular,
PRC Corp. Output 1800 available from Landing, Landing, NJ
CW CO ₂ lasers, such as watt lasers, are particularly desirable.

The reactant that has passed through the reactant inlet 206 in the injection nozzle 202 becomes a reactant flow. This reaction stream passes through reaction zone 224, where it entrains and reacts with the metal precursor compound. The heating of the gas in the reaction zone 224 is extremely fast,
Depending on the particular conditions, it is on the order of 10 ⁵ ° C / sec. Upon exiting reaction zone 224, the reaction is rapidly cooled and particles 228 are formed in the reaction stream. Since this process is a non-equilibrium reaction, it is possible to produce nanoparticles having a very uniform particle size distribution and high structural homogeneity.

The path of the molecular flow continues to the collection nozzle 230. The collection nozzle 230 is about 2 cm away from the injection nozzle 202. Injection nozzle 202 and collection nozzle 230
The small clearance distance helps reduce contamination of reaction chamber 104 by reactants and products. The collection nozzle 230 has an annular opening 232, as shown in the upper inset of FIG. An annular opening 232 is provided in the collection device 106.
Send to

The pressure in the chamber is monitored by a pressure gauge mounted on the main chamber. The recommended pressure in this chamber for the production of the desired oxide is typically about 80 T
orr to about 650 Torr.

The reaction chamber 104 has two additional tubular sections not shown. One of the additional tubular sections extends toward the plane of the cross-sectional view of FIG. 2, and a second additional tubular section protrudes from the plane of the cross-sectional view of FIG. When viewed from above, the four tubular sections are approximately symmetrically distributed around the center of the chamber. These additional tubular sections have windows for viewing the interior of the chamber. In this relative arrangement, these two additional tubular sections are not used to facilitate the production of particles.

The collection device 106 has a curved conduit 270 leading to the collection nozzle 230.
It is desirable to include. Because the particles are small in size, the product particles
Flow about the gas flow. The collecting device 106 collects the product particles.
To this end, a filter 272 is included in the gas stream. Section 270 curves
As such, this filter is not supported directly above the chamber. Te
A variety of materials such as CFCs, glass fibers and similar materials are used for this filter, as long as they are inert and fine enough to capture the particles. Recommended materials for this filter are, for example, ACE Glass Inc. Glass Fiber Filter from AF Equipment Co., Vineland, NJ. Sunnyvale, CA. Cylindrical Nomex from ^RFilter.

A pump 274 is used to maintain the collection device 106 at a predetermined pressure.
A variety of different pumps can be used. Pumps suitable for use as pump 274 are described, for example, in Busch, Inc. , Virginia Beac
h, Bus with exhaust performance of about 25 cubic feet / minute (cfm) from VA
ch Model B0024 Pump and Leybold Vacuum
A Leybold Model SV300 pump with about 195 cfm pumping performance from Products, Export, PA. The pump exhaust preferably flows through a scrubber 276 to remove any remaining reactive chemicals before exiting to the atmosphere. All devices 100 are placed in a fume hood for ventilation purposes and safety. Generally, the laser device is located outside its fume hood due to its large size.

This device is controlled by a computer. Generally, this computer
The light source is controlled and the pressure in the reaction chamber is monitored. This computer is used to control the flow of reactants and / or shielding gas. Pumping speed is controlled by either a manual needle valve or an automatic throttle valve inserted between pump 274 and filter 272.
As the pressure in the chamber increases due to the accumulation of particles on the filter 272, its manual or throttle valve can be adjusted to maintain the pumping speed and the corresponding chamber pressure.

The reaction continues until enough particles are collected on filter 272 such that pump 274 can no longer maintain the desired pressure in reaction chamber 104.
If the pressure in the reaction chamber 104 can no longer be maintained at the desired value, the reaction is stopped and the filter 272 is removed. In this embodiment, about 1-300 grams of particles can be collected in a single run before the chamber pressure can no longer be maintained. A single run usually lasts up to about 10 hours, depending on the type of particles produced and the type of filter used.

The reaction conditions can be controlled relatively accurately. In particular, mass flow controllers are extremely accurate. This laser typically has a power stability of about 0.5 percent. The pressure in the chamber can be controlled to within about one percent by a manually controlled valve or a throttle valve.

The relative arrangement of the reactant supply device 102 and the collection device 106 can be reversed. In this alternative arrangement, the reactants are supplied from the top of the reaction chamber,
Product particles are then collected from the bottom of the chamber. In this alternative arrangement, the collection device does not include a curved portion of the collection device such that the collection filter is mounted directly below the reaction chamber.

2. Second Laser Pyrolysis Reaction Chamber Another alternative design of a laser pyrolysis apparatus is the "Laser Pyrolysis Apparatus," herein incorporated by reference.
U.S. Pat. No. 5,958,3 entitled "Efficient Production of Particles by Chemical Reaction"
No. 48 describes this. This alternative design is intended to facilitate the production of commercially produced quantities of particles by laser pyrolysis. The reaction chamber extends along a light beam in a dimension perpendicular to the reactant stream to provide increased throughput of reactants and products. The original design of this device was based purely on the introduction of gaseous reactants. A special embodiment for introducing an aerosol into this device is described below. Additional embodiments for introducing an aerosol with one or more aerosol generators into an elongated reaction chamber are described in co-pending US patent application Ser. No. 09 / 188,092, incorporated herein by reference. , 6
No. 70 [Inventor: Gardner et al., Name: "Reactant delivery device", Filing date: 19
Nov. 9, 1998].

Generally, this alternative pyrolysis unit comprises a reaction chamber designed to reduce particulate contamination of the chamber walls to increase production capacity and to make efficient use of feedstock. ing. To achieve these objectives, the reaction chamber is elongated to provide a large throughput of reactants and products without a corresponding increase in the dead volume of the chamber. A reaction chamber is used. This dead space of the chamber can be contaminated by unreacted compounds and / or reaction products.

The design of an improved reaction chamber 300 is schematically illustrated in FIG. Reactant inlet 302 reaches main chamber 304. Reactant inlet 302 is generally in the shape of main chamber 304. For example, the introduction of reactants through reactant inlet 302 for the production of lithium manganese oxide particles applies the above discussion regarding the introduction of aerosol and / or gaseous precursors using the laser pyrolysis apparatus of FIG. Thus, when the reactant inlet has an alternative structure, it is appropriately adapted. Generally, the reactant inlet has a length of about 5 mm to about 1 m when using a 1800 watt CO ₂ laser.

The main chamber 304 includes an outlet 306 along the molecular stream for removing particulate products, any unreacted gases and inert gases. Shielding gas inlets 310 are provided on both sides of reactant inlet 302. Shielding gas inlets are used to form a blanket of inert gas on the sides of the reactant stream to inhibit contact of the chamber walls with reactants or products.

Annular sections 320, 322 extend from main chamber 304. Annular sections 320, 322 provide a path 32 for the light beam through reaction chamber 300.
8 for holding the windows 324 and 326. Annular section 320,
322 includes inert gas inlets 330, 332 for introducing inert gas into the annular sections 320, 322.

Referring to FIGS. 6-8, a particular embodiment of a laser pyrolysis reactor having an elongated reaction chamber is shown. In this aspect, the aerosol reactant delivery device is adapted for use in the elongated reaction chamber. The laser pyrolysis reactor 350 includes a reaction chamber 352, a particle collector 354, a laser 356, and a reactant delivery device (described below). Reaction chamber 352 includes a reactant inlet 364 at the bottom of reaction chamber 352, where a reactant delivery device is coupled to reaction chamber 352. In this embodiment, the reactants are delivered from the bottom of the reaction chamber, while the products are collected from the top of the reaction chamber. This relative arrangement can be reversed, if desired, with reactants fed from the top and products collected at the bottom.

The shielding gas introduction pipes 365 are located at the front and back of the reactant inlet 364. The inert gas is delivered to the shielding gas introduction pipe 365 through the port 367. The shielding gas introduction tube directs the shielding gas along the walls of the reaction chamber to inhibit reactant gases or products from contacting the walls.

The reaction chamber 352 is elongated in the dimension indicated by “W” in FIG. Laser beam path 366 enters the reaction chamber through window 368, travels from main chamber 372 along tube 370, and passes through the elongated direction of reaction chamber 352. This laser beam exits window 376 through tube 374. In one preferred embodiment, tubes 370 and 374 are fitted with windows 368 and 3
76 is offset from main chamber 372 by about 11 inches. The laser beam ends in a beam dump 378. In operation, the laser beam intersects the reactant stream generated through the reactant inlet.

The uppermost part of the main chamber 372 is open to the particle collector 354. The particle trap 354 includes an outlet duct 380 connected to the top of the main chamber 372 to receive flow from the main chamber 372. Outlet duct 380 carries product particles from the face of the reaction stream to cylindrical filter 382. The filter 382 has a cap 384 at one end. The other end of the filter 382 is fastened to the disk 386. Vent 388 is clamped to the center of disk 386 to provide access to the center of filter 382. Vent 388 is attached to the pump by a duct. Thus, the product particles flow from the reaction chamber 352 to the pump and thereby to the filter 3.
82. Suitable pumps have been described above in connection with the first laser pyrolyzer in FIG. Filters 382 suitable for use as filters include, for example, a Saab 9000 automotive air cleaner filter impregnated with Plasticol wax.
part A44-67) or polyurethane end cap 384.

Referring to FIG. 9, aerosol delivery device 480 includes an aerosol generator 482 supported by mount 484 and cap 486. The aerosol delivery device 480 is anchored at the reactant inlet 364 of the reaction chamber 352 to extend into the main chamber 372 shown in FIGS. 6-8. Mount 484 is coupled to substrate 488. Substrate 488 is clamped to reactant inlet 364 with bolts 490. Substrate 488 and reactant inlet 36
An O-ring or similar, suitably shaped to seal between the four, is placed in a hollow 492.

Referring to FIGS. 10 and 11, mount 484 is generally cylindrical. Mount 484 includes a lip (l) extending into cylindrical cavity 508.
ip: seal lip) 506. Lip 506 serves to support aerosol generator 482. In this aspect, lip 506 includes a notch 510 that allows a portion of aerosol generator 482 to extend through lip 506. The top surface 512 of the mount 484 is provided with the cap 4 described below.
It includes a hollow 514 for holding an O-ring or the like for sealing with 86 or spacers. The mount 484 further
The outer surface 520 includes a thread 518.

Referring to FIGS. 10, 12 and 13, cap 486 is mounted on the top of mount 484. Cap 486 includes a thread 528 that mates with thread 518 on mount 484. Flange 530 is O
-Used to form a seal with a ring or the like. Surface 532 includes hollow 534. Hollow 534 holds an O-ring or the like to form a seal with aerosol generator 482 or wedge, as described further below.

The tube 536 is in a fluid connection bridge having a cavity 538. Tube 536
A gas flow is provided to the cavity 538. Cavity 538 communicates with port 540. A plurality of tubes 542 direct fluid flow through channels 544 to radiant tubes 546.
To provide. In this embodiment, four emission tubes 546 are provided by aerosol generator 482.
And radiate toward the fluid stream coming from port 540. The four emission tubes 546 are symmetrically distributed around port 540. If desired, more or less than four emission tubes 546 are used. Gas is supplied to tube 536 and tube 542 through stainless steel or similar tubing, through substrate 488 (FIG. 9), and through one or more ports 547.

The use of a radiation tube 546 is particularly useful for further mixing reactants in a reaction chamber remote from the aerosol generator 482. When the radiation tube 546 is used, a gas such as a reactant gas and / or a radiation absorbing gas is supplied to the aerosol generator 4.
The reactants from 82 and / or port 540 are mixed inside the reactant chamber. The optical path 548 of the laser beam intersects the reaction flow just above the emission tube 546.

The location of the aerosol generator 482 relative to the port 540 can affect the nature of the resulting reactant stream, and thus the nature of the reaction product. When using an ultrasonic aerosol generator, it is desirable that the tip of the aerosol generator be located just below the cap surface to just above the cap surface.

