CN104332599A - Preparation method of lithium cobalt oxide solid solution precursor - Google Patents

Preparation method of lithium cobalt oxide solid solution precursor Download PDF

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CN104332599A
CN104332599A CN201410639430.8A CN201410639430A CN104332599A CN 104332599 A CN104332599 A CN 104332599A CN 201410639430 A CN201410639430 A CN 201410639430A CN 104332599 A CN104332599 A CN 104332599A
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lithium
cobalt
preparation
solid solution
oxides solid
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CN104332599B (en
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李永昌
李旭
王志兴
蒋湘康
唐泽勋
谭欣欣
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BASF Shanshan Battery Materials Co Ltd
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HUNAN SHANSHAN NEW MATERIAL CO Ltd
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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
    • 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
    • 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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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a preparation method of a lithium cobalt oxide solid solution precursor. The preparation method comprises the following steps: (1) weighing a cobalt source, a lithium source and an M source according to the ratio of CoyM1-yOz.xLiO1/2, respectively dissolving the raw materials into de-ionized water, and uniformly mixing obtained solutions; (2) adding a mixed salt solution into a mixed solution of oleic acid, octadecene and ethylene glycol, and reacting for 1-48 hours while keeping heating and agitating; and (3) after stopping the reaction, carrying out suction filtering under an air atmosphere and collecting reaction sediment, and sintering at a temperature of 100-700 DEG C for 1-48 hours to obtain the product. The preparation method is simple in preparation process and generated grains have controllable size and appearance; all elements in crystal grains are uniformly distributed and the structure of crystals is stable; the stability of the structure of the prepared product is improved when lithium ions are embedded and released at a high-voltage region; and a lithium cobaltate material prepared from the precursor has excellent circulating performance and safety performance.

Description

A kind of preparation method of lithium and cobalt oxides solid solution presoma
Technical field
The present invention relates to a kind of preparation method of lithium and cobalt oxides solid solution presoma.
Background technology
In recent years, people deepen continuously for the positive electrode research of the lithium ion batteries such as cobalt oxidate for lithium, nickel oxidate for lithium, manganese oxidate for lithium, achieve many achievements, but due to cobalt acid lithium, to have operating voltage high, and there is good cycle performance and security performance, and be easy to the series of advantages such as preparation, still causing the extensive concern of people, is one of current business-like main lithium battery product.
The traditional production method of cobalt acid lithium adopts the presoma containing cobalt and the presoma containing lithium after physical mixed, then obtain through long high-temperature calcination.The cobalt acid lithium that this kind of method is prepared exists that uneven components, sintering temperature are high, product reaction not exclusively, a series of shortcoming such as sintering time is long, crystal structure is unstable, finally can produce certain impact to the cycle performance of product and security performance.
But the requirement of portable set is constantly improved along with people, the energy density of lithium ion battery material and security performance are had higher requirement, need to improve the preparation technology of cobalt acid lithium and presoma, common process is all carried out mixing, sintering preparation by the presoma of the presoma of cobalt and lithium, but the sample that this technique is prepared easily cause local lithium content too high or disappearance, at high voltage region Lithium-ion embeding with when deviating from, the structural stability of material is deteriorated, finally affects the cycle performance of material.
Summary of the invention
The technical problem to be solved in the present invention is, overcome the deficiencies in the prior art, provide the preparation method of a kind of preparation method simple lithium and cobalt oxides solid solution presoma, gained precursor power becomes battery, Lithium-ion embeding in high voltage region is with when deviating from, and structural stability is better.
The technical scheme that the present invention solves the employing of its technical problem is that a kind of preparation method of lithium and cobalt oxides solid solution presoma, comprises the following steps:
(1) according to proportioning Co ym 1-yo zxLiO 1/2take cobalt source, lithium source, M source, and be dissolved in respectively in deionized water, be mixed with the solution that concentration is 0.1-1mol/L, gained solution mixed, obtains mixing salt solution;
The general formula Co of described lithium and cobalt oxides solid solution presoma ym 1-yo zxLiO 1/2in, M is alkaline earth ion, is Ni, Mn, Al, Ti, Zr, Mg, V, Nb, Sb, Y, Yb, Ln(lanthanide series) one or more, 0.5≤y≤1,0.8≤x≤1.2, z is the adjustment factor of oxygen atom, relevant with sintering temperature, sintering temperature is higher, and z is larger, 1≤z≤1.5;
(2) step (1) gained mixing salt solution is joined in the mixed liquor of oleic acid, octadecylene, ethylene glycol, in described mixed liquor, the mass ratio of oleic acid, octadecylene, ethylene glycol is the preferred 2:1:2 of 2:0.5-1.5:1-3(), and keep heating and stir, computer heating control temperature is 80-160 DEG C (preferred 140-160 DEG C), mixing speed is the preferred 300r/min of 250-350 r/min(), reaction time is the preferred 10-24h of 1-48h(), the form of the precipitation that reaction system generates is lithium cobalt oleate;
(3) after stopping reaction, suction filtration under the atmosphere of air, collect reaction precipitation thing, then sinter at 100-700 DEG C of (preferably 400 DEG C-600 DEG C) temperature, sintering time is the preferred 22-24h of 1-48h(), obtain lithium and cobalt oxides solid solution presoma.
