JP2001052758A - Battery having ion conductive vitreous layer and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the production of a dendroid crystal and degradation in conjunction with it when metal lithium is used as an active material and thereby provide a battery having an improved clone rate by providing at least one of a first electrode and a second electrode with a collector having a surface and a vitreous layer associated with the surface of the collector. SOLUTION: This battery 50 comprises a first electrode 52, a second electrode 54, an electrolyte 56 and a vitreous layer 58. A transition metal, an alkaline metal or the like can be used for a metal collector, and the electrolyte 56 is formed of a salt of LiPF6 or the like dissolved in a solvent of propylene carbonate or the like. Preferably, the first electrode provided with a collector having a surface is manufactured, the vitreous layer is associated with the surface of the collector, the second electrode having a surface is manufactured, and at least one kind of electrolyte is associated with the first and second electrodes. Preferably, the vitreous layer contains an inorganic acid salt of lithium, and lithium polysilicate, and the battery has a channel capable of passing lithium ions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a battery, and more particularly, to a battery having a vitreous layer associated with a current collector surface, preventing direct contact between an electrode and an electrolyte, and suppressing dendrite formation. The present invention relates to a battery having improved coulomb efficiency.
The present invention further relates to a method for manufacturing the battery.

[0002]

2. Description of the Related Art Lithium-based batteries are known. Further, experimental research related to a lithium-based battery having an intercalation-type electrode has been conducted. While research related to batteries using intercalable electrodes is widespread, there are still significant problems with energy density and battery voltage. For this reason, lithium metal is reversibly plated directly on the current collector and then re-dissolved (stri) while substantially preventing dendrite formation and associated degradation at the electrode interface.
Pping methods have been studied.

It is preferable to use lithium metal as an active material because a battery having a higher energy density can be obtained as compared with a conventional active material. During operation of such batteries, the deposition and dissolution of metallic lithium on the current collector instead of the lithium intercalation / deintercalation and / or alloying / dealloying actions in conventional battery cycles. Happens. Further, the voltage characteristics of the battery using the metal lithium active material are better than the voltage characteristics of the battery using the intercalation type electrode.
However, to date, no such effective method has yet been found.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a lithium battery which has substantially improved prevention of dendritic crystal formation and accompanying degradation when lithium metal is used as an active material, and which has improved coulombic efficiency. To provide.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, by using a specific layer related to the current collector surface, direct contact between the electrode and the electrolyte has been achieved. And found that the above issues could be solved,
The present invention has been completed.

The present invention has been completed based on the above findings, and a first gist thereof is a battery having an electrolyte, a first electrode and a second electrode, wherein the first electrode and the second electrode are provided. At least one of the electrodes includes a current collector having a surface and a vitreous layer associated with the surface of the current collector.

A second aspect of the present invention resides in the battery according to the first aspect, wherein the vitreous layer contains an inorganic acid salt of lithium.

[0008] A third aspect of the present invention resides in the battery according to the first or second aspect, wherein the vitreous layer contains lithium polysilicate.

A fourth aspect of the present invention is a step of manufacturing a first electrode having a current collector having a surface; a step of associating a vitreous layer with the surface of the current collector; and a second step having a surface. A method of manufacturing a battery, comprising: a step of manufacturing an electrode; and a step of associating at least one electrolyte with the first and second electrodes.

According to a fifth aspect of the present invention, there is provided a semiconductor device having a first electrode and a second electrode, and at least one electrolyte associated with the first electrode and the second electrode, wherein at least one of the electrodes is made of glass. An electrolyte process in a battery including a current collector having a surface associated with a vitreous layer, wherein the battery is charged (CHARGE); and at least one ion on the current collector surface associated with the vitreous layer. And a step of substantially uniformly depositing

A sixth gist of the present invention is that the vitreous layer has first to fourth channels having channels through which lithium ions can flow.
The battery according to any one of the above aspects.

A seventh aspect of the present invention is a lithium secondary battery having an electrolyte, a first electrode and a second electrode, wherein at least one of the first electrode and the second electrode is
There is provided a lithium secondary battery comprising a current collector and a porous layer provided on the current collector and having a channel through which lithium ions can flow.