The spacer 550 shown in FIG. 14 is placed between the cap 486 and the mount 484 to change the position of the aerosol generator 482 relative to the port 540. Spacer 550 is a cylindrical piece with a hollow along top surface 554 to hold an O-ring or the like. Top surface 554 is sealed to flange 530 of cap 486.
The lower surface 556 of the spacer 550 is sealed to the upper surface 512 of the mount 484. As shown in FIG. 15, the wedge 558 is correspondingly
And an aerosol generator 482. The upper surface 560 of the wedge 558
An O-ring is fitted into recess 534. Aerosol generator 482 fits over flange 562.

The flow of reactants into the main chamber 372 is affected by the way the cap bushing is placed at the port 540 opening. More specifically, the cap bushing helps to better confine the reaction stream within the main chamber 372. Three aspects of the cap bushing, 570, 572, 574, are shown in FIGS. 16-18, respectively. Referring to FIG. 16, the cap bushing 570 has a cylindrical passage 576 and a smooth upper surface 578 is generally
Perpendicular to the central axis of the cylindrical passage. Referring to FIG. 17, the cap bushing 572 has a conical passage 580 and a smooth upper surface 582
Usually, it is perpendicular to the axis of symmetry of the conical passage. Referring to FIG. 18, the cap bushing 574 has a conical passage 584 and an upper surface having a smooth cross section 586 and a conical cross section 588. A preferred embodiment of the cap bushing is
It has a sharp edge between its internal passage and the upper surface.

The reaction chamber 352 and reactant supply 480 are preferably made of stainless steel or other corrosion resistant metal. O-rings and other seals are made from natural or synthetic rubber or other polymers.

Referring to FIG. 10, in one preferred embodiment, the aerosol generator 482 includes an ultrasonic nozzle 600 and a nozzle supply.
ply) 602. The recommended ultrasonic nozzle 600 is a Sono-T
Model 8700 from ek Corporation Milton, NY
120. Referring to FIGS. 19-20, the ultrasonic nozzle 600 is connected directly to the nozzle tip 604, nozzle body 606, connector 608 for connection to an ultrasonic generator, and liquid storage or by a nozzle supply 602. A liquid connection 610 for connection. At the end of the nozzle tip 604 is the atomizing surface 612. The size and shape of the atomization surface 612 can be varied to obtain the desired spatial distribution of the aerosol particles.

[0109] The nozzle tip 604 is connected to the nozzle body 606 at or near the top surface 614. The ultrasonic transducer 616 is placed at a position suitable for vibrating the nozzle tip 604 in the nozzle body 606. Generally, the ultrasonic transducer 616 is placed toward the upper surface 614. Among the recommended ultrasonic transducers are piezoelectric transducers. The ultrasonic transducer 616 oscillates in phase in phase so that the amplitudes of these two oscillating piezoelectric transducers are added to create additional force at the atomizing surface 612. Preferably, two or more piezoelectric transducers 618 are included.

The ultrasonic transducer 616 is connected to an ultrasonic generator by a connector 608. Preferably, the ultrasonic generator is a broadband generator operating over a frequency range of about 20 kHz to about 120 kHz. The electric signal from the ultrasonic generator is transmitted from the coupler 608 to the ultrasonic vibrator 616 via the conductor 620.

The liquid flows from the liquid connection 610 to the atomization surface 612 through a channel 622 through the nozzle body 606. Referring to FIG. 10, the nozzle supply 602 is connected to the liquid connection 610 by a liquid coupling 630. Nozzle supply 602 includes a pneumatically controlled needle valve.
Nozzle supply 602 includes air-controlled inlet 632, needle valve adjustment device 6
34 and a supply liquid reservoir inlet 636. The air control inlet 632 and the supply liquid reservoir inlet 636 communicate through a central channel 508 that extends through the substrate 488.

The supply liquid reservoir inlet 636 is connected to a liquid supply 640, shown schematically in FIG. The liquid supply device 640 includes at least one liquid source 64.
2, including an outlet tube 644 and a gas supply tube 646. Tube 644 is connected to fitting 64
At 8 is connected to the supply liquid reservoir inlet 636. Similarly, tube 644 is directly or indirectly connected to liquid source 642. The liquid source 642 also has a gas supply pipe 646.
Is connected to. The gas supply tube is a gas source 66 which is a gas cylinder or the like.
6. The flow from the gas source 666 to the gas supply tube is controlled by one or more valves 668. Pressurized gas from gas supply tube 646 forces liquid from liquid source 642 into tube 644.

If the position of the liquid source 642 is properly set, the pressure can be supplied by gravity instead of using the gas pressure. In another aspect, a mechanical pump is used to supply a relatively constant amount of pressure within the tube 644. Suitable pumps include, for example, a centrifugal pump and a plurality of syringe pumps operating sequentially.

In use, the aerosol generator 482 produces a liquid aerosol supplied to the aerosol generator 482. The aerosol generator 482 can deliver gas with the aerosol. The aerosol can also be mixed with the gas supplied through tube 536. Thus, the aerosol generator 4
The aerosol and any gas supplied from 82 and / or tube 636 are directed to a reaction chamber near port 540 of cap 486. The aerosol and any gas emitted from aerosol generator 482 and / or tube 536 may be further combined within reaction chamber 352 with additional gas from emission tube 546. The resulting mixture of aerosol and gas is then
The reaction is performed in the reaction chamber 352.

When carrying out a reaction synthesis based on laser pyrolysis, the aerosol / gas mixture is usually one or more aerosol-shaped reactants, optionally one or more additional reactant gases, If the reactants and / or solvent (s) do not adequately absorb the laser radiation, include a laser absorbing gas, and optionally an inert gas. These gases are supplied from pressurized cylinders or other suitable containers. The reactants may be mixed in a liquid phase and delivered as an aerosol thereof.

An alternative aerosol generator having an elongated reaction chamber may be used. Further, one or more aerosol generators can be adapted to the elongated reaction chamber in various ways.

B. Heat processing 1. As noted above in the conditioning of the particles, the properties of the metal oxide particles can be modified by further processing. Suitable starting materials for this heat treatment include metal oxide particles such as lithium manganese oxide particles produced by laser pyrolysis. Furthermore, the particles used as starting material are subjected to one or more preheating steps under different conditions. In the case of heat treatment of metal oxide particles prepared by laser pyrolysis, this additional heat treatment improves its crystallinity, removes contaminants such as elemental carbon, and preferably, for example, additional oxygen Alternatively, its stoichiometry can be altered by the incorporation of atoms from other gaseous species. Mild enough conditions, ie
Using a temperature well below the melting point of the particles allows the particles to be processed without significantly sintering the particles into larger particles.

While nanoscale particles are the recommended starting material, the starting material can generally be particles of any size and shape. This nanoscale particle has a size of about 1000 n.
m, and preferably from about 5 nm to about 500 nm, and more preferably from about 5 nm to about 150 nm. Suitable nanoscale starting materials have been produced by laser pyrolysis.

[0119] The metal oxide particles are usually desirably heated in an oven or similar device so as to receive uniform heating. The processing conditions are usually mild conditions such that sintering of a significant amount of particles does not occur. Desirably, the heating temperature is low relative to the melting points of both the starting material and the product.

For a given target product particle, once equilibrated, additional heating does not change the particle composition further. The atmosphere in the heating step is an oxidizing atmosphere or an inert atmosphere. In particular, in the conversion of amorphous particles into crystalline particles or from one crystal structure to a different crystal structure having basically the same stoichiometric composition, the atmosphere is generally an inert atmosphere. The atmosphere above these particles may be stationary or gas may be flowing through the system.

Suitable oxidizing gases are, for example, O ₂ , O ₃ , CO, CO ₂ and combinations thereof. O ₂ may be supplied as air. The oxidizing gas may be A
r, sometimes mixed with an inert gas such as He and N _2. When the inert gas is mixed with the oxidizing gas, the gas mixture may comprise from about 1 percent oxidizing gas to about 99 percent oxidizing gas, and more preferably from about 5 percent oxidizing gas to about 99 percent. An oxidizing gas may be included. Alternatively, if desired, either essentially pure oxidizing gas or pure inert gas can be used.

The precise conditions can be changed to change the type of metal oxide particles produced. For example, temperature, heating time, heating and cooling rates, gases and exposure conditions to gases are all varied as desired. Generally, when heating in an oxidizing atmosphere, the longer the heating time, the greater the amount of oxygen incorporated into the material before equilibrium is reached. Once equilibrium conditions are reached, the overall conditions determine the crystalline phase of the powder.

A variety of ovens or similar devices are used to perform this heating. An example of an apparatus 660 that performs this step is shown in FIG. 22A. A device 660 made of glass or other inert material includes a jar 662 in which the particles are placed. A suitable glass reactor jar is Ace Glass (Vineland,
NJ). The top of the glass jar 662 is sealed to the glass cap 664 with Teflon ^R (Teflon) gasket 666 between jar 662 and the cap 664. Cap 664 is held down by one or more clamps. Cap 664, with a bushing of Teflon ^R respectively include a plurality of ports 668. Center port 6 of cap 664
Preferably, a stainless steel stir bar 670 with a plurality of blades is inserted through 68. The stir bar 670 is connected to a suitable motor.

One or more tubes 672 have been inserted through port 668 to introduce gas into jar 662. Tube 672 is made from stainless steel or other inert material. A diffuser 674 is included at the tip of tube 672 to distribute gas into jar 662. Heater / furnace 676 is typically located around jar 662. A suitable resistance heater is Glas-col (
Terre Haute, IN). Preferably, one port includes one T-connection 678. The temperature in the jar 662 is measured with a thermocouple 678 inserted through a tee 678. The T-connection 678 may be further connected to a vent 680. Vent 680 is provided to access gas circulated through jar 662. Vent 680 desirably communicates with a fume hood or alternative ventilator.

The desired gas is desirably flowed through jar 662. Tube 672 is generally connected to an oxidizing gas source and / or an inert gas source. An oxidizing gas, an inert gas, or a combination thereof, to form the desired atmosphere, is placed into jar 662 from a suitable gas source (s). Various flow rates can be used. This flow rate is desirably about 1 standard cubic centimeter / minute (scc
m: standard cubic centimeter) to about 1000 seem, and more desirably from about 10 seem to about 500 seem. This flow rate is usually constant during this processing step, but the gas flow rate and composition can be systematically varied over the processing duration, if desired. Alternatively, a stationary gas atmosphere can be used.

When processing manganese oxide and lithium manganese oxide nanoparticles, for example, the temperature is preferably between about 50 ° C. and about 600 ° C., and more preferably between about 50 ° C. and about 550 ° C. And more desirably, about 60 ° C. and about 400 ° C.
Sometimes between. This heating preferably lasts about 5 minutes or more, and generally lasts from about 2 hours to about 120 hours, preferably from about 2 hours to about 25 hours.
Some empirical adjustment may be required to create the appropriate conditions to obtain the desired material. The use of mild conditions avoids sintering between the larger particles. In some cases, the sintering of the particles may be performed at a somewhat elevated temperature and with some control to somewhat increase the average particle size.

Crystalline VO ₂ to orthorhombic V ₂ O ₅ and 2-D crystalline V ₂ O ₅ , and amorphous V ₂ O ₅ to orthorhombic V ₂ O ₅ and 2 -Conditions for converting to crystalline V ₂ O ₅ are disclosed in US patent application Ser. / 897,903
(Inventor: Bi et al.).

[0128] 2. Thermal Production of Lithium Manganese Oxide In an alternative method for preparing lithium manganese oxide nanoparticles, it has been found that heat processing methods can be used to prepare nanoscale lithium manganese oxide. In the recommended method for the thermal preparation of lithium manganese oxide, manganese oxide nanoparticles are first mixed with a mixture of lithium compounds. The resulting mixture is
Heated in an oven to prepare lithium manganese oxide. This heating, which results in the incorporation of lithium into the manganese oxide lattice, is performed in an oxidizing or inert atmosphere. The heating step, in either type of atmosphere, generally results in changing the oxygen / manganese ratio, lithium / manganese ratio, lithium / oxygen ratio, or a combination thereof.

Using mild enough conditions, ie, temperatures sufficiently below the melting point of the manganese oxide particles, results in the incorporation of lithium into the manganese oxide particles without significantly sintering the particles into larger particles. The manganese oxide particles used in the lithiation step are preferably nanoscale manganese oxide particles. Spinel lithium manganese oxide has been found to be prepared from manganese oxide in an oxidation state of +4 or less. In particular, manganese oxide in the oxidation state of +2 (MnO) to +4 (MnO ₂ ) is used for preparing a lithium manganese oxide spinel. Suitable manganese oxide nanoparticles, for example, MnO, an _{Mn 3 O 4, Mn 2 O} 3, Mn 5 O 8, MnO 2 and the corresponding mixed phase material.