Further, in step (1), described lithium source can be one or more of the carbonate of lithium, hydroxide, acetate, oxalates, oxide, fluoride, chloride, nitrate or sulfate.Cobalt source can be one or more of cobalt nitrate, cobalt acetate, cobalt chloride, cobalt carbonate, cobalt hydroxide, cobalt oxide or hydroxy cobalt oxide.M source can be one or more of the oxide of M, chloride or nitrate.
The present invention, using oleic acid as surfactant, adopts organic solvent ethylene glycol and octadecylene to form uniform solution, adopts the synthesis of thermal cracking synthetic method.
The domain size distribution of gained lithium and cobalt oxides solid solution presoma of the present invention is 100nm-25 μm (100 nanometer-25 microns), and pattern is spherical loose structure.
Preparation technology of the present invention is simple, the particle size, the morphology controllable that generate, various elements in crystal grain are uniformly distributed, crystal structure is stablized, particularly prepare in production process at cobalt acid lithium, effectively can simplify and production technology, the Lithium-ion embeding of product in high voltage region and the stability of structure when deviating from prepared can be improved, use the cobalt of this precursor power acid lithium material to have excellent cycle performance and security performance.
Accompanying drawing explanation
Fig. 1 is gained lithium and cobalt oxides solid solution presoma CoO in the embodiment of the present invention 1 4/3liO 1/2electronic scanning Electronic Speculum (SEM) photo, multiplication factor is 1000 times;
Fig. 2 is CoO in the embodiment of the present invention 1 4/3liO 1/2the cyclic curve of the battery be assembled into as positive electrode after oversintering, wherein: charge-discharge magnification is 0.5C, charging/discharging voltage is 3.0-4.6V.
Fig. 3 is Co in the embodiment of the present invention 2 0.95y 0.01al 0.04oLiO 1/2the curve of double curvature of the battery be assembled into as positive electrode after oversintering, wherein: rate of charge is 0.2C, and discharge-rate the 1 to 2 week is 0.2C, the 3rd week is 0.5C, and the 4th week is 1C, and the 5th week is 2C, and the 6th week is 5C; Charging/discharging voltage is 3.0-4.5V;
Fig. 4 is Co in the embodiment of the present invention 3 0.96mg 0.02ti 0.02o 1.20.9LiO 1/2the battery be assembled into as positive electrode after oversintering cyclic curve, wherein: charge-discharge magnification is 1C, charging/discharging voltage is 3.0-4.5V.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
The present embodiment comprises the following steps:
(1) according to proportioning CoO 4/3liO 1/2take cobalt chloride, lithium nitrate, and be dissolved in respectively in deionized water, it is the lithium nitrate solution of 1mol/L, the cobalt chloride solution of 1mol/L that concentration is made in acid, is mixed by gained solution, obtains mixing salt solution;
(2) step (1) gained mixing salt solution is joined in the mixed liquor of oleic acid, octadecylene, ethylene glycol, in described mixed liquor, the mass ratio of oleic acid, octadecylene, ethylene glycol is 2:1:2, and keep heating and stir, computer heating control temperature is 160 DEG C, mixing speed is 300r/min, reaction time is 24h, and the form of the precipitation that reaction system generates is lithium cobalt oleate;
(3), after stopping reaction, suction filtration under the atmosphere of air, collect reaction precipitation thing, then sinter at the temperature of 500 DEG C, sintering time is 15h, obtains lithium and cobalt oxides solid solution presoma CoO 4/3liO 1/2.
The present embodiment gained lithium and cobalt oxides solid solution presoma CoO 4/3liO 1/2middle particle diameter is 15.6 microns.