An eighth aspect of the present invention resides in the lithium secondary battery according to the seventh aspect, wherein the porous layer contains an inorganic acid salt of lithium.

A ninth aspect of the present invention resides in the lithium secondary battery according to the seventh or eighth aspect, wherein the porous layer contains lithium polysilicate.

According to a tenth aspect of the present invention, there is provided an electrolyte having a first electrode and a second electrode, wherein at least one of the first electrode and the second electrode is provided on a current collector and on the current collector. A method for charging and discharging a battery having a porous layer having a channel through which lithium ions can flow, comprising performing charging and discharging by depositing and dissolving lithium on the surface of the current collector. It lies in the characteristic charge / discharge method.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the drawings. The present invention is not limited to the embodiments and descriptions illustrated below, as the invention is capable of various embodiments.

FIG. 1 is a schematic view of a conventional battery before initial charging. The conventional battery 10 before the initial charge usually has the first electrode 12, the second electrode 14, and the electrolyte 16. Conventionally, the first electrode 12 is made of a transition metal such as copper,
4 is conventionally formed from a transition metal oxide. Electrolyte 1
6 may contain an organic solvent (not shown) such as propylene carbonate (PC) or ethylene carbonate (EC).

FIG. 2 is a schematic view of a conventional battery after charging. The conventional battery 10 after the charge / discharge cycle normally has the first
An electrode 12, a second electrode 14, an electrolyte 16 and a dendritic crystal product 18 are included. As will be described in more detail below, dendritic crystal formation reduces the Coulomb efficiency of the battery and shortens the battery life. Further, although not shown, the solvent in the electrolyte of the battery chemically reacts with the electrode surface and generates gas upon subsequent decomposition, which not only renders the battery inoperable but also dangerous.

FIG. 3 is a schematic view of a battery according to the present invention. The battery 50 according to the present invention before the initial charge generally has a first electrode 52, a second electrode 54, an electrolyte 56, and a vitreous layer (porous layer) 58. One of the electrodes 52 and 54 includes a metal current collector. As the metal current collector, a transition metal, an alkali metal, an alkaline metal, a transition metal oxide or other metal species can be used, and among them, copper is preferable.

As the electrolyte 56, commercially available or conventionally used solvents and salts or electrochemical systems (such as liquid, polymer, gel and plastic systems) can be used. Typically, propylene carbonate (PC) or ethylene carbonate (PC) is used. EC) LiPF ₆ or Li dissolved in a conventional solvent such as
Consists conventional salts AsF ₆ or the like.

A vitreous layer 58 is associated by being formed on the current collector surface 60 of the first electrode 52. Any of the conventional techniques such as spraying, roll coating, or application of a vitreous material onto a current collector may be used as the method for associating.

The vitreous layer 58 is 1) stably present with lithium; 2) capable of controlled ion (especially Li ²⁺ ) transfer from and to the electrode; and 3) conventional battery additives. There is no particular limitation as long as it is a vitreous material having compatibility.
Such glassy materials include, for example, inorganic salts of metals, especially lithium, such as aluminates, borates and silicates. Above all, it is preferable to be made of lithium polysilicate glass. In the following examples, a vitreous layer made of lithium polysilicate glass is used, but this specific compound is merely an example and is not limited to this.

The lithium polysilicate used for the glassy layer (porous layer) 58 is generally sold in the form of an aqueous solution, and its composition is generally X ₁ SiO ₂ + Y ₁ Li ₂ O
(Where X ₁ and Y ₁ represent the molar ratio of the composition of SiO ₂ and Li ₂ O). In the present invention, usually X
₁ / Y ₁ is usually 0.1 to 50, preferably 0.2 to 3
0, more preferably about 0.5 to 20. Also,
The lithium polysilicate can also be represented by the general formula Li _x Si _y O _{z, in} which case x is preferably 1 or more, y is 2 or more, z is 1 or more, and y
Is 1 or less. Commercially available lithium polysilicates include a composition Li ₂ Si ₅ O ₁₁ manufactured by DuPont.
There is something shown by. The content of lithium polysilicate in the glassy layer (porous layer) is usually at least 10% by weight, preferably at least 20% by weight, more preferably at least 40% by weight.
% By weight or more, most preferably 50% by weight or more.