Suitable lithium compounds include, for example, lithium nitrate (LiNO_Three),
Lithium chloride (LiCl), Li_TwoCO_Three, LiOH, LiOH.H_TwoO, Li_TwoC _Two O_Four, LiHC_TwoO_Four, LiHC_TwoO_Four・ H_TwoO, Li_ThreeC₆H_FiveO₇・ 4H_TwoO, LiC
OOH ・ H_TwoO and LiC_TwoH_ThreeO_Two・ H_TwoO. Of these lithium compounds
Incorporation of lithium into manganese oxide nanoparticles by some requires a heating step
Requires oxygen in the atmosphere. Suitable oxidizing gases include, for example, O 2_Two
, O_Three, CO, CO_TwoAnd combinations thereof. The reactant gases are Ar, He and
And N_TwoCan be diluted with an inert gas such as Eg air and / or
Clean and dry air can be used as oxygen source and inert gas. is there
Alternatively, the gas atmosphere may be an inert gas containing no other gas.
. Lithium manganese oxide is used in an inert atmosphere as described in the Examples below.
Or manufactured in an oxidizing atmosphere.

Further, this heat treatment may result in modification of the crystal lattice and / or removal of compounds adsorbed on the particles, improving the properties of the particles. The processing of metal oxide nanoparticles in an oven is described in co-pending U.S. patent application Ser. No. 08 / 88,897, entitled "Processing Vanadium Oxide Particles by Heating", which is hereby incorporated by reference. No. 897,903 (filing date: July 2, 1997)
1) are discussed more generally. In particular, heat processing under mild conditions is used to change the crystal structure of lithium manganese oxide nanoparticles prepared by laser pyrolysis. In particular, amorphous lithium manganese oxide can be converted to crystalline cubic spinel lithium manganese oxide by slow cooling heat treatment into larger particles without sintering the particles.

[0132] Various devices are used to perform heat processing for incorporation of lithium and / or annealing heat treatment of a sample. For example, the heating device shown in FIG. 22A as described above is used to perform a heating process for incorporating lithium. Another embodiment of an apparatus 700 for performing this processing is shown in FIG. 22B.
Apparatus 700 includes a tube 702 into which particles are placed. Tube 702 is
It is connected to a reactant gas source 704 and an inert gas source 706. To create the desired atmosphere, reactant gas, inert gas, or a combination thereof, is added to the tube 702.
Inside.

Preferably, the desired gas is flowed through tube 702. Tube 702 is placed in an oven or furnace 708. Oven 708 maintains a suitable portion of the tube at a relatively constant temperature, which can be varied systematically during the processing if desired. The temperature in the oven 708 is usually
Measured at 10. Vials 712 prevent particles from being depleted by the gas flow. The vial 712 is typically placed with its open end facing the gas flow source. To prepare lithium manganese oxide during this heating step, a mixture of manganese oxide particles and particles of a lithium compound is placed in a tube 702 in a vial 712. In an alternative embodiment, lithium manganese oxide produced by laser pyrolysis is placed in a vial 712 for heating in tube 702.

Precise conditions are selected to produce the desired type of product, including the type of oxidizing gas (if any), the concentration of the oxidizing gas, the pressure or flow rate of the gas, the temperature and the processing time. Is done. The temperature is generally mild, ie, a temperature significantly below the melting point of the material. The use of mild conditions avoids intergranular sintering of larger grain sizes. Oven 70 to produce a slightly larger average particle size.
In FIG. 8, the sintering of the particles can also be carried out at a somewhat higher temperature and with a certain control.

To incorporate lithium into the manganese oxide, the temperature is desirably about 60 ° C.
To about 600 ° C, and more desirably from about 100 ° C to about 550 ° C. The particles are desirably heated for about 5 minutes to about 100 hours. For heat processing (anneal heat treatment) of lithium manganese oxide produced by laser pyrolysis, the temperature is preferably in the range of about 50 ° C. to about 600 ° C., and more preferably about 50 ° C. to about 600 ° C. 550 ° C. The lithium manganese oxide particles are desirably heated for about 5 minutes to about 100 hours. Some empirical adjustments may be required to create the appropriate conditions to obtain the desired material.

C. The nature of the particles, for example, the population of particles in question, including either manganese oxide or lithium manganese oxide, is generally less than about 500 nm, preferably from about 5 nm to about 100 nm, and even more desirably from about 5 nm to about 50 nm. Has the average particle size of the primary particles. The primary particles usually have a generally spherical and glossy appearance. Upon closer inspection, crystalline particles usually have facets corresponding to the underlying crystal lattice. Nevertheless, crystalline primary particles tend to grow approximately equally in the physical three-dimensional direction and exhibit a shiny, spherical appearance. In a preferred embodiment, 95 percent of the primary particles, and preferably 9 percent
Nine percent has a ratio of dimension along the major axis / dimension along the minor axis of about 2 or less. The measurement of the diameter for particles having an asymmetric axis is based on the average of the measured lengths along the main axis of the particle.

Due to their small size, the primary particles tend to form loose aggregates between adjacent particles due to van der Waals forces and other electromagnetic forces. Nevertheless, the nanometer-scale primary particles are clearly observable in transmission electron micrographs of the particles. The particles typically have a surface area corresponding to particles on the nanometer scale as observed in their electron micrographs. In addition, the particles exhibit unique properties due to their small size and high surface area per weight of material. For example, vanadium oxide nanoparticles are described in “Batteries With El.”
Lithium batteries generally exhibit surprisingly high energy densities, as described in U.S. Pat. No. 5,952,125, entitled "Electroactive Nanoparticles").

The primary particles desirably have high uniformity in size. As mentioned above, laser pyrolysis generally produces primary particles having a very narrow size range. Furthermore, heat processing under mild conditions does not change this very narrow particle size range. In aerosol delivery methods, the particle size distribution is particularly sensitive to reaction conditions. Nevertheless, if the reaction conditions are properly controlled, a very narrow particle size range can be obtained with the aerosol delivery system as described above. As determined from transmission electron microscopy studies, the primary particles generally have at least about 95 percent, and preferably 99 percent, of the primary particles are greater than about 40 percent of the average particle size, and About 160
It has a particle size distribution such that it has a diameter less than a percent. The primary particles have at least about 95 percent, and preferably 99 percent, of the primary particles are greater than about 60 percent of the average particle size and about 140 percent of the average particle size.
Desirably, the particle size distribution has a diameter less than a percent.

Still further, in a preferred embodiment, all primary particles have an average particle size of about four times the average particle size, and preferably three times the average particle size, and more preferably more than twice the average particle size. Do not have. In other words, the particle size distribution has virtually no tail indicating a small number of particles having a significantly larger diameter. This is the result of a small reaction zone and a corresponding rapid cooling of the particles. Substantially cut-off at the tail (broken), the particles having a diameter greater than a particular cutoff value on the average particle size suggests that less than about 1 particle in 10 ⁶ particles. Because of this narrow particle size distribution and its taillessness, and its spherical morphology, it can be used in a variety of applications.

In addition, the nanoparticles generally have a very high level of purity. Crystalline manganese oxide and lithium manganese oxide nanoparticles produced by the methods described above may have a higher purity than the reactants, as the crystal formation process tends to exclude impurities from the crystal lattice. Be expected. Furthermore, crystalline manganese oxide particles produced by laser pyrolysis have a high degree of crystallinity. Similarly, crystalline lithium manganese oxide nanoparticles produced by heat processing have high crystallinity.
Impurities on the surface of these particles are removed by heating the particles, so that not only high crystal purity but also high overall purity can be achieved.

Manganese oxide is known to exist in a wide range of oxidation states from +2 to +4. Among the most common stoichiometric compositions for manganese oxide are MnO, M
n ₃ O ₄ , Mn ₂ O ₃ , Mn ₅ O ₈ and MnO ₂ . MnO and Mn ₅ O ₈ has only one known crystal phases. In particular, MnO has a cubic structure while Mn ₅
O ₈ has a monoclinic crystal structure. Some of these manganese oxides have other alternative crystal structures. For example, Mn ₃ O ₄ has either a tetragonal or orthorhombic crystal structure. Mn ₂ O ₃ has either a cubic or hexagonal crystal structure. MnO ₂ has any of a cubic, orthorhombic or tetragonal crystal structure.

Lithium manganese oxide has a complex phase diagram reflecting some of the complexity of its manganese oxide phase diagram. The lithium-rich spinel phase of lithium manganese oxide can have a stoichiometric composition ranging from Li _{1 + X} Mn _2-X O ₄ (0 ≦ x ≦ 0.33). Further, LiMn ₂ O _{4 + y} (−0.40 ≦ y ≦ 0.5
) There is an oxygen-rich (defective, y is negative) defective spinel phase having a stoichiometric composition of: Furthermore, lithium manganese oxide is Li _{1 + Z} Mn ₂ O ₄ (0 ≦ z ≦ 0.
In some cases, lithium is deficient corresponding to the stoichiometric composition of 2). as a whole,
These spinels and defective spinels are composed of Li _{1 + XZ} Mn _2-X O _{4 + y} (0 ≦ x ≦ 0.
33, 0.4 ≦ y ≦ 0.5 and 0 ≦ z ≦ 0.2).
Li ₂ MnO ₃ , Li _0.33 MnO ₂ , Li ₄ Mn ₅ O ₁₂ , tetragonal Li _X Mn ₂ O ₄ (1
. Other states of lithium manganese oxide are known, such as 8 ≦ x ≦ 2.2), LiMnO ₂ , and λ-MnO ₂ . λ-MnO ₂ can be prepared by chemically extracting lithium from LiMn ₂ O _{4 with} an acid such as 1M H ₂ SO ₄ or HNO ₃ . λ-MnO ₂ is Li _x Mn ₂ O ₄ (0.
05 ≦ x ≦ 0.20).

D. Application of Lithium Manganese Oxide to Battery Referring to FIG. 23, the battery 750 has a cathode 752, an anode 757, and a separator 756 between the cathode 752 and the anode 754. A single battery may include many anodes and / or cathodes. The electrolyte is provided in a variety of ways as described further below. Battery 750 preferably includes current collectors 758, 760 connected to cathode 752 and anode 754, respectively. A plurality of current collectors may be connected to each electrode as desired.

Since lithium is the lightest metal and the metal with the highest electropositivity, it has been used for reduction / oxidation reactions in batteries. Certain forms of manganese oxide are known to incorporate additional lithium ions into their structure by mechanisms such as intercalation or similar topochemical absorption. Intercalation of lithium ions into an appropriately shaped lithiated manganese oxide lattice produces Li _x MnO _Y.

In the lithium manganese oxide spinel, a part of the lithium is present in a tetrahedral spinel lattice site. Changes due to the incorporation of lithium into the lattice may change the amount of lithium at its tetrahedral sites from about 0.1 to about 1.0 per two manganese atoms. If the lithium concentration is low enough, the spinel crystal structure will be broken. On the other hand, however, once the tetrahedral site is essentially full, additional lithium may occupy the octahedral interlayer site in the spinel lattice.

[0146] Lithium is intercalated into the lithium manganese oxide lattice during discharge of the battery. Upon discharge, the anode acts as a cathode, and the cathode acts as an anode. Upon recharging, the lithium leaves the grid. That is, when a voltage is applied to the battery so that current flows to the anode, the lithium leaves the lattice due to the application of external EMF (electromotive force) to the battery. Suitable lithium manganese oxides are effective electroactive materials for anodes in lithium or lithium ion batteries.

[0147] Several forms of suitable for use as anode active materials in lithium-based batteries are provided.
There is a lithium manganese oxide spinel. Stoichiometric spinel, LiMn _Two O_FourOccupies one-eighth of the tetrahedral position and one-half of the octahedral position.
A standard spinel consisting of an oxygen close packed lattice containing manganese. Electrochemistry
When lithium is removed from this material in a typical battery, the voltage of the battery will generally be about
3.5V or higher, typically 3.8V or higher, about 4.4V or higher
In some cases. Such a voltage profile is 4
Called the volt curve, and the capacity drawn from the battery is called the 4 volt capacity
It is. A material having an appreciable amount of 4 volt capacity is called a 4 volt material.