Product in the present embodiment is obtained positive active material through 950 DEG C of high temperature sintering 10h, positive electrode active materials, PVDF and acetylene black is pressed the mass ratio mixing of 94:3:3, add NMP, stir and make slurry.Slurry is coated on aluminium foil, dry at 120 DEG C, make positive plate; Using metal lithium sheet as negative plate; Barrier film is the polypropylene microporous barrier (Celgard 2400) of import; Electrolyte is 1mol/L LiPF6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1:1), is assembled into CR2032 experimental button cell in glove box.The charge-discharge performance test of battery is at room temperature carried out, the mode of first constant current constant voltage is again adopted to charge, charge cutoff voltage is 4.6V, adopt constant-current discharge, cut-ff voltage is 3.0V, charging and discharging currents density be 0.5C multiplying power (contrast sample is that technique traditionally prepares presoma cobaltosic oxide, and and lithium carbonate mix, adopting and use the same method sintering and prepare battery).
Accompanying drawing 1 is CoO 4/3liO 1/2electronic scanning Electronic Speculum (SEM) picture.
Fig. 2 is CoO in the present embodiment 4/3liO 1/2the cyclic curve of the battery be assembled into as positive electrode after oversintering, wherein: charge-discharge magnification is 0.5C, charging/discharging voltage is 3.0-4.6V.
Embodiment 2
The present embodiment comprises the following steps:
(1) according to proportioning Co 0.95y 0.01al 0.04oLiO 1/2take lithium chloride, cobalt acetate, aluminum nitrate, yttrium nitrate, and be dissolved in respectively in deionized water, be mixed with the lithium chloride solution of 1mol/L, the cobalt acetate solution of 1mol/L, the aluminum nitrate solution of 0.1mol/L, the yttrium nitrate solution of 0.1mol/L, gained solution is mixed, obtains mixing salt solution;
(2) step (1) gained mixing salt solution is joined in the mixed liquor of oleic acid, octadecylene, ethylene glycol, in described mixed liquor, the mass ratio of oleic acid, octadecylene, ethylene glycol is 2:1:3, and keep heating and stir, computer heating control temperature is 100 DEG C, mixing speed is 320r/min, reaction time is 5h, and the form of the precipitation that reaction system generates is lithium cobalt oleate;
(3), after stopping reaction, suction filtration under the atmosphere of air, collect reaction precipitation thing, then sinter at the temperature of 300 DEG C, sintering time is 2h, obtains lithium and cobalt oxides solid solution presoma.
The present embodiment gained lithium and cobalt oxides solid solution presoma Co 0.95y 0.01al 0.04oLiO 1/2middle particle diameter is 0.35 micron, spherical porous structure.
Product in the present embodiment is obtained positive active material through 850 DEG C of high temperature sintering 10h, positive electrode active materials, PVDF and acetylene black is pressed the mass ratio mixing of 94:3:3, add NMP, stir and make slurry.Slurry is coated on aluminium foil, dry at 120 DEG C, make positive plate; Using metal lithium sheet as negative plate; Barrier film is the polypropylene microporous barrier (Celgard 2400) of import; Electrolyte is 1mol/L LiPF6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1:1), is assembled into CR2032 experimental button cell in glove box.The charge-discharge performance test of battery is at room temperature carried out, and adopt the mode of first constant current constant voltage again to charge, charge cutoff voltage is 4.5V, and adopt constant-current discharge, cut-ff voltage is 3.0V, and the density of charging current is 0.2C multiplying power.(contrast sample is that technique traditionally prepares presoma cobaltosic oxide, and and lithium carbonate, aluminum nitrate, yttrium nitrate mix, adopting and use the same method sintering and prepare battery)
Fig. 3 is Co in the present embodiment 0.95y 0.01al 0.04oLiO 1/2the cyclic curve of the battery be assembled into as positive electrode after oversintering, wherein: rate of charge is 0.2C, and discharge-rate the 1 to 2 week is 0.2C, the 3rd week is 0.5C, and the 4th week is 1C, and the 5th week is 2C, and the 6th week is 5C.Charging/discharging voltage is 3.0-4.5V.
Embodiment 3
The present embodiment comprises the following steps:
(1) according to proportioning Co 0.96mg 0.02ti 0.02o 1.20.9LiO 1/2take lithium nitrate, cobalt nitrate, magnesium chloride, Titanium Nitrate, and be dissolved in respectively in deionized water, be configured to the lithium nitrate solution of 1mol/L, the cobalt nitrate solution of 1mol/L, the magnesium chloride solution of 0.1mol/L, the Titanium Nitrate solution of 0.1mol/L, gained solution is mixed, obtains mixing salt solution;
(2) step (1) gained mixing salt solution is joined in the mixed liquor of oleic acid, octadecylene, ethylene glycol, in described mixed liquor, the mass ratio of oleic acid, octadecylene, ethylene glycol is 2:0.8:1.5, and keep heating and stir, control temperature is 160 DEG C, mixing speed is 300r/min, reaction time is 24h, and the form of the precipitation that reaction system generates is lithium cobalt oleate;
(3), after stopping reaction, suction filtration under the atmosphere of air, collect reaction precipitation thing, then sinter at the temperature of 500 DEG C DEG C, sintering time is 7h, obtains lithium and cobalt oxides solid solution presoma.
