CN1545158A - Method for preparing positive electrode material LiNi0.5Mn0.5O2 of lithium ion battery - Google Patents
Method for preparing positive electrode material LiNi0.5Mn0.5O2 of lithium ion battery Download PDFInfo
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- CN1545158A CN1545158A CNA2003101088420A CN200310108842A CN1545158A CN 1545158 A CN1545158 A CN 1545158A CN A2003101088420 A CNA2003101088420 A CN A2003101088420A CN 200310108842 A CN200310108842 A CN 200310108842A CN 1545158 A CN1545158 A CN 1545158A
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- manganese
- lithium
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- nickel
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a method of preparing high-performance layered positive material LiNi0.5Mn0.5O2 of a Li ion cell. It is a template agent method and its steps as follows: first, respectively dissolve Ni, Mn and Li compounds in alcohol or water, then add in propylene alcohol/ polypropylene/polyethylene ether surface active agent as template agent, heat and evaporate the solvent, grind and then burn at 300-400 deg.C for 3-4 hours and then at 500-1000deg.C for 6-48 hours. The material has the advantages of large specific capacity, stable circulating performance, and low cost, an optimum replacer for positive material LiCoO2 and the method has simple steps, convenient operation, and low production cost, suitable for industrial production.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of high performance anode material for lithium-ion batteries LiNi
0.5Mn
0.5O
2The preparation method.The material of preparation has specific capacity height, superior, the low cost and other advantages of cycle performance.
Background technology
Lithium ion battery is a high-energy-density chemical power source of new generation.Since throwing in market, be widely used in mobile phone, portable electric appts, military equipment power supply and grapefruit satellite power supply, also be the first-selected supporting power supply of electric bicycle and electric automobile simultaneously.At present, the positive electrode of lithium ion battery is mainly LiCoO on the market
2, its specific capacity can reach 140mAh/g, but its price higher, certain environmental pollution arranged.From development, need a kind of inexpensive, performance better material replacement LiCoO
2Become inevitable trend.Stratiform LiNi
1/2Mn
1/2O
2Since specific capacity height, good cycle, the low new direction that has become the anode material for lithium-ion batteries development of cost.People [J.Electrochem.Soc., 145,1113-1121 (1998)] such as Michael E.Spahr adopt the LiNi of the method preparation of bromine water oxidation and coprecipitation
1/2Mn
1/2O
2Cycle performance is poor, seriously polluted.People such as T.Ohzuku [Chemistry Letters, 744 (2001)] utilize nickel, manganese hydroxide and the lithium hydroxide bought to mix, need be 1000 ℃ high-temperature calcination.People such as Z.Lu [Electrochem.Solid State Lett.4, A191 (2001)] and people [Electrochem.Commun.4 such as J.-S.Kim, 205-209 (2002)] the first co-precipitation hydroxide of preparation nickel, manganese, mix the stratiform LiNi of 900 ℃ of calcinings preparation in 3 hours then with lithium hydroxide
1/2Mn
1/2O
2Specific capacity is low, and at the operation interval of 2.5-4.3V, specific capacity only is about 125mAh/g.
Summary of the invention
The objective of the invention is to propose that a kind of preparation process is simple, easy to operate, production cost is low, be fit to the anode material for lithium-ion batteries LiNi of suitability for industrialized production
0.5Mn
0.5O
2The preparation method, with shortcoming that overcomes existing preparation method and the chemical property that improves material.
The preparation method of the anode material for lithium-ion batteries that the present invention proposes adopts template agent method, and concrete steps are as follows:
(1) with nickel compound, manganese compound and and lithium compound be dissolved in alcohol or the water;
(2) adding propylene glycol polypropylene-polyethylene ethers surfactant in step (1) is template, and heating boils off solvent;
(3) product that step (2) is obtained grinds, and after 300-400 ℃ of temperature lower calcination 3-4 hour, again at 500-1000 ℃ of temperature lower calcination 6-48 hour, behind the cool to room temperature, grinds, and sieving with 300 order sub-sieves promptly gets product.
Among the present invention, the nickel compound described in the step (1) can be in nickel acetate, nickelous carbonate, nickel chloride, six water nickel chlorides, two water nickel formates, six water nickel nitrates, nickelous sulfate, nickel sulfate hexahydrate, the seven water nickelous sulfates any.