In the presence of excess lithium, a lithium-substituted spinel, Li _{1 + y} Mn _2-y O _4, is formed, the excess lithium occupying the manganese site. y is about 0.33
At lower values, lithium is still extractable, and batteries containing this material must exhibit a 4 volt curve. As y increases, the amount of lithium that can be extracted decreases with a concomitant decrease in 4 volt capacity.

[0149] Almost 0 with a stoichiometric composition of Li _1.33 Mn _1.67 O ₄ or Li ₄ Mn ₅ O ₁₂
. At a value of 33, this material is a 3 volt material since only a small 4 volt capacity remains. Such a curve is called a 3 volt curve, and the capacity drawn from the battery is called a 3 volt capacity. This material having a recognizable amount of 3 volt capacity is called 3 volt material.

[0150] As a case where in the spinel there is cationic vacancies, the general formula: defects spinel having Li _1- δMn _{2- 2} δO ₄ is produced. The common form is a defective spinel with z = 0.11, yielding Li _0.89 Mn _1.78 O ₄ or Li ₂ Mn ₄ O ₉ . This material is primarily a three volt material. In addition, this material is a low temperature material that is typically synthesized in an oxygen-rich atmosphere. When heated to a high temperature in an oxygen atmosphere or when heated in an inert atmosphere, Li ₂ Mn ₄ O ₉ is converted to LiMn ₂ O ₄ .

[0151] The anode 754 includes electroactive nanoparticles, such as lithium manganese oxide nanoparticles, bound with a binder, such as a polymeric binder. The nanoparticles used in the anode 754 typically have any shape, for example, generally spherical nanoparticles or elongated nanoparticles. In addition to lithium manganese oxide, anode 754
Other electroactive nanoparticles such as TiO ₂ nanoparticles, vanadium oxide nanoparticles and / or manganese oxide nanoparticles may be included. The preparation of TiO ₂ nanoparticles is described in US Pat. No. 4,705,762, which is incorporated herein by reference. The use of vanadium oxide nanoparticles in lithium-based batteries is described in “Batteries Containing Electroactive Nanoparticles”, which is incorporated herein by reference.
("Batteries With Electroactive Nanop
This is described in U.S. Patent No. 5,952,125 entitled "articles".

[0152] Some of the electroactive materials are modest electrical conductors, but the anode generally includes, in addition to the electroactive nanoparticles, electrically conductive particles. These auxiliary electrically conductive particles are also usually held by a binder. Suitable electrically conductive particles include carbon particles such as carbon black, metal particles such as silver particles, and the like.

The loading of particles in the binder can be large. The particles desirably comprise at least about 80 weight percent of the anode, and more desirably at least about 90 weight percent. The binder is polyvinylidene fluoride, polyethylene oxide, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylate, ethylene- (propylene-diene monomer) copolymer (EPDM
) And their mixtures and their copolymers.

[0154] Cathode 752 is comprised of a variety of materials suitable for use with lithium ion electrolytes. In the case of a lithium battery, the cathode comprises lithium metal or a lithium alloy in the form of either a foil, grid or metal particles in a binder.

Lithium ion batteries use particles of a composition that can intercalate lithium.
The particles are held in the cathode by a binder. Suitable intercalation compounds are
For example, graphite, synthetic graphite, coke, mesocarbon, doped carbon, fullerene, niobium pentoxide, tin alloys, SnO ₂ and mixtures thereof and a composite material.

Current collectors 758 and 760 facilitate the flow of electricity from battery 750. Current collector 7
58,760 are electrically conductive, generally made of nickel, iron, stainless steel, aluminum and copper, and are metal foils or, preferably, metal grids. Current collectors 758, 760 may be on the surface of their associated electrodes or may be embedded within their associated electrodes.

The separator element 756 is electrically insulating and provides a path for at least some types of ions. The permeation of ions through the separator provides electrical neutrality in different compartments of the battery. The separator generally prevents the electroactive compound in the cathode from contacting the electroactive compound in the anode.

Various materials are used for the separation plate. For example, the separator may be prepared from glass fibers that form a porous matrix. Recommended separators are prepared from polymers such as polymers suitable for use as binders. The polymer separator may be porous to provide ionic conductivity. Alternatively, the polymer separator may be a solid electrolyte prepared from a polymer such as polyethylene oxide. For a solid electrolyte, the electrolyte is incorporated into the polymer matrix to provide ionic conductivity without the need for a liquid solvent.

A variety of lithium salts are included in the electrolyte for a lithium battery or a lithium ion battery. The recommended lithium salts have an inert anion and are non-toxic. Suitable lithium salts include, for example, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium bis (trifluoromethylsulfonylimide), lithium trifluoromethanesulfonate, lithium tris (trifluoromethylsulfonyl) methide , Lithium tetrafluoroborate, lithium perchlorate, lithium tetrachloroaluminate, lithium chloride and lithium perfluorobutane.

When a liquid solvent is used to dissolve the electrolyte, it is desirable that the solvent be inert and not dissolve the electroactive material. In general, suitable solvents are propylene carbonate, dimethyl carbonate, diethyl carbonate, 2-methyltetrahydrofuran, dioxolane, tetrahydrofuran, 1,2-dimethoxyethane, ethylene carbonate, γ-butyrolactone, dimethyl sulfoxide, acetonitrile, formamide, dimethylformamide and nitromethane It is.

The shape of the battery components is adjusted to suit the desired end product, for example, coin batteries, rectangular or cylindrical batteries. The battery generally includes a casing having portions suitable for making electrical contact with the current collector and / or the electrodes of the battery. If a liquid electrolyte is used, the casing must prevent leakage of the electrolyte. This casing helps keep the battery elements close to each other to reduce the resistance in the battery. A plurality of battery cells can be connected in series or in parallel in one case.

Particle Synthesis Examples Example 1-Manganese Oxide Particle Synthesis. Gas Phase Reactants The synthesis of the manganese oxide particles described in this example was performed by laser pyrolysis.
These particles were produced essentially using the laser pyrolysis apparatus of FIG. 2 described above, using the reactant delivery apparatus of FIG. 3 with the solid precursor delivery system shown schematically in FIG. .

Manganese carbonyl (Stream Chemical, Inc., Newb
(urryport, MA) precursor vapor is carried to the reaction chamber by Ar gas flowing through its solid precursor delivery device containing Mn ₂ (CO) ₁₀ . This precursor was heated to the temperature shown in Table 1. C ₂ H ₄ gas was used as the laser absorbing gas and argon was used as the inert gas. This reaction gas mixture comprising Mn ₂ (CO) ₁₀ , Ar, O ₂ and C ₂ H ₄ was introduced into a reactant gas nozzle for injection into the reaction chamber. This reactant gas nozzle, dimensions: 5/8 inch x 1
It has a / 16 inch opening. Additional parameters for laser pyrolysis synthesis relating to the particles of Example 1 are specified in Table 1.

[0164]

[Table 1] sccm = cubic centimeters per minute at standard conditions slm = liters per minute at standard conditions Argon-Window (Win) = Argon flow through inlet tubes 216, 218 Argon-Shielding (Sld) = Argon through annular channel 142 Flow.

The production rate of manganese oxide particles was typically about 1 g / hour. In order to evaluate the atomic arrangement, these samples were subjected to a Siemens D500
Investigated by X-ray diffraction using X-ray diffractometer with Cu (Ka) radiation. The X-ray diffraction patterns of the samples manufactured under the conditions specified in the three columns of Table 1 are shown in FIG.
4-26. Under the set of conditions specified in Table 1, these particles exhibited an X-ray diffraction pattern corresponding to chlorite (cubic) MnO. Particles produced under the conditions in column 3 of Table 1 exhibited ark at 65 ^° caused by the aluminum sample holder. The sample holder is sometimes seen in this diffractogram. These diffractograms also show peaks suggesting the presence of small amounts of amorphous carbon that may form as a coating on the particles. This amorphous carbon can be removed by light heating in an oxygen atmosphere. Such amorphous carbon coatings are described in co-pending U.S. patent application Ser. No. 09 / 93,978, entitled "Aluminum Oxide Particles," herein incorporated by reference. / 136
483, further described.

Transmission electron microscopy (TEM) was used to determine particle size and morphology. Table 1
FIG. 27 shows a TEM micrograph of the particles produced under the conditions in column 2 of FIG. A part of this TEM micrograph was examined and an average particle size of about 9 nm was obtained.
The corresponding particle size distribution is shown in FIG. The particle size of the particles clearly seen in the micrograph of FIG. 27 was manually measured to determine the approximate particle size distribution. To avoid distorted or out-of-focus areas in the micrograph, only particles with distinct grain boundaries were measured. The measurement results obtained in this way must be more accurate and unbiased because a single observation does not give a clear image of all particles. It is significant that these particles are distributed over a rather narrow size range.

Example 2-Manganese Oxide Particle Synthesis-Aerosol Metal Precursor, First Laser Pyrolysis Device The synthesis of manganese oxide particles described in this example was performed by laser pyrolysis.
These particles were basically obtained using the laser pyrolysis apparatus of FIG.
Manufactured using the reactant delivery device of

Manganese chloride (Alfa Aesar Inc., Ward Hill, MA)
) The precursor vapor was sent to the reaction chamber as an aerosol of an aqueous solution prepared with deionized water. C ₂ H ₄ gas was used as the laser absorbing gas and argon was used as the inert gas. A reactant mixture comprising MnCl ₂ , Ar, O ₂ and C ₂ H ₄ was introduced into a reactant gas nozzle for injection into the reaction chamber. The reactant nozzle has an opening with dimensions: 5/8 inch x 1/16 inch. Additional parameters for laser pyrolysis synthesis relating to the particles of Example 2 are identified in Table 2.

[0169]

[Table 2] sccm = cubic centimeters per minute at standard conditions slm = liters per minute at standard conditions Argon-Window (Win) = Argon flow through inlet tubes 216, 218 Argon-Shielding (Sld) = Argon through annular channel 142 Flow.

The production rate of manganese oxide particles was typically about 1 g / hour. To evaluate their atomic arrangement, the samples were analyzed on a Siemens 500 X-ray diffractometer with Cu
(Ka) Investigated by X-ray diffraction using radiation. The X-ray diffraction pattern of the sample produced under the conditions specified in Table 2 is shown in FIG. The particles also showed an X-ray diffraction pattern corresponding to manganese ore (cubic) MnO, but the peak in the X-ray diffraction pattern was very weak, indicating that these particles were substantially non- It was shown to be crystalline. On the basis of these results, if the reaction conditions are changed, amorphous MnO or higher crystalline MnO must be obtained.

[0171] Transmission electron microscopy (TEM) was used to determine particle size and morphology. Table 2
FIG. 30 shows a transmission electron micrograph of the particles produced under the conditions of (1) and (2). The corresponding particle size distribution is shown in FIG. This particle size distribution was obtained according to the method described in Example 1.

Example 3-Manganese Oxide Particle Heat Treated Sample In accordance with the conditions specified in column 2 of Tables 1 and 2, a sample of manganese oxide nanoparticles produced by laser pyrolysis was placed in an oven under oxidizing conditions. And heated. Three samples were heat treated. Another two samples were thermally processed starting from the nanoparticles produced under the conditions in Table 2. The oven is basically the one described above in FIG. Approximately 100 and 300 mg of the nanoparticles were placed in a 1 cc open vial inside a quartz tube inserted through the oven. Oxygen was flowed through a 1.0 inch diameter quartz tube. Other parameters of the heating process are specified in Table 3.

[0173]

[Table 3] Sample 1-Samples prepared from particles made according to the parameters in column 2 of Table 1 Samples 2A and 2B-Samples prepared from particles made according to the parameters in Table 2.

The crystal structure of the obtained heat-treated particles was determined by X-ray diffraction. Samples 1 and 2 in Table 3
The X-ray diffractograms of A and 2B are shown in FIGS. 32-34, respectively. FIG.
Shows that the manganese oxide in sample 1 was converted to a form having a stoichiometric composition of Mn ₅ O ₈ . The X-ray diffractogram of sample 2A shown in FIG. 33 shows the presence of Mn ₃ O ₄ , with additional peaks in the spectrum at 23 ^° and 33 ^° corresponding to very small amounts of Mn ₂ O _3. ing. The X-ray diffraction diagram of Sample 2B in FIG. 34 shows that manganese oxide was converted to Mn ₃ O ₄ . It is not clear why this MnO sample becomes manganese oxide of different stoichiometric composition by heat treatment. The different results may be due to different starting material properties and different heating times.