The present embodiment gained lithium and cobalt oxides solid solution presoma Co 0.96mg 0.02ti 0.02o 1.20.9LiO 1/2middle particle diameter is 9.2 microns, spherical porous structure.
Product in the present embodiment is obtained positive active material through 900 DEG C of high temperature sintering 10h, positive electrode active materials, PVDF and acetylene black is pressed the mass ratio mixing of 94:3:3, add NMP, stir and make slurry.Slurry is coated on aluminium foil, dry at 120 DEG C, make positive plate; Using metal lithium sheet as negative plate; Barrier film is the polypropylene microporous barrier (Celgard 2400) of import; Electrolyte is 1mol/L LiPF6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1:1), is assembled into CR2032 experimental button cell in glove box.The charge-discharge performance test of battery is at room temperature carried out, and adopt the mode of first constant current constant voltage again to charge, charge cutoff voltage is 4.5V, adopt constant-current discharge, cut-ff voltage is 3.0V, and the density of charging current is 1C multiplying power, and first charge-discharge efficiency and specific discharge capacity are 93.8% and 188.8mAh/g.(contrast sample is that technique traditionally prepares presoma cobaltosic oxide, and and lithium carbonate, magnesium chloride, Titanium Nitrate mix, adopting and use the same method sintering and prepare battery).
Fig. 4 is Co in the present embodiment 0.96mg 0.02ti 0.02o 1.20.9LiO 1/2the cyclic curve of the battery be assembled into as positive electrode after oversintering, wherein: charge-discharge magnification is 1C, charging/discharging voltage is 3.0-4.5V.
Embodiment 4
The present embodiment comprises the following steps:
(1) according to proportioning Co 0.94zr 0.01yb 0.01ni 0.04o 4/31.1LiO 1/2take lithium nitrate, cobalt chloride, nickel nitrate, zirconium nitrate, ytterbium nitrate, and be dissolved in respectively in deionized water, be configured to the lithium nitrate solution of 1mol/L, the cobalt chloride solution of 1mol/L, the nickel nitrate solution of 0.1mol/L, the ytterbium nitrate solution of 0.1mol/L, the zirconium nitrate solution of 0.1mol/L, gained solution is mixed, obtains mixing salt solution;
(2) step (1) gained mixing salt solution is joined in the mixed liquor of oleic acid, octadecylene, ethylene glycol, in described mixed liquor, the mass ratio of oleic acid, octadecylene, ethylene glycol is 2:1:1, and keep heating and stir, computer heating control temperature is 160 DEG C, mixing speed is 300r/min, reaction time is 24h, and the form of the precipitation that reaction system generates is lithium cobalt oleate;
(3), after stopping reaction, suction filtration under the atmosphere of air, collect reaction precipitation thing, then sinter at the temperature of 600 DEG C, sintering time is 24h, obtains lithium and cobalt oxides solid solution presoma Co 0.94zr 0.01yb 0.01ni 0.04o 4/31.1LiO 1/2.
The present embodiment gained lithium and cobalt oxides solid solution presoma Co 0.94zr 0.01yb 0.01ni 0.04o 4/31.1LiO 1/2co, Zr, Y, Ni, Li in crystal grain are uniformly distributed, and middle particle diameter is 11.62 microns.