Among the present invention, the manganese compound described in the step (1) can be in manganese acetate, four water acetic acid manganese, manganese carbonate, manganous chloride, four water manganous chloride, manganese tetrachloride, six water manganese nitrates, manganese sulfate, manganese sulfate monohydrate, sulfate dihydrate manganese, three water manganese sulfates, four water manganese sulfates, Manganese sulfate pentahydrate, six water manganese sulfates, the seven water manganese sulfates any.
Among the present invention, the lithium compound described in the step (1) can be in lithium chloride, lithium carbonate, lithium acetate, lithium nitrate, nitrate trihydrate lithium, lithium sulfate, sulfuric acid monohydrate lithium, the Lithium hydroxide monohydrate any.
Among the present invention, the alcohol described in the step (1) can be methyl alcohol, ethanol, propyl alcohol, butanols, 1,2-propylene glycol, 2, ammediol, 2,3-butanediol, isopropyl alcohol, any in the isobutanol.
Among the present invention, the template described in the step (2) can be propylene glycol polypropylene-polyethylene ethers surfactant.
Among the present invention, the template described in the step (2) can be triblock copolymer (P (EO)-P (PO)-P (EO)).
Among the present invention, in the molecular weight of the template described in the step (2) between 1000-30000.
The material LiNi of the present invention's preparation
0.5Mn
0.5O
2Be layer structure.
The high performance lithium ion battery anode material LiNi that the present invention proposes
0.5Mn
0.5O
2The preparation method following distinguishing feature is arranged:
(1) stratiform LiNi
0.5Mn
0.5O
2Superior performance, at the 2.5-4.3V operation interval, specific capacity is up to more than the 150mAh/g and good cycle.
(2) preparation process is simple, easy to operate, and production cost is low, is fit to suitability for industrialized production.
Description of drawings
Fig. 1 is the stratiform LiNi that utilizes the template agent method preparation that the present invention introduces
1/2Mn
1/2O
2X-ray diffractogram of powder.
Fig. 2 is the stratiform LiNi that utilizes the template agent method preparation that the present invention introduces
1/2Mn
1/2O
2X-ray diffractogram of powder.
Fig. 3 is the stratiform LiNi that utilizes the template agent method preparation that the present invention introduces
1/2Mn
1/2O
2Be assembled into the first charge-discharge curve of 2025 type button cells with lithium metal.
Embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1:
At first nickel chloride, manganous chloride, the lithium chloride with stoichiometric proportion is dissolved in methyl alcohol, heat then toward wherein adding template P123, boil off solvent, grind, after 300-400 ℃ of temperature lower calcination 3-4 hour,, be cooled to take out after the room temperature and grind at last in 700 ℃ of calcinings 12 hours, cross 300 order sub-sieves, can make stratiform LiNi
1/2Mn
1/2O
2, its X-ray powder diffraction pattern is seen Fig. 1.
Embodiment 2:
At first nickel acetate, four water acetic acid manganese, the lithium acetate with stoichiometric proportion is dissolved in ethanol, heat then toward wherein adding template P123, boil off solvent, grind, at 400 ℃ of temperature lower calcinations after 4 hours,, be cooled to take out after the room temperature and grind at last in 850 ℃ of calcinings 24 hours, cross 300 order sub-sieves, can make stratiform LiNi
1/2Mn
1/2O
2, its X-ray powder diffraction pattern is seen Fig. 2.
Embodiment 3:
At first that nickel nitrate, manganese nitrate, the nitrate trihydrate lithium of stoichiometric proportion is water-soluble, heat then toward wherein adding template P123, boil off solvent, grind, at 300 ℃ of temperature lower calcinations after 3 hours,, be cooled to take out after the room temperature and grind at last in 950 ℃ of calcinings 6 hours, cross 300 order sub-sieves, can make stratiform LiNi
1/2Mn
1/2O
2, its charging and discharging curve is seen Fig. 3.
Claims (8)
1, a kind of anode material for lithium-ion batteries LiNi
0.5Mn
0.5O
2The preparation method, it is characterized in that adopting template agent method, concrete steps are as follows:
(1) with nickel compound, manganese compound and and lithium compound be dissolved in alcohol or the water;
(2) adding propylene glycol polypropylene-polyethylene ethers surfactant in step (1) is template, and heating boils off solvent;
(3) product that step (2) is obtained grinds, and after 300-400 ℃ of temperature lower calcination 3-4 hour, again at 500-1000 ℃ of temperature lower calcination 6-48 hour, behind the cool to room temperature, grinds, and sieving with 300 order sub-sieves promptly gets product.