Example 4-Manganese oxide particle synthesis-aerosol metal precursor. Second laser pyrolysis apparatus The synthesis of the manganese oxide particles described in this example was performed by laser pyrolysis.
These particles are basically divided into a laser pyrolyzer as shown in FIGS. 6-13 described above, and a laser pyrolyzer as shown in FIGS. Was manufactured using an ultrasonic nozzle as shown in FIGS. 19-20. No cap bushing was used. Approximately up to the top of the cap, spacers 550 and wedges 558 were used to raise the level of the ultrasonic nozzle. The solution delivered by aerosol delivery devices, 99 percent isopropyl alcohol and 5mL of 38% HCl in a solvent prepared from an aqueous solution 2 moles of _{MnNO 3 · H 2 O (Strem} Chemical of 495 ml, Inc., Newburyport MA
). Isopropyl alcohol acts as an infrared absorber. Oxygen is mixed with the aerosol by being sent through tube 536. The emission tube 486 of FIG. 10 does not exist. The top of cap 486 is approximately 0.85 inches from the centerline of the laser beam. Additional parameters for the two tests are shown in Table 4.

[0176]

[Table 4] sccm = cubic centimeters per minute at standard conditions slm = liters per minute at standard conditions Argon-Window (Win) = Argon flow through inlets 330, 332 Argon-Shielding (Sld) = Through shielding gas conduit 365 Argon flow Laser power (input) = laser power entering the reaction chamber Laser power (output) = laser power exiting the reaction chamber towards the beam dump.

The manganese oxide particles were produced at a rate of approximately 20 g / hour. The conditions specified in column 1 of Table 4 resulted in a brown powder, while the parameters specified in column 2 of Table 4 resulted in a yellow powder.

To evaluate the atomic arrangement, the samples were examined by X-ray diffraction on a Siemens D500 X-ray diffractometer using Cu (Ka) radiation. Columns 1 and 2 in Table 4
The X-ray diffraction patterns of the samples manufactured under the conditions specified in the column are respectively shown in FIG.
-36. Particles produced under the conditions of columns 1 and 2 of Table 4 indicate the presence of chlorite (cubic) MnO and black manganese Mn ₃ O ₄ .

[0179] EXAMPLE 5 Lithium manganese oxide particles by laser pyrolysis - Synthesis of aerosol metal before precursor manganese oxide / lithium manganese oxide particles described in this Example was carried out in laser pyrolysis. These particles were produced essentially using the laser pyrolysis apparatus of FIG. 2 described above and the reactant delivery apparatus of FIG. 4A.

Manganese chloride (Alfa Aesar Inc., Ward Hill, MA)
) Precursor and lithium chloride (Alfa Aesar Inc.) precursor were dissolved in deionized water. The concentration of LiCl in this aqueous solution was 4 mol, and the concentration of MnCl ₄ was also 4 mol. The aqueous solution containing the two metal precursors was sent to the reaction chamber as an aerosol. C ₂ H ₄ gas was used as the laser absorbing gas and argon was used as the inert gas. O _2, Ar and C ₂ H ₄ is delivered to the supply pipe of the reactant supply system. A reactant mixture comprising MnCl ₂ , LiCl ₂ , Ar, O ₂ and C ₂ H ₄ was introduced into a reactant gas nozzle for injection into the reaction chamber. The reactant nozzle has an opening with dimensions: 5/8 inch x 1/16 inch.
Additional parameters for laser pyrolysis synthesis relating to the particles of Example 1 are identified in Table 5.

[0181]

[Table 5] sccm = cubic centimeters per minute at standard conditions slm = liters per minute at standard conditions Argon-Window (Win) = Argon flow through inlet tubes 216, 218 Argon-Shielding (Sld) = Argon through annular channel 142 Flow Argon = argon directly mixed with the aerosol.

The production rate of manganese oxide / lithium manganese oxide particles is typically about 1 g / g
It was time. In order to evaluate the atomic arrangement, these samples were subjected to Siemens D5
Examined by X-ray diffraction with a 00X-ray diffractometer using Cu (Ka) radiation. The X-ray diffractogram of the sample produced under the conditions specified in Table 5 is shown in FIG. The X-ray diffractogram shown in FIG. 37 shows that the sample is amorphous. In particular, the broad peak from about 27 ^° to about 35 ^° corresponds to amorphous lithium manganese oxide. The sharp peak at about 15 ^° is due to the presence of traces of manganese chloride.
The sharp peak at about 53 ^° is due to traces of unidentified contaminants.

Example 6 Lithium Manganese Oxide Particles Produced by Laser Pyrolysis Heat Treatment A sample of manganese oxide / lithium manganese oxide nanoparticles produced by laser pyrolysis was placed in an oven according to the conditions specified in Example 5. , Heated under oxidizing conditions. The oven is basically that described above in FIG. About 100 and 3
Between 00 mg of nanoparticles was placed in a 1 cc open vial inside a quartz tube inserted through the oven. Oxygen was flowed through a 1.0 inch diameter quartz tube at a flow rate of 308 / min. The oven was heated to 400C. The particles were heated for about 16 hours.

The crystal structure of the obtained heat-treated particles was determined by X-ray diffraction. The X-ray diffraction diagram of the heated sample is shown in FIG. The X-ray diffraction diagram shown in FIG. 38 contains the aggregate mixture phase material of this particle, and the main components: LiMn ₂ O ₄ (about 60% by volume) and M
n ₃ O ₄ (about 30% by volume) and minor component: Mn ₂ O ₃ (about 10% by volume). This LiMn ₂ O ₄ compound has a cubic spinel crystal structure. The sample may include additional amorphous phase material. In particular, based on the amount of lithium introduced into the reaction stream, the sample probably contains additional lithium that has not been identified in the crystalline phase.

Example 7 Lithium Incorporation into Manganese Oxide Particles The manganese oxide particles produced as described in Example 4 were further processed to prepare lithium manganese oxide. The manganese oxide particles used were a mixture of particles prepared under the synthesis conditions specified in columns 1 and 2 of Table 4. About 2.0 g of nanocrystalline manganese oxide is about 1.2 g of lithium nitrate, LiNO ₃ (Alfa
Aesar Inc. , Ward Hill, MA). The mixture was heated in an oven under pure O ₂ or under pure Ar. The oven is
This is basically the one described above with reference to FIG. 22B. The mixture of nanocrystalline manganese oxide and lithium nitrate was placed in an aluminum boat inside a quartz tube inserted through the oven. The selected gas was flowed through a 1.0 inch diameter quartz tube at a rate of about 40 cc / min. The oven was heated to about 400C. The particles were heated for about 16 hours.

[0186] Three samples were processed. The first sample had a weight ratio of LiNO ₃ nanocrystalline MnO / 1 part of 1.84 parts. The second sample had 1.66 parts of nanocrystalline M
It had a weight ratio of nO / 1 part of LiNO ₃ . Samples 1 and 2 were heat-treated under an oxygen gas flow. Sample 3 had a weight ratio of LiNO ₃ nanocrystalline MnO / 1 part of 1.63 parts. Sample 3 was heat treated under a flow of argon.

To evaluate the crystal structure of this material after heat treatment, the samples were examined by X-ray diffraction on a Siemens D500 X-ray diffractometer using Cu (Ka) radiation. The X-ray diffraction spectrum for Sample 1-3 is depicted in FIG. The spectrum for Sample 1 has a peak corresponding to unreacted manganese oxide. When the ratio of manganese oxide / lithium nitrate was reduced from 1.84 to 1.66, complete reaction of manganese oxide was observed. The lithium manganese oxide of Sample 2 had a lattice parameter of about 8.17 Å, similar to the defective spinel Li ₂ Mn ₄ O ₉ . Sample 3
Had a lattice parameter of about 8.23 angstroms, similar to that of LiMn ₂ O ₄ .

A transmission electron microscope (TEM) was used to determine the particle size and morphology of the lithium manganese oxide and manganese oxide starting materials. A TEM micrograph of the manganese oxide nanoparticle starting material is shown in FIG. FIG. 41 shows a TEM micrograph of the lithium manganese oxide of Sample 1. It should be noted that during this heating, the particle size does not change, if at all. Due to the lack of optimization of the aerosol conditions, the manganese oxide particles shown in FIG. 40 have a broader particle size distribution than found in the manganese oxides in Examples 1 and 2 above. Even if lithium is mixed with the manganese oxide nanoparticles, the particle size does not change significantly. Therefore, the manganese oxide nanoparticles described above can be used to prepare lithium manganese oxide having a narrow particle size distribution.

[0189] Synthesis of direct laser heat decomposition synthetic crystalline lithium manganese oxide particles described in this example of the crystalline lithium manganese oxide with EXAMPLE 8 Aerosol was conducted by laser pyrolysis. These particles were produced essentially using the laser pyrolysis apparatus of FIG. 2 described above and the reactant delivery apparatus of FIG. 4B or 4C.

Manganese nitrate [Mn (NO_Three)_TwoAlfa Aesar Inc. ] Precursor, nitrate
Lithium oxide (Alfa Aesar Inc.) precursor and urea (CH_FourN_TwoO
), Two solutions were prepared. The first solution was used for preparing sample 3 in Table 6.
I was. The first solution contains 3 molar LiNO._ThreeAnd 4 molar Mn (NO_Three) _Two Was an aqueous solution having The solvent for the second solution was isopropyl alcohol.
It was a 50:50 weight percent mixture with ionic water. The second solution is 2
LiNO_Three, 2 moles of Mn (NO_Three)_TwoAnd with a urea concentration of 3.6 molar
Was. This second solution was used for preparing the first and second samples in Table 6.

The selected solution containing the bimetallic precursor was sent to the reaction chamber as an aerosol. C ₂ H ₄ gas is used as a laser absorbing gas, and Argon was used as the inert gas. O ₂ , Ar and C ₂ H ₄ were sent to the gas supply pipe of the reactant supply system. _{Mn (NO 3) 2, LiNO} 3, Ar, the reaction mixture containing O ₂ and C ₂ H ₄ was introduced to the reaction nozzles for delivery to the reaction chamber. The reactant nozzle has an opening with dimensions: 5/8 inch x 1/4 inch. The first two samples were prepared essentially with a reactant delivery device as shown in FIG. 4B. A third sample was prepared essentially with a reactant delivery device as shown in FIG. 4C. Relevant additional parameters for laser pyrolysis synthesis are specified in the first two columns of Table 6.

[0192]

[Table 6] slm = liters per minute at standard conditions Argon-Window (Win) = Argon flow through inlet tubes 216, 218 Argon-Shielding (Sld) = Argon flow through annular channel 142 Argon = Argon directly mixed with aerosol .

To evaluate the atomic arrangement, the samples were examined by X-ray diffraction on a Siemens D500 X-ray diffractometer using Cu (Ka) radiation. The X-ray diffractogram of the sample produced under the conditions of columns 1 and 2 specified in Table 6 is shown in FIG. This is a representative diffractogram, but some samples showed relatively small peaks due to Mn ₃ O ₄ contamination. The X-ray diffraction peak characteristic of spinel lithium manganese oxide is clearly seen in the diffraction diagram. Small differences in stoichiometry in the spinel structure are difficult to clarify from X-ray diffractograms. further,
The peak in the X-ray diffractogram is broad, which is due to its small particle size or non-uniform broadening either due to the inclusion of mixed phase material or stoichiometric variations. It may be due to. Nevertheless, this diffractogram is consistent with samples containing LiMn ₂ O ₄ and Li ₄ Mn ₅ O ₁₂ or mixtures of materials of intermediate stoichiometry. These conclusions are confirmed by the electrochemical evaluation described below. In each case, the crystalline lithium manganese oxide is believed to contain the material in one form or another as a major component (about 50% or more).