The vitreous layer may further contain a conductive substance. Examples of such a conductive substance include carbon black, graphite, metal powder, and a conductive polymer. It may also contain an inert filler such as glass or fumed silica.
The content of these conductive substances and inert fillers is usually 70% by weight or less, preferably 50% by weight, based on the entire vitreous material.
% By weight, more preferably 40% by weight or less, most preferably 30% by weight or less.

The vitreous layer can contain various additives as required.

The vitreous layer can be usually formed by applying a paint containing the above-mentioned components on a current collector and then drying. As the solvent used in the paint, various inorganic and organic solvents can be used in addition to water.

The average thickness of the vitreous layer is generally 0.1 μm or more, since the thicker the area in which lithium can be deposited, the more difficult it is to deposit and dissolve uniformly.
Preferably 0.5 μm or more, more preferably 1.0 μm
m or more, most preferably 1.5 μm or more,
Usually 200 μm or less, preferably 150 μm or less, more preferably 100 μm or less, most preferably 50 μm
It is as follows.

By associating the vitreous layer 58 with the metal current collector surface 60 of the electrode 52, the battery 50 can be charged and discharged multiple times without the formation of dendrites near the current collector.

FIG. 4 is a partial schematic view of a battery according to the present invention. The glassy layer (porous layer) 58 is substantially porous and has a very large number of channels 57. The channel 57 accommodates, for example, lithium ions,
In one stage of charging and discharging of the battery, lithium ions are circulated through the electrolyte 56 toward the current collector of the electrode 52.
Although not shown, lithium may be partially deposited on the inner wall of the channel 57. By this deposition on the inner wall, the total surface area that can be deposited can be effectively increased. In addition, the channel 57 directs the region of lithium deposition under control over the current collector, resulting in a current collector having a substantially uniform deposition surface. Such uniform deposition minimizes the formation of dendritic crystals in the battery and improves Coulomb efficiency compared to batteries without a vitreous layer.

While lithium ions are transported through the channels of the vitreous layer to the current collector surface, the ions pass through a substantially unobstructed path without deposition, thus minimizing dendrite formation. can do. Further, the porous discontinuity of the surface of the vitreous layer minimizes electrode degradation. The reason for this is that ions can be plated directly on the current collector without being present outside the channel of the vitreous layer, for example below it. If ions are present below the vitreous layer, the vitreous layer separates from the current collector during battery cycling and accelerates degradation.

FIG. 5 shows a flow chart of the manufacturing method according to the invention and the actual electrolyte process that takes place in the battery during the initial charging. This process includes the following steps.
First, the electrodes 52 and 54 are manufactured. For example, the electrode 52
Can be formed as an anode having a current collector, and the electrode 54 can be formed as a cathode. In another battery configuration,
Depending on whether the battery is in charge or discharge,
The anode and cathode are interchangeable. Batteries 52 and 54 can be formed by conventional methods.

Next, a vitreous layer 58 is associated with the current collector surface by forming it on the current collector of the electrode 52. The vitreous layer 58 can be associated with the surface of the current collector, for example, by spraying, rolling, dipping, or coating. In addition, the vitreous layer 58 is formed by the second
It may be associated with the current collector of the electrode 54.

Next, the electrolyte 56 is applied to the electrodes 52 and 54.
Associated with each of the The electrolyte 56 is PC or EC
And a salt such as LiAsF ₆ dissolved in at least one solvent such as The electrolyte can be manufactured using conventional methods and can be associated with an electrode.

Next, the battery is charged (CHARGE). By providing the vitreous layer 58, the vitreous layer 5
8. The permeation of the solvent in the electrolyte through 8 is substantially prevented,
Chemical interaction between the metal current collector surface and the solvent is substantially prevented, while controlled transfer of ions (such as Li ⁺ ) toward and away from the current collector through the vitreous layer is possible. Become. As described above, the vitreous layer 58 substantially suppresses the formation of dendritic crystals near the surface of the first electrode 52. Further, a battery using such a vitreous layer has substantially improved electrochemical performance.