2, preparation method according to claim 1 is characterized in that the nickel compound described in the step (1) is any in nickel acetate, nickelous carbonate, nickel chloride, six water nickel chlorides, two water nickel formates, six water nickel nitrates, nickelous sulfate, nickel sulfate hexahydrate, the seven water nickelous sulfates.
3, preparation method according to claim 1 is characterized in that the manganese compound described in the step (1) is any in manganese acetate, four water acetic acid manganese, manganese carbonate, manganous chloride, four water manganous chloride, manganese tetrachloride, six water manganese nitrates, manganese sulfate, manganese sulfate monohydrate, sulfate dihydrate manganese, three water manganese sulfates, four water manganese sulfates, Manganese sulfate pentahydrate, six water manganese sulfates, the seven water manganese sulfates.
4, preparation method according to claim 1 is characterized in that the lithium compound described in the step (1) is any in lithium chloride, lithium carbonate, lithium acetate, lithium nitrate, nitrate trihydrate lithium, lithium sulfate, sulfuric acid monohydrate lithium, the Lithium hydroxide monohydrate.
5, preparation method according to claim 1 is characterized in that the alcohol described in the step (1) is methyl alcohol, ethanol, propyl alcohol, butanols, 1,2-propylene glycol, 2, ammediol, 2,3-butanediol, isopropyl alcohol, any in the isobutanol.
6, preparation method according to claim 1 is characterized in that the template described in the step (2) is a propylene glycol polypropylene-polyethylene ethers surfactant.
7, preparation method according to claim 1 is characterized in that the template described in the step (2) is triblock copolymer (P (EO)-P (PO)-P (EO)).
8, preparation method according to claim 1, the molecular weight that it is characterized in that the template described in the step (2) is between 1000-30000.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2003101088420A CN1545158A (en) | 2003-11-25 | 2003-11-25 | Method for preparing positive electrode material LiNi0.5Mn0.5O2 of lithium ion battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2003101088420A CN1545158A (en) | 2003-11-25 | 2003-11-25 | Method for preparing positive electrode material LiNi0.5Mn0.5O2 of lithium ion battery |
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|---|---|
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100459238C (en) * | 2005-11-16 | 2009-02-04 | 比亚迪股份有限公司 | Preparing method of anode material of lithium cobalt, nickel, manganese, oxygen lithium ion battery |
| CN102386381A (en) * | 2010-08-30 | 2012-03-21 | 机械科学研究总院先进制造技术研究中心 | Preparation method of nano positive material for lithium ion battery |
| US8153301B2 (en) | 2008-07-21 | 2012-04-10 | 3M Innovative Properties Company | Cathode compositions for lithium-ion electrochemical cells |
| CN103904315A (en) * | 2012-12-24 | 2014-07-02 | 天津工业大学 | Solid solution material containing nickel manganese and preparation method thereof |
| CN106784783A (en) * | 2015-11-19 | 2017-05-31 | 荆门市格林美新材料有限公司 | The method of synthesizing lithium ion battery nickel cobalt manganese anode material |
-
2003
- 2003-11-25 CN CNA2003101088420A patent/CN1545158A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100459238C (en) * | 2005-11-16 | 2009-02-04 | 比亚迪股份有限公司 | Preparing method of anode material of lithium cobalt, nickel, manganese, oxygen lithium ion battery |
| US8153301B2 (en) | 2008-07-21 | 2012-04-10 | 3M Innovative Properties Company | Cathode compositions for lithium-ion electrochemical cells |
| CN102386381A (en) * | 2010-08-30 | 2012-03-21 | 机械科学研究总院先进制造技术研究中心 | Preparation method of nano positive material for lithium ion battery |
| CN102386381B (en) * | 2010-08-30 | 2014-01-15 | 机械科学研究总院先进制造技术研究中心 | Preparation method of nano positive material for lithium ion battery |
| CN103904315A (en) * | 2012-12-24 | 2014-07-02 | 天津工业大学 | Solid solution material containing nickel manganese and preparation method thereof |
| CN106784783A (en) * | 2015-11-19 | 2017-05-31 | 荆门市格林美新材料有限公司 | The method of synthesizing lithium ion battery nickel cobalt manganese anode material |
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