Transmission electron microscopy (TEM) was used to determine the particle size and morphology of as-synthesized crystalline lithium manganese oxide. A TEM micrograph of a sample of lithium manganese oxide produced under the conditions in the second column of Table 6 is shown in FIG.
The corresponding particle size distribution is shown in FIG. The particle size distribution was obtained according to the method described in Example 1. This average particle size is about 40 nm. This particle size distribution shows a relatively wide particle size distribution as compared with the particle size distribution generally obtained by laser pyrolysis. Delivery of reactants by the reactant delivery device of FIG. 4C provides greater reactant throughput and a correspondingly higher production rate as compared to the aerosol delivery devices of FIGS. 4A and 4B. The aerosol produced with the device of FIG. 4C is clearly evident. Not as homogeneous as aerosols made with the other two units. The particle size distribution using the reactant delivery device of FIG. 4C is approximately 200-300 Torr to obtain the desired phase product.
Using a pressure lower than the, and by increasing the flow rate of O _2, it can be narrowed.

Example 9-Silver Vanadium Oxide Nanoparticles The synthesis of the silver vanadium oxide nanoparticles described in this example was performed by laser pyrolysis. These particles were produced essentially using the laser pyrolysis apparatus of FIG. 2 described above and using the reactant delivery system of FIG. 4B or 4C.

Two solutions were prepared for delivery to the reaction chamber as an aerosol. Both solutions were made with similar vanadium precursor solutions. To prepare the first vanadium precursor solution, Aldrich Chemical (Milwaukee, W.)
10.0 g of vanadium (III) oxide (V ₂ O ₃ ) from I)
In deionized water. To this vanadium (III) oxide suspension, 30 mL of a 70% aqueous solution of nitric acid (HNO ₃ ) was added dropwise with vigorous stirring. This reaction is an exothermic reaction, and caution is required because a brown gas suspected of being NO ₂ is released. The resulting vanadium precursor solution (about 150 mL) was a dark blue solution. For the second vanadium precursor solution, the first precursor solution was scaled up to triple all components.

To make the first silver solution, Aldrich Chemical (Milw
A solution of silver carbonate (Ag ₂ CO ₃ ) from Auckee, Wis. was prepared by suspending 9.2 g of silver carbonate in 100 mL of deionized water. With vigorous stirring, 10 mL of a 70% by weight aqueous solution of nitric acid (HNO ₃ ) was added dropwise. When the addition of nitric acid was completed, a colorless and transparent solution was obtained. This silver solution was added to the first vanadium precursor solution with constant stirring to produce a first metal mixture solution for aerosol delivery. The resulting dark blue first metal mixture solution had a vanadium: silver molar ratio of about 2: 1.

To prepare a second silver solution, Aldrich Chemical (Milw
34.0 g of silver nitrate (AgNO ₃ ) from Auake, WI) was dissolved in 300 mL of deionized water. To produce a second metal mixture solution for aerosol delivery,
This silver nitrate solution was added to the second vanadium precursor solution while stirring at a constant speed. The resulting dark blue second metal mixture solution also had a vanadium: silver molar ratio of about 2: 1.

The selected aqueous solution containing the vanadium and silver precursor was sent to the reaction chamber as an aerosol. C ₂ H ₄ gas is used as a laser absorbing gas, and Argon was used as the inert gas. O ₂ , Ar and C ₂ H ₄ were sent to the gas supply pipe of the reactant supply system. Vanadium oxide, silver nitrate, Ar, the reaction mixture containing O ₂ and C ₂ H ₄ was introduced to the reaction nozzles for delivery to the reaction chamber. The reactant nozzle has an opening with dimensions: 5/8 inch x 1/4 inch. Additional parameters for laser pyrolysis synthesis related to this particle synthesis are identified in Table 7. Sample 1 was prepared essentially with a reactant delivery device as shown in FIG. 4B, while Sample 2 was basically prepared with a reactant delivery device as shown in FIG. 4C. Was prepared.

[0200]

[Table 7] slm = liters per minute at standard conditions Argon-window = argon flow through inlets 216, 218 Argon-shielding = argon flow through annular channel 142 Argon = argon directly mixed with aerosol.

To evaluate the atomic arrangement, the samples were examined by X-ray diffraction on a Siemens D500 X-ray diffractometer using Cu (Ka) radiation. The X-ray diffraction patterns of Sample 1 (lower curve) and Sample 2 (upper curve) manufactured under the conditions specified in Table 7 are shown in FIG. These samples have peaks corresponding to VO ₂ , elemental silver and multiple peaks not corresponding to known substances. The major crystalline phases corresponding to these samples showed peaks at 2θ equal to about 30-31 ^° , 32 ^° , 33 ^° and 35 ^° . This phase is believed to be a previously unidentified silver vanadium oxide phase. The crystalline silver vanadium oxide phase was prepared under conditions where the vanadium oxide nanoparticles were mixed with silver nitrate and the samples were heated for an insufficient time to produce Ag ₂ V ₄ O ₁₁ . Observed in the sample. The specific capacity of Sample 1 measured in the coin battery is consistent with this interpretation.

[0202] The powders of the samples produced under the conditions specified in Table 7 were further analyzed using a transmission electron microscope. TEM micrographs are shown in FIG. 46A (column 1 of Table 7) and 46B.
(Second column of Table 7). This TEM micrograph has particles that fall into different particle size distributions. This is characteristic of mixed phase materials produced by laser pyrolysis, where each material generally has a very narrow particle size distribution. The fraction of silver vanadium oxide in this mixed phase material must increase due to increased oxygen flow rates, reduced laser power and reduced pressure. The production of silver vanadium oxide particles by laser pyrolysis is further described in Reitz et al., US patent application Ser. No. 09 / 311,506, entitled "Metal Vanadium Oxide Particles," which is hereby incorporated by reference. Have been.

Battery Examples Further, the performance of the lithium manganese oxide based battery was evaluated by measuring the charge capacity and energy density of the lithium manganese oxide powder used as the active material in the positive electrode. The batteries tested in Examples 9-11 were all manufactured according to a common method. These lithium manganese oxide powders (LMO) were mixed with conductive acetylene black powder (AB) (Chevron Corp. catalog number 55) at a ratio of 80:10. This powder mixture was ground with a mortar and pestle to thoroughly mix the powder.

[0204] To this homogeneous powder mixture was added a few drops of a solution of polytetrafluoroethylene (PTFE). This 10% PTFE solution contains PTFE (Al
drich Chemical Co. , Milwaukee, WI) solution. The final ratio of LMO: AB: PTFE was 80:10:10. A small amount of methyl alcohol (Aldrich Chemical Co.)
. , Milwaukee, WI). In addition, isopropyl alcohol (Aldrich Chemical Co.,
Milwaukee, WI) was added.

To thoroughly mix the slurry, it was placed in a blender and the solution was filtered through a vacuum filter to remove the solvent. The resulting powder mixture was thoroughly mixed and roll formed to 5 mil (5-mil) thickness. An aluminum mesh (Dekler, Brandford CT) was placed on top of this mixture and rolled further to a final thickness with a 5 mil mesh. The mixture containing the aluminum mesh was baked at 250 ° C. for 2 hours in a vacuum oven to remove residual solvent and melt the PTFE. Take out of the oven and 16m
m electrodes were pressed and pressurized at a pressure of 5000 pounds. The extruded electrode was placed again in a vacuum oven at 120 ° C. overnight to remove residual moisture. Immediately after removal from the oven, the electrodes were placed in a glove box (Vacuum Atmosphere Co., Hawthone, CA) under an argon atmosphere.
Put in. In the glove box, the electrodes were weighed and the thickness was measured.

This sample was tested in a battery 800 having an airtight two-electrode structure as shown in FIG. The casing 802 for the sample battery is manufactured by Hohsen Co. , Osaka,
Obtained from Japan. The casing includes a top 804 and a bottom 806 and is secured with four screws 808. The other two screws not shown in FIG. 47 are behind the screws shown. Lithium metal (Alfa / Ae
sar, Ward Hill, MA) was used as the cathode 812. Cathode 8
12 was placed in the bottom 806. Separation plate 814 Celgard ^R 2400 (
Hoechst Celanese, Charlotte NC) was placed over lithium metal. A Teflon ^R ring 816 was placed on the separator 814.
The anode 818 was placed on the mesh side in a Teflon ^R ring 816. Aluminum pellets 820 were placed on the anode 818 and the electrolyte was added. EM
Electrolyte from industrial (Hawthorne, NY) electrolyte from 1: 1M-LiPF ₆ dissolved in 1 ethylene carbonate / dimethyl carbonate. Teflon ^R O-rings, in order to electrically insulate the two electrodes are placed between the top 804 and bottom 806. Similarly, the screws 808 are connected to the top 804 and the bottom 80
6, Teflon ^R sleeve in order to electrically insulate the screw 808 (sleev
e). Electrical contact between the battery tester and the battery 800 is made by the top 804 and the bottom 806.

The samples were tested at a constant discharge / charge rate of 0.5 mA / cm ² ,
At 5 ° C., between 2.5 V and 4.4 V, or between 2.2 V and 3.3 V or 3
. It was tested by cycling between 5V and 4.4V. This measurement is based on Arbin
Arb from Instruments, CollegeStation, TX
in Battery Testing System, Model BT40
23. The charge / discharge curve was recorded and the capacity of the active material was determined.

The energy density was evaluated by integrating (voltage × current / mass of active material) over the discharge time. The current during the test was 1 mA / cm ² , corresponding to a current density of 0.5 mA / cm ² . The mass of the active material is from about 30 to about 50
mg.

Example 10-4 Volt Cycling Behavior-Thermal Synthesis of Lithium Manganese Oxide This example examined the 4 Volt cycling behavior of four different lithium manganese oxide materials. The battery was manufactured according to the method outlined above using the materials manufactured as in Samples 2 and 3 of Example 7. For comparison,
Batteries using standard LiMn ₂ O ₄ and Li ₂ Mn ₄ O ₉ were also made. Commercial LiM
n ₂ O ₄ is available from Alfa Aesar, a Johnson Mattey Com.
pany, Ward Hill, MA. Li ₂ Mn ₄ O ₉ (standard Li ₂ Mn ₄ O ₉ ) is a mixture of manganese carbonate and lithium carbonate at about 400 ° C.
Synthesized using standard methods based on heating for about 60 hours. Its cycling behavior in the 4 volt range was examined by charging the material to 4.40 volts and discharging the material. The obtained discharge curve is shown in FIG. In FIG. 48, the cycling behavior of the battery made with the nanoparticles of Example 7 is designated as Sample 2 and Sample 3, as appropriate, and the cycling behavior of the battery made with commercially available or standard powder is: Indicated by their stoichiometric composition, together with the designation "commercially available". The battery in sample 2 had a similar discharge curve to the commercial Li ₂ Mn ₄ O ₉ material, and the battery in sample 3 had a similar discharge curve to the commercial LiMn ₂ O ₄ material Please note.

Example 11-3 Volt Cycling Behavior-Thermal Synthesis of Lithium Manganese Oxide This example examined the 3 Volt cycling behavior of four different lithium manganese oxide materials. The battery was manufactured according to the method outlined above using the materials manufactured as in Samples 2 and 3 of Example 7. For comparison, batteries using commercially available LiMn ₂ O ₄ and Li ₂ Mn ₄ O ₉ were also manufactured. Cycling behavior in the 3 volt range was examined by charging the material to 3.30 volts and discharging the material. The obtained discharge curve is shown in FIG. In FIG. 49, the cycling behavior of the battery made with the nanoparticles of Example 7 is designated as Sample 2 and Sample 3, as appropriate, and the cycling behavior of the battery made with the commercial powder is “commercial” , And their stoichiometry. Note that the battery in sample 2 has a similar insertion potential to the commercially available Li ₂ Mn ₄ O ₉ material, and the battery in sample 3 has a similar insertion potential to the commercially available LiMn ₂ O ₄ material. I want to be.

Example 12-Cycling Properties-Thermal Synthesis of Lithium Manganese Oxide The cycling behavior of the battery produced as described above was investigated for four different anode materials. The battery was manufactured according to the method outlined above using the materials manufactured as in Samples 2 and 3 of Example 7. For comparison, batteries using commercially available LiMn ₂ O ₄ and Li ₂ Mn ₄ O ₉ were also manufactured. Batteries with anode material from Sample 2 and commercial LiMn ₂ O ₄ were fabricated and tested in duplicate. In the material of sample 3, only one battery was manufactured, but commercially available LiMn ₂
In O ₄ 3 pieces of batteries are manufactured and tested. In each cycle, mAh / g
Was evaluated. These cells were cycled between about 3.3 volts and 2.0 volts. The results are plotted in FIG.