As a result of the charging, lithium ions passing through the channel are deposited as lithium on the surface of the current collector and possibly in the channel.

On the other hand, in the discharging process, lithium deposited on the surface of the current collector and, in some cases, in the channel is dissolved (stripped), so that lithium ions pass through the channel and move to the other electrode.

The above description is merely illustrative, and the present invention
Various modifications and changes can be made without departing from the gist of the invention. Hereinafter, as an example of the above change, a configuration of a lithium ion battery preferably used as a battery will be described.

A lithium ion battery usually comprises first and second electrodes corresponding to a positive electrode and a negative electrode, and an electrolyte layer interposed therebetween. The first electrode and the second electrode can be formed by binding an active material over a current collector.

Current collector: The material of the current collector can be appropriately selected from the various materials described above depending on the active material used. Preferably, aluminum is used as the current collector of the positive electrode, and copper is used as the current collector of the negative electrode.

The thickness of the current collector is appropriately selected, but is preferably 1 to 30 μm, more preferably 1 to 20 μm. If it is too thin, the mechanical strength tends to be weak, which is a problem in production. If it is too thick, the capacity of the battery as a whole decreases.

It is preferable that the surface of the current collector is previously subjected to a surface roughening treatment, since the adhesive strength of the electrode material is increased. Examples of the surface roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method. Examples of the mechanical polishing method include a method of polishing the surface of the current collector with a polishing cloth paper having abrasive particles fixed thereon, a grindstone, an emery buff, a wire brush provided with a steel wire, or the like. Further, an intermediate layer may be formed on the surface of the current collector to increase the adhesive strength and the conductivity.

The shape of the current collector may be a plate shape other than the metal mesh.

Active material: The active material used for the first electrode or the second electrode may be appropriately selected according to the type and characteristics of the battery to be manufactured. In the present invention, as described above, at least one of the first electrode and the second electrode is provided with a vitreous layer or a porous layer on a current collector, and deposits and dissolves lithium at least on the current collector surface. I do. The electrode provided with the vitreous layer or the porous layer may be used as a positive electrode or a negative electrode, but is preferably used as a negative electrode.

When an electrode provided with a vitreous layer or a porous layer is used as the first electrode, the active material used for the second electrode may be an inorganic compound or an organic compound as long as it can function as a battery. Can be used. As an inorganic compound,
Transition metal oxide, LiNiO ₂ , LiCoO ₂ , Li
Examples thereof include complex oxides of lithium and a transition metal such as Mn ₂ O ₄ , and chalcogen compounds such as a transition metal sulfide. Here, Fe, Co, Ni, Mn, or the like is used as the transition metal. Specifically, MnO, V ₂ O ₅ , V ₆ O ₁₃ , TiO ₂
And transition metal sulfides such as TiS ₂ , FeS, MoS _2, and the like, and transition metal oxides such as, for example, lithium nickelate, lithium cobaltate, and lithium manganate. These compounds may be partially substituted with elements in order to improve their properties. Further, carbonaceous particles such as graphite and coke can also be used. Such carbon-based materials are metals,
It can also be used in the form of a mixture or coating with a metal salt, an oxide or the like. Furthermore, oxides and sulfates of silicon, tin, zinc, manganese, iron, nickel, etc., metallic lithium,
Lithium alloys such as Li-Al, Li-Bi-Cd, and Li-Sn-Cd, lithium transition metal nitrides, and silicon can also be used. Examples of the organic compound include polyaniline, polypyrrole, polyacene, disulfide compounds, polysulfide compounds, and the like. Of course, a plurality of these can be used in combination. Preferably, it is a composite oxide of lithium and a transition metal, particularly a composite oxide of lithium and at least one transition metal selected from the group consisting of cobalt, nickel and manganese.