Product in the present embodiment is obtained positive active material through 900 DEG C of high temperature sintering 10h, be assembled into 063048 type rectangular cell, table 1 is that active material, PVDF and the conductive black mass ratio by 95.5:2.3:2.2 (mixes, adds NMP, stir and make slurry by battery testing data.Slurry is coated on aluminium foil, dry at 120 DEG C, make positive plate; 063048 type battery is assembled into negative plate, barrier film, electrolyte etc.The charge-discharge performance test of battery is at room temperature carried out, and adopt the mode of first constant current constant voltage again to charge, charge cutoff voltage is 4.35V, and adopt constant-current discharge, cut-ff voltage is 3.0V, and the density of charging current is 0.5C multiplying power.Contrast sample is that technique traditionally prepares presoma cobaltosic oxide, and and lithium carbonate, nickel nitrate, zirconium nitrate, ytterbium nitrate mix, adopting the preparation of use the same method sintering and battery.In table, the detection method of hot case test preserves 0.5h under the high temperature of 150 DEG C, battery explosion or on fire, is NG, otherwise is then Pass.The detection method overcharging test is charged to 5V with the charging current of 1A, battery tympanites on fire or blast be then NG, otherwise be Pass.）
The full battery performance test data of products obtained therefrom in table 1 embodiment 4

Claims (10)

1. a preparation method for lithium and cobalt oxides solid solution presoma, is characterized in that, comprises the following steps:
(1) according to proportioning Co ym 1-yo zxLiO 1/2take cobalt source, lithium source, M source, and be dissolved in respectively in deionized water, be mixed with the solution that concentration is 0.1-1mol/L, gained solution mixed, obtains mixing salt solution;
The general formula Co of described lithium and cobalt oxides solid solution presoma ym 1-yo zxLiO 1/2in, M is alkaline earth ion, is one or more of Ni, Mn, Al, Ti, Zr, Mg, V, Nb, Sb, Y, Yb, Ln, 0.5≤y≤1,0.8≤x≤1.2,1≤z≤1.5;
(2) step (1) gained mixing salt solution is joined in the mixed liquor of oleic acid, octadecylene, ethylene glycol, in described mixed liquor, the mass ratio of oleic acid, octadecylene, ethylene glycol is 2:0.5-1.5:1-3, and keep heating and stir, computer heating control temperature is 80-160 DEG C, mixing speed is 250-350 r/min, reaction time is 1-48h, and the form of the precipitation that reaction system generates is lithium cobalt oleate;
(3), after stopping reaction, suction filtration under the atmosphere of air, collect reaction precipitation thing, then sinter at 100-700 DEG C of temperature, sintering time is 1-48h, obtains lithium and cobalt oxides solid solution presoma.
2. the preparation method of lithium and cobalt oxides solid solution presoma according to claim 1, is characterized in that, in step (2), in described mixed liquor, the mass ratio of oleic acid, octadecylene, ethylene glycol is 2:1:2.
3. the preparation method of lithium and cobalt oxides solid solution presoma according to claim 1 and 2, is characterized in that, in step (2), control heating-up temperature is 140-160 DEG C.
4. the preparation method of lithium and cobalt oxides solid solution presoma according to claim 1 and 2, is characterized in that, in step (2), control mixing speed is 300r/min.
5. the preparation method of lithium and cobalt oxides solid solution presoma according to claim 1 and 2, is characterized in that, in step (2), the control reaction time is 10-24h.
6. the preparation method of lithium and cobalt oxides solid solution presoma according to claim 1 and 2, is characterized in that, in step (3), sintering temperature is 400 DEG C-600 DEG C.
7. the preparation method of lithium and cobalt oxides solid solution presoma according to claim 1 and 2, is characterized in that, in step (3), sintering time is 22-24h.
8. the preparation method of lithium and cobalt oxides solid solution presoma according to claim 1 and 2, it is characterized in that, in step (1), described lithium source is one or more of the carbonate of lithium, hydroxide, acetate, oxalates, oxide, fluoride, chloride, nitrate or sulfate.
9. the preparation method of lithium and cobalt oxides solid solution presoma according to claim 1 and 2, it is characterized in that, in step (1), cobalt source is one or more of cobalt nitrate, cobalt acetate, cobalt chloride, cobalt carbonate, cobalt hydroxide, cobalt oxide or hydroxy cobalt oxide.
10. the preparation method of lithium and cobalt oxides solid solution presoma according to claim 1 and 2, is characterized in that, in step (1), M source is one or more of the oxide of M, chloride or nitrate.
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CN105047906A (en) * 2015-08-21 2015-11-11 湖南杉杉新材料有限公司 Lithium-cobalt composite oxide cathode material and preparation method thereof
CN107863526A (en) * 2017-10-23 2018-03-30 兰州金川新材料科技股份有限公司 A kind of preparation method for adulterating cobalt acid lithium
CN107863525A (en) * 2017-10-23 2018-03-30 兰州金川新材料科技股份有限公司 A kind of preparation method of grade doping cobalt acid lithium

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CN101770868A (en) * 2009-01-06 2010-07-07 中国科学院化学研究所 Compound of metal/metal oxide and preparation method and application thereof
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Publication number Priority date Publication date Assignee Title
CN1763997A (en) * 2004-10-21 2006-04-26 北京化工大学 Cobalt acid lithium battery material adulterated alkaline-earth metal between layers and its