[0212] The results of this cycling test show that batteries made with nanoparticles have greater cycling stability. This improved cycling stability is due to its structural resistance to repeated volume expansion and contraction associated with lithium insertion and extraction. Thus, this data is based on lithium,
This demonstrates the superiority of nanoscale lithium manganese oxide particles as an active material for rechargeable batteries.

[0213] The properties of the directly produced crystalline lithium manganese oxide beaker cell test laser pyrolysis synthesis of directly manufacturing the lithium manganese oxide in Example 13 laser pyrolysis synthesis was investigated in a beaker cell test. Test batteries were fabricated with two nanomaterial samples. First
Was prepared under the conditions shown in column 1 of Table 6 of Example 8, and a second sample was prepared under the conditions shown in column 2 of Table 6. The major component in both samples was LiMn ₂ O ₄ and the minor component phase was Mn ₃ O ₄ .

To manufacture batteries for beaker battery testing, lithium manganese oxide powder and conductive acetylene black powder (Chevron Corp. catalog no. 55)
) Were mixed at a ratio of 60:30. This powder mixture is ground with a mortar and pestle,
The powder was mixed thoroughly.

To this homogeneous powder mixture was added a few drops of a solution of polyvinylidene fluoride (PVDF). This 10 percent PVDF solution was prepared by dissolving PVDF (type 714, Elf Atochem North) dissolved in 1-methyl-2-pyrrolidinone (Aldrich Chemical Co., Milwaukee, Wis.).
America, Inc. , Philadelphia, PA).
_{Li X Mn Y O Z: AB} : final ratio of PVDF is 60: 30: 10. The resulting slurry was spread on a pre-weighed aluminum metal mesh. The mesh containing the slurry is placed in a vacuum oven for 1 hour to remove solvent and residual moisture.
Baking at 20 ° C. overnight. Immediately after removal from the oven, these electrodes were placed in a glove box (Vacuum Atmosphere) under an argon atmosphere.
Co. , Hawthorne, CA) and weighed again.

[0216] All discharge / charge experiments were performed in this glove box. When the concentrations of water and oxygen in this glove box were measured, they were 1 ppm or less and 1.5 ppm or less, respectively. These samples, as shown in FIG.
Tested in a three electrode configuration. In this test assembly, aluminum mesh 834 was used.
The upper cathode 832 was placed in the container 836. The container 836 contains a liquid electrolyte 838. The container 836 also contains a counter electrode 840 and a reference electrode 842. Lithium metal is used as both the counter electrode and the reference electrode. These electrodes are connected to a battery test system 844.

In the relative configuration of this test, the separators are not needed because the electrodes are physically separated. Alternatively, the liquid electrolyte can be regarded as a separator. The liquid electrolyte (from Merck & Co., Inc.) was a 1M LiClO ₄ solution in propylene carbonate.

The charge and discharge experiments were performed at a constant current approximately equal to about 5 mA / g-the oxide in the electrode. Each electrode contained approximately 10 mg of the nanoparticles. Thus, the current was about 0.05 mA. Assuming that the material is pure lithium manganese oxide, this charge / discharge rate corresponds to the rate of C / 30 (ie, the rate at which the cathode must be fully discharged in 30 hours). The cells were first charged to 4.4 volts from their open circuit voltage and then discharged to 2.0 volts.

[0219] This measurement was performed using Arbin Instruments, College Sta.
Arbin Battery Testing System from Tion, TX
em, Model BT4023. Record the charge / discharge curve,
And the specific capacity was determined. The specific capacity was evaluated as discharge capacity / mass of active material. The differential capacity (δx / δV) was obtained as a differential coefficient of the discharge capacity with respect to the voltage. Therefore, this differential capacity shows opposite slopes with respect to voltage in charging and discharging. The peak in the plot of differential capacity versus voltage indicates the voltage at which lithium enters the host material. For lithium metal batteries, the battery voltage is roughly proportional to the chemical potential of Li ^{+ in} the host material. Therefore, the differential capacity can be used to characterize and / or identify the material and its structure.

FIG. 52 shows the discharge curves of Samples 1 and 2 in comparison with those of commercially available bulk LiMn ₂ O ₄ . Lithium manganese oxide synthesized by laser pyrolysis
While having a significantly lower specific capacity, the nanoparticles have a much higher specific capacity. The differential capacities of the nanoparticles and bulk / commercial material shown in FIG. 53 show similar peak positions and shapes. This indicates that the electrochemically active phases of all three materials have approximately the same insertion behavior. Thus, the crystal structures of these three materials were the same. The lower specific capacity of the nanoparticles can be attributed to the electrochemically inactive phase in this test involving lithium not incorporated into manganese oxide and lithium manganese oxide.

[0221] The embodiments described above are intended to be illustrative, not limiting. Additional embodiments of the present invention are within the following claims. Although the present invention has been described by reference to preferred embodiments, those skilled in the art will appreciate that changes may be made in form and detail without departing from the spirit and scope of the invention. Would admit.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a solid precursor delivery device cut through a plane passing through the center of the device.

FIG. 2 is a schematic cross-sectional view of one embodiment of laser pyrolysis, the cross section being cut by a plane passing through the center of the laser radiation path. The upper inset is a bottom view of the collection nozzle, and the lower inset is a top view of the injection nozzle.

3 is a schematic side view of a reactant delivery device for delivering a gaseous reactant to the laser pyrolysis device of FIG.

FIG. 4A is a schematic side view of a reactant delivery device for delivering an aerosol reactant to the laser pyrolysis device of FIG. 2; FIG. 4B is a schematic side view of one alternative embodiment of a reactant delivery device for delivering an aerosol reactant to the laser pyrolysis device of FIG. FIG. 4C is a schematic side view of another alternative embodiment of a reactant delivery device for delivering an aerosol reactant to the laser pyrolysis device of FIG.

FIG. 5 is a schematic perspective view of an elongated reaction chamber for performing a laser pyrolysis apparatus, wherein the constituent materials of the reaction chamber are shown transparent to reveal the internal structure.

FIG. 6 is a perspective view of one embodiment of an elongated reaction chamber for performing a laser pyrolysis apparatus.

7 is a cut-away side view of the reaction chamber of FIG.

FIG. 8 is a partially cutaway front view of the reaction chamber of FIG. 6 taken along the line 8-8 in FIG. 6;

9 is a cut-away front view of a reactant delivery device for delivering an aerosol reactant to the reaction chamber of FIG. 6, with a cross-section cut through a plane passing through the center of the reactant delivery device.

FIG. 10 is an exploded cross-sectional front view of the top portion of the reactant delivery device of FIG.

FIG. 11 is a top view of a mount of the reactant delivery device of FIG. 9;

FIG. 12 is a top view of the cap of the aerosol delivery device of FIG. 9;

FIG. 13 is a cross-sectional view of the cap of FIG. 12 taken along the line 13-13.

14 is a cross-sectional side view of a spacer used in the aerosol delivery device of FIG. 9,
The cross section is cut by a plane passing through the center of the spacer.

FIG. 15 is a cross-sectional side view of a shim used in the aerosol delivery device of FIG. 9, the cross section being cut by a plane passing through the center of the wedge.

FIG. 16 is a cross-sectional side view of one embodiment of a brushing cap used in the aerosol delivery device of FIG. 9, with a cross-section cut through a plane passing through the center of the brushing cap.

FIG. 17 is a cross-sectional side view of one alternative embodiment of a brushing cap used in the aerosol delivery device of FIG. 9, with a cross-section cut through a plane passing through the center of the brushing cap.

FIG. 18 is a cross-sectional side view of a second alternative embodiment of a brushing cap used in the aerosol delivery device of FIG. 9, the cross section being cut by a plane passing through the center of the brushing cap.

FIG. 19 is a side view of an ultrasonic aerosol generator having an atomized surface.

20 is a cross-sectional side view of the ultrasonic aerosol generator of FIG. 19, the cross section of which is cut by a plane passing through the center of the device.

FIG. 21 is a schematic side view of a liquid supply device for supplying a liquid to the aerosol generator of FIGS. 19 and 20.

FIG. 22A is a schematic cross-sectional view of an apparatus for heat treating nanoparticles, the cross section being cut by a plane passing through the center of the apparatus. FIG. 22B is a schematic cross-sectional view of an oven for heat-treating the nanoparticles, the cross section being cut by a plane passing through the center of the quartz tube.

FIG. 23 is a schematic perspective view of the battery of the present invention.

FIG. 24 is an X-ray diffraction pattern of manganese oxide nanoparticles produced by laser pyrolysis using a gaseous reactant according to the parameters specified in column 1 of Table 1.

FIG. 25 is an X-ray diffractogram of manganese oxide nanoparticles produced by laser pyrolysis using a gaseous reactant according to the parameters specified in column 2 of Table 1.

FIG. 26 is an X-ray diffractogram of manganese oxide nanoparticles produced by laser pyrolysis using a gaseous reactant according to the parameters specified in column 3 of Table 1.

FIG. 27 is a transmission electron micrograph (micrograms) of manganese oxide nanoparticles produced by laser pyrolysis using a gaseous reactant according to the parameters specified in column 2 of Table 1.

FIG. 28 is a plot of the particle size distribution of the particles shown in the transmission electron microscopy micrograms shown in FIG. 27.

FIG. 29 is an X-ray diffractogram of manganese oxide nanoparticles produced by laser pyrolysis using an aerosol manganese precursor according to the parameters specified in Table 2.

FIG. 30 is a transmission electron microgram of manganese oxide nanoparticles produced by laser pyrolysis using an aerosol manganese precursor according to the parameters specified in Table 2.

31 is a plot of the particle size distribution of the particles shown in the transmission electron microscopy microgram of FIG. 30.

FIG. 32 is an X-ray diffraction diagram of manganese oxide nanoparticles after heat treatment of particles produced by laser pyrolysis, Sample 1 in Table 3.

FIG. 33 is an X-ray diffraction diagram of manganese oxide nanoparticles after heat treatment of particles produced by laser pyrolysis, Sample 2A of Table 3.

FIG. 34 is an X-ray diffraction diagram of manganese oxide nanoparticles after heat treatment of particles produced by laser pyrolysis, Sample 2B of Table 3.

FIG. 35 is an X-ray diffraction pattern of manganese oxide nanoparticles produced by laser pyrolysis using an aerosol reactant according to the parameters specified in column 1 of Table 4.

FIG. 36 is an X-ray diffraction diagram of manganese oxide nanoparticles produced by laser pyrolysis using an aerosol reactant according to the parameters specified in column 2 of Table 4.

FIG. 37 is an X-ray diffraction diagram of lithium manganese oxide nanoparticles produced by laser pyrolysis of a reactant stream using an aerosol.

FIG. 38 is an X-ray diffraction pattern of lithium manganese oxide nanoparticles produced by laser pyrolysis followed by heating in an oven.

FIG. 39 is a plot of three X-ray diffraction diagrams of three samples prepared by heat treatment of a mixture of nanocrystalline manganese oxide and lithium nitrate.

FIG. 40 is a transmission electron microscope microgram of manganese oxide nanoparticles used for further heating to lithium manganese oxide.

41 is a transmission electron microscope microgram of lithium manganese oxide nanoparticles of Sample 1. FIG.

FIG. 42 is an X-ray diffraction diagram of lithium manganese oxide particles directly produced by laser pyrolysis.

FIG. 43 is a transmission electron microscope microgram of lithium manganese oxide particles corresponding to the X-ray diffraction pattern of FIG. 42.

FIG. 44 is a plot of two X-ray diffractograms of a mixed phase material containing silver vanadium oxide nanoparticles directly produced by laser pyrolysis, each plot obtained with a material produced under slightly different conditions. Can be

FIG. 45A is a transmission electron micrograph of a material from a sample corresponding to the upper diffraction pattern of FIG. 44. FIG. 45B is a transmission electron microscope microgram of material from the sample corresponding to the diffractogram below FIG.

FIG. 46 is a plot of particle size distribution for the particles shown in the transmission electron microscopy microgram of FIG. 45.

FIG. 47 is a schematic perspective view of a two-electrode arrangement used in the examples.