The particle size of the active material may be appropriately selected depending on the balance with other components of the battery.
The thickness is preferably from 30 to 30 μm, particularly from 1 to 10 μm, since battery characteristics such as initial efficiency and cycle characteristics are improved.

Other Structure of Electrode: It is preferable to use a binder in order to bind the active material on the current collector. As the binder, inorganic compounds such as silicate and glass, and various resins mainly composed of polymers can be used.

Examples of the resin include alkane-based polymers such as polyethylene, polypropylene and poly-1,1-dimethylethylene; unsaturated polymers such as polybutadiene and polyisoprene; polystyrene, polymethylstyrene, polyvinylpyridine and poly-N -Polymers having a ring such as vinylpyrrolidone; acrylic polymers such as polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polyacrylic acid, polymethacrylic acid and polyacrylamide Fluorinated resins such as polyvinyl fluoride, polyvinylidene fluoride (PVDF), and polytetrafluoroethylene; CN group-containing polymers such as polyacrylonitrile and polyvinylidene cyanide; polyvinyl acetate, polyvinyl Polyvinyl alcohol polymers, such as alcohol; polyvinyl chloride, halogen-containing polymers such as polyvinylidene chloride; and conductive polymers such as polyaniline can be used. Further, a mixture of the above-mentioned polymers and the like, a modified product, a derivative, a random copolymer, an alternating copolymer, a graft copolymer, a block copolymer and the like can also be used.

The amount of the binder to be added to 100 parts by weight of the active material is preferably 0.1 to 30 parts by weight, more preferably 1 to 15 parts by weight. If the amount of the resin is too small, the strength of the electrode may decrease. If the amount of the resin is too large, the capacity may decrease, or the late characteristics may decrease.

The electrode may contain additives, such as conductive materials and reinforcing materials, exhibiting various functions such as reinforcing materials, powders, fillers, and the like, if necessary. The conductive material is not particularly limited as long as it can impart conductivity by mixing an appropriate amount with the active material, but usually, acetylene black, carbon black, carbon powder such as graphite, and various metal fibers,
Foil and the like. As additives, trifluoropropylene carbonate, vinylene carbonate, 1,6-
Dioxaspiro [4,4] nonane-2,7
-Dione, 12-crown-4-ether and the like can be used to increase the stability and life of the battery. As the reinforcing material, various inorganic or organic spherical or fibrous fillers can be used.

As a method of forming an electrode on a current collector,
For example, a method in which a powdery active material is mixed with a solvent together with a binder, and if necessary, a ball mill, a sand mill, a twin-screw kneader or the like is used to form a dispersion paint, and then applied on a current collector and dried. Done. In this case, the type of the solvent used is not particularly limited as long as it is inert to the electrode material and can dissolve the binder. For example, any of commonly used inorganic and organic solvents such as N-methylpyrrolidone can be used. Can also be used.

Further, the electrode material layer can be formed by a method in which the active material is mixed with a binder and heated and then softened by pressing or spraying on the current collector. Furthermore, it can be formed by firing the active material alone on the current collector.

The thickness of the active material layer is usually at least 1 μm, preferably at least 10 μm. In addition, usually 200
μm or less, preferably 150 μm or less. If it is too thin, it becomes difficult to ensure uniformity of the active material layer, and the capacity tends to decrease. On the other hand, if the thickness is too large, the rate characteristics tend to decrease.

A primer layer can be provided between the current collecting substrate and the active material layer. As a result, the adhesiveness between the current collecting substrate and the active material layer can be further improved. The primer layer is a paint containing a conductive material, a binder and a solvent,
It can be formed by drying after coating on the current collecting substrate.

As the conductive material used for the primer layer, various materials such as carbonaceous particles such as carbon black and graphite, metal powders, and conductive polymers can be used. The same binder and solvent as those used for the active material layer can be used for the primer layer. The thickness of the primer layer is usually 0.05 μm or more, preferably 0.1 μm or more, and usually 20 μm or less, preferably 10 μm or less. If it is too thin, it tends to be difficult to ensure uniformity of the primer layer. If the thickness is too large, the capacity rate characteristics of the battery tend to decrease.