FIG. 48 is a plot of battery voltage over a range of 4 volts for four different anode active materials.

FIG. 49 is a plot of battery voltage over a range of 3 volts for four different anode active materials.

FIG. 50 is a plot of capacity as a function of cycle number for eight different cells made with four different anode active materials.

FIG. 51 is a schematic perspective view of three types of electrode arrangements used in the following tests.

FIG. 52 is a plot of voltage as a function of specific capacity for two nanoscale samples and commercial lithium manganese oxide.

FIG. 53 is a plot of differential capacity for the sample used in FIG. 52.

──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number 09 / 203,414 (32) Priority date December 2, 1998 (1998.12.2) (33) Priority claim country United States (US) ( 31) Priority claim number 09 / 334,203 (32) Priority date June 16, 1999 (June 16, 1999) (33) Priority claim country United States (US) (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), CA, CN, JP, KR (72) Inventor Horn , Craig Earl, 94110, California, United States of America, Twenty-Street, San Francisco 3924 (72) Inventor Haliclear, Doris Reates 95050, California, United States of America Santa Clara, New Hall Street 2147, Number 212 (72) Inventor Gardner, James T. Tantau Avenue, Calif., 95501, California, USA 10251 (72) Inventor Mosso, Ronald Jay, 94439, Fremont, California, United States , Chaparral Drive 46553 (72) Inventor Kanbe, Nobuyuki 94025, Menlo Park, Hobart Street, Menlo Park 940F, California 840 F term (reference) 4G048 AA02 AA04 AB01 AB05 AC06 AD04 AD06 AE05 5H029 AJ03 AJ05 AK03 AL02 AL06 AM03 AM04 AM07 AM16 AM16 DJ16 DJ17 HJ02 HJ05 HJ13 HJ19 5H050 AA07 AA08 BA17 CA05 CA09 CB02 CB07 FA17 FA19 HA02 HA05 HA13 HA19

Claims (75)

[Claims] Claims: 1. An aggregate of particles comprising manganese oxide, wherein the aggregate of particles has an average particle size of about 500 nm or less;
Crystalline MnO, has a structure selected from the group consisting of crystalline Mn ₅ O ₈ and crystalline Mn ₂ O _3, aggregation of particles. 2. The aggregate of particles has an average particle size from about 5 nm to about 250 nm.
An aggregate of the particles according to claim 1. 3. The aggregate of particles has an average particle size of about 5 nm to about 100 nm.
An aggregate of the particles according to claim 1. 4. The collection of particles according to claim 1, wherein the collection of particles has an average particle size of about 5 nm to about 50 nm. 5. The aggregate of particles according to claim 1, wherein the particles comprise crystalline MnO. 6. The aggregate of particles according to claim 1, wherein the particles comprise crystalline crystalline Mn ₂ O ₃ . 7. The aggregate of particles according to claim 1, wherein the particles comprise crystalline Mn ₅ O ₈ . 8. The collection of particles according to claim 1, wherein the collection of particles is substantially free of particles having a diameter greater than about four times the average particle size of the collection of particles. 9. The aggregate of particles has a particle size distribution such that at least about 95 percent of the particles are greater than about 40 percent of the average particle size and less than about 160 percent of the average particle size. Item 2. An aggregate of the particles according to Item 1. 10. A method comprising reacting an aerosol in a reaction chamber to prepare metal oxide particles, wherein the aerosol comprises a metal precursor and the metal oxide particles have a particle size of about 500 nm. A method for producing a metal oxide powder having the following average particle size. 11. The method according to claim 10, wherein the metal oxide comprises manganese oxide. 12. The method according to claim 10, wherein the metal precursor comprises a compound selected from the group consisting of MnCl ₂ and MnNO ₃ . 13. The method according to claim 10, wherein the reaction is driven by heat absorbed from the laser beam. 14. The reaction chamber has a cross section along a direction perpendicular to the reaction stream,
The method of claim 10, wherein the cross-section has a dimension along a major axis that is greater than about twice the dimension along a minor axis. 15. The method of claim 10, wherein the aerosol is generated by an ultrasonic aerosol generator. 16. The method of claim 10, wherein the aerosol is generated by a mechanically atomized aerosol generator. 17. The method according to claim 10, wherein the reaction occurs in the presence of a source of oxygen. 18. A method for altering the stoichiometry of a manganese oxide particle assembly, comprising heating the manganese oxide particles in an oxidizing atmosphere at a temperature of about 600 ° C. or less. 19. The collection of particles according to claim 18, wherein the collection of manganese oxide particles has an average particle size of about 5 nm to about 500 nm. 20. A battery having a cathode comprising manganese oxide particles, wherein the manganese oxide particles have an average particle size of about 250 nm or less. 21. A method comprising reacting an aerosol to prepare a powder of composite metal oxide particles having an average particle size of less than about 1 micron,
A method for producing composite metal oxide particles, wherein the aerosol includes a first metal compound precursor and a second metal compound precursor. 22. The method of claim 21, wherein the composite metal oxide comprises lithiated manganese oxide. 23. The method of claim 21, wherein the composite metal oxide comprises lithiated vanadium oxide. 24. The method according to claim 21, wherein the metal precursor comprises a compound selected from the group consisting of MnCl ₂ and MnNO ₃ . 25. The method according to claim 21, wherein the metal precursor comprises a compound selected from the group consisting of LiCl and LiNO ₃ . 26. The method according to claim 21, wherein the metal precursor comprises VOCl ₂ . 27. The reaction according to claim 2, wherein the reaction is driven by heat absorbed from the light beam.
2. The method according to 1. 28. The method according to claim 27, wherein the laser beam is generated by an infrared laser. 29. The method of claim 21, wherein the precursor comprises a third metal precursor. 30. The method of claim 21, wherein the reaction occurs in the presence of a source of oxygen. 31. A method for producing a lithium metal oxide comprising pyrolyzing a reactant stream in a reaction chamber, the reactant stream comprising a lithium precursor, a non-lithium metal precursor, an oxidizing agent and an infrared absorber. A method comprising the agent, wherein the pyrolysis is driven by heat absorbed from the light beam. 32. The method of claim 31, wherein the reactant stream comprises an aerosol. 33. The method of claim 32, wherein the aerosol comprises a solution comprising a metal compound and a lithium compound. 34. The method of claim 33, wherein the metal compound comprises a manganese compound. 35. An aggregate of particles comprising lithium manganese oxide having an average particle size of about 250 nm or less, wherein at least about 95 percent of the particles have at least about 95 percent of the average particle size. An aggregate of particles having a particle size distribution such that the particles have a diameter greater than about 40 percent and less than about 160 percent of the average particle size. 36. The aggregate of particles has an average particle size from about 5 nm to about 25 nm.
An aggregate of particles according to claim 35. 37. The lithium manganese oxide is substantially LiMn ₂ O _x (where x ≧ 3.8
36. The aggregate of particles according to claim 35, having a stoichiometric composition of). 38. The lithium manganese oxide has a cubic spinel crystal structure.
An aggregate of particles according to claim 35. 39. The assembly of particles, wherein at least about 95 percent of the particles are:
36. The aggregate of particles according to claim 35, having a particle size distribution such that the particles have a diameter greater than about 60 percent of the average particle size and less than about 140 percent of the average particle size. 40. A method of producing lithium manganese oxide particles comprising heating a mixture of manganese monoxide (MnO) particles and a lithium compound, wherein the manganese monoxide (MnO) particles have an average particle size of about 250 nm or less. Having a particle size. 41. The method of claim 40, wherein the lithium compound comprises LiNO ₃ . 42. The method according to claim 40, wherein the heating is performed at a temperature of about 200 to about 600 ° C.
The method described in. 43. The method of claim 40, wherein the heating is performed under an atmosphere comprising O ₂ . 44. The method of claim 40, wherein the lithium manganese oxide has a cubic pinel crystal structure. 45. A method of producing lithium manganese oxide particles comprising heating a mixture of manganese oxide particles and a lithium compound, wherein the manganese oxide particles have an average particle size of about 250 nm or less; The method wherein the resulting lithium manganese oxide particles have a particle size distribution such that at least about 95 percent of the particles have a diameter greater than about 40 percent of the average particle size and less than about 160 percent of the average particle size. . 46. The method according to claim 45, wherein the heating is performed at a temperature of about 200 to about 500 ° C.
The method described in. 47. The method of claim 45, wherein the manganese compound comprises manganese oxide having manganese in the +2 to +4 oxidation state. 48. A battery comprising lithium manganese oxide particles, wherein the particles of lithium manganese oxide have an average particle size of about 250 nm or less, wherein at least about 95 percent of the particles have a mean particle size of about 40 nm. A battery having a particle size distribution such that it has a diameter greater than percent and less than about 160 percent of its average particle size. 49. The battery of claim 48, wherein the lithium manganese oxide particles have an average particle size of about 100 nm or less. 50. A battery comprising lithium manganese oxide having a 4 volt voltage curve having cycling stability within about 20 percent of its initial value after 25 cycles. 51. A battery comprising lithium manganese oxide, comprising: 120 mA
A battery having an initial capacity of at least h / g. 52. The battery according to claim 51, wherein the battery has an initial capacity of 125 mAh / g or more.
The battery according to 1. 53. An aggregate of particles comprising lithium manganese oxide, wherein the aggregate of particles has an average diameter of about 250 nm or less, and wherein the lithium manganese oxide comprises Li ₂ Mn ₄ O ₉ . 54. The aggregate of particles has a particle size distribution such that at least about 95 percent of the particles have a diameter greater than about 40 percent of the average particle size and less than about 160 percent of the average particle size. 54. An aggregate of particles according to claim 53 comprising 55. An aggregate of particles comprising lithium manganese oxide, wherein the aggregate of particles has an average diameter of about 250 nm or less, and wherein the lithium manganese oxide has an average diameter of 8 nm.
. A collection of particles having an on-axis lattice parameter of 23 Angstroms or less. 56. A process for producing crystalline ternary particles comprising reacting a reactant stream comprising a precursor containing three atoms of a product ternary particle, the method comprising reacting a reactant stream. The method wherein the relative amounts of the three atoms therein and the reaction conditions are selected to produce crystalline ternary particles. 57. The method of claim 56, wherein the crystalline ternary particles make up about 25 weight percent of the product particles. 58. The method of claim 56, wherein the crystalline ternary particles make up at least about 40 weight percent of the product particles. 59. The method of claim 56, wherein the crystalline ternary particles make up at least about 50 weight percent of the product particles. 60. The method of claim 56, wherein the crystalline ternary particles comprise a metal oxide comprising two metals. 61. The method of claim 60, wherein the metal oxide comprises a lithium metal oxide. 62. The method of claim 61, wherein the lithium metal oxide comprises lithium manganese oxide. 63. The method of claim 56, wherein the reactant stream comprises an aerosol. 64. The method of claim 63, wherein the aerosol comprises two metal species. 65. The method of claim 56, wherein the reactant stream comprises molecular oxygen. 66. A method of producing crystalline lithium manganese oxide particles comprising reacting a reactant stream comprising a manganese precursor and a lithium precursor, wherein the reaction is driven by energy from electromagnetic radiation. How. 67. The method of claim 66, wherein the reactant stream comprises an aerosol. 68. The method of claim 67, wherein the aerosol is directed with gas through an elongated inlet for delivery to the reaction chamber. 69. The reaction stream of claim 6, further comprising a radiation absorbing gas.
7. The method according to 6. 70. The method of claim 66, wherein the pyrolysis is performed with a carbon dioxide laser. 71. An aggregate of particles comprising a crystalline multi-component metal oxide having an average particle size of about 500 nm or less, wherein the lithium manganese oxide particles comprise at least about 95 percent of the particles. An aggregate of particles having a particle size distribution such that they have a diameter greater than about 40 percent of the average particle size and less than about 160 percent of the average particle size. 72. The aggregate of particles according to claim 71, wherein the aggregate of particles has an average particle size of about 100 nm or less. 73. The aggregate of particles has an average particle size of about 50 nm or less.
An aggregate of the particles according to 1. 74. The collection of particles according to claim 71, wherein the collection of particles is substantially free of particles having a diameter greater than about three times the average particle size of the collection of particles. 75. The aggregate of particles according to claim 71, wherein the aggregate of particles comprises at least about 40 weight percent of the crystalline ternary particles.