Electrolyte: The electrolyte interacts with the first and second electrodes and participates in ion transfer between the electrodes. The electrolyte usually exists as an electrolyte layer between the electrodes and also exists in the active material layer, and comes into contact with at least a part of the surface of the active material. The electrolyte can be related to the electrode or the electrode active material by being brought into contact with the first electrode or the second electrode by a method such as coating.

The electrolyte generally includes various electrolytes such as an electrolyte having fluidity and a non-fluid electrolyte such as a gel electrolyte and a completely solid electrolyte. An electrolyte or a gel electrolyte is preferable in terms of battery characteristics, and a non-fluid electrolyte is preferable in terms of safety. In particular, when a non-fluid electrolyte is used, liquid leakage can be more effectively prevented for a battery using a conventional electrolyte.

The electrolytic solution used as the electrolyte is usually obtained by dissolving a supporting electrolyte in a non-aqueous solvent.

As the supporting electrolyte, any non-aqueous substance which is stable to the positive electrode and the negative electrode as an electrolyte and which can cause lithium ions to move to perform an electrochemical reaction with the positive electrode active material or the negative electrode active material can be used. Can also be used. Specifically, the LiAsF
₆ , LiBF ₄ , LiPF ₆ , LiSbF ₆ , LiCl
O ₄ , LiI, LiBr, LiCl, LiAlCl, L
Lithium salts such as iHF ₂ , LiSCN, and LiSO ₃ CF ₂ are mentioned. Of these, LiPF ₆ , Li
ClO ₄ is preferred.

When these supporting electrolytes are used in the state of being dissolved in a non-aqueous solvent, the concentration is usually 0.5 to 3 mol / mol.
L, preferably 0.5 to 2.5 mol / L.

As the solvent, a solvent having a relatively high dielectric constant is preferably used. Specifically, cyclic carbonates including ethylene carbonate and propylene carbonate, acyclic carbonates such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, glymes such as tetrahydrofuran, 2-methyltetrahydrofuran and dimethoxyethane, and γ- Lactones such as butyrolactone, sulfur compounds such as sulfolane,
Examples thereof include nitriles such as acetonitrile. Also, one or a mixture of two or more of these can be used. Of these, especially ethylene carbonate,
One or more solvents selected from cyclic carbonates such as propylene carbonate, and non-cyclic carbonates such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate are preferred. In addition, those in which a part of hydrogen atoms in these molecules are substituted with halogen or the like can also be used. Other preferred solvents include cyclic carbonates, especially propylene carbonate.

The gel electrolyte that can be used as the electrolyte is
Usually, the above electrolyte is held by a polymer. In other words, the gel electrolyte is one in which the electrolyte is usually held in a polymer network and the fluidity as a whole is significantly reduced. Such a gel electrolyte exhibits properties such as ionic conductivity that are close to those of a normal electrolyte solution, but fluidity, volatility and the like are significantly suppressed, and safety is enhanced. The ratio of the polymer in the gel electrolyte is preferably 1 to
50% by weight. If the temperature is too low, the electrolyte cannot be held, and a liquid leak may occur. If it is too high, the ionic conductivity tends to decrease and battery characteristics tend to deteriorate.

As the polymer used for the gel electrolyte,
There is no particular limitation as long as it is a polymer that can form a gel together with the electrolytic solution, and polyester, polyamide, polycarbonate, those produced by polycondensation such as polyimide,
Polyurethane, polyurea, etc. produced by polyaddition, acrylic derivative polymers such as polymethyl methacrylate, and polyadditions produced by polyvinyl polymerization such as polyvinyl acetate, polyvinyl chloride, polyvinylidene fluoride, etc. and so on. Preferred polymers include polyacrylonitrile and polyvinylidene fluoride. Here, the polyvinylidene fluoride includes not only a homopolymer of vinylidene fluoride but also a copolymer with another monomer component such as hexafluoropropylene. Also, acrylic acid, methyl acrylate,
Ethyl acrylate, ethoxyethyl acrylate, methoxyethyl acrylate, ethoxyethoxyethyl acrylate, polyethylene glycol monoacrylate,
Ethoxyethyl methacrylate, methoxyethyl methacrylate, ethoxyethoxyethyl methacrylate, polyethylene glycol monomethacrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate, allyl acrylate, acrylonitrile, N-vinylpyrrolidone, diethylene glycol di Acrylic derivative obtained by polymerizing monomers such as acrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate. system Rimmer can also be preferably used.

The weight average molecular weight of the above polymer is usually 10
000 to 5,000,000. If the molecular weight is low, it is difficult to form a gel. If the molecular weight is high, the viscosity becomes too high and handling becomes difficult. The concentration of the polymer in the electrolytic solution may be appropriately selected according to the molecular weight, but is preferably from 0.1% by weight to 30% by weight. If the concentration is too low, it is difficult to form a gel, the retention of the electrolytic solution is reduced, and problems of flow and liquid leakage may occur. If the concentration is too high, the viscosity becomes too high, which causes difficulties in the process, and the proportion of the electrolytic solution is reduced, the ionic conductivity is reduced, and the battery characteristics such as rate characteristics may be reduced.

A completely solid electrolyte can be used as the electrolyte. As such a solid electrolyte, various solid electrolytes known so far can be used. For example, it can be formed by mixing the polymer used in the gel electrolyte and the supporting electrolyte salt at an appropriate ratio. In this case, in order to increase the conductivity, it is preferable to use a polymer having a high polarity and to have a skeleton having many side chains.

[0065]

The battery having a glassy layer associated with the current collector surface of the present invention has an improved coulombic efficiency to prevent direct contact between the electrode and the electrolyte and to suppress the formation of dendritic crystals. Therefore, the industrial value of the present invention is high.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a conventional battery before initial charging.

FIG. 2 is a schematic diagram of a conventional battery after initial charging.

FIG. 3 is a schematic view of a battery according to the present invention.

FIG. 4 is a partial schematic view of a battery according to the present invention.

FIG. 5 is a flowchart of a manufacturing method and an electrolyte process according to the present invention.

[Explanation of symbols]

 10: conventional battery before initial charge 12: first electrode 14: second electrode 16: electrolyte 18: dendritic crystal product 50: battery according to the present invention before initial charge application 52: first electrode 54: second Electrode 56: Electrolyte 58: Vitreous layer 60: Current collector surface 57: Channel

Claims (10)

[Claims] 1. A battery having an electrolyte, a first electrode and a second electrode, wherein at least one of the first electrode and the second electrode has a surface and a surface of the current collector. And a vitreous layer associated therewith. 2. The battery according to claim 1, wherein the vitreous layer contains an inorganic acid salt of lithium. 3. The battery according to claim 1, wherein the vitreous layer contains lithium polysilicate. Manufacturing a first electrode having a current collector having a surface; associating a vitreous layer with the surface of the current collector; manufacturing a second electrode having a surface;
Associating at least one electrolyte with the first and second electrodes. 5. A semiconductor device comprising: a first electrode and a second electrode; and at least one electrolyte associated with the first and second electrodes, wherein at least one of the electrodes has a surface associated with a vitreous layer. An electrolyte process in a battery comprising a current collector comprising: charging the battery (CHARGE); substantially uniformly depositing at least one ion on the current collector surface associated with the vitreous layer. An electrolyte process. 6. The battery according to claim 1, wherein the vitreous layer has a channel through which lithium ions can flow. 7. A lithium secondary battery having an electrolyte, a first electrode and a second electrode, wherein at least one of the first electrode and the second electrode is provided on a current collector and on the current collector. And a porous layer having a channel through which lithium ions can flow. 8. The lithium secondary battery according to claim 7, wherein the porous layer contains an inorganic acid salt of lithium. 9. The lithium secondary battery according to claim 7, wherein the porous layer contains lithium polysilicate. 10. An electrolyte, a first electrode, and a second electrode, wherein at least one of the first electrode and the second electrode is provided on the current collector and is capable of flowing lithium ions. And charging and discharging the battery by depositing and dissolving lithium on the surface of the current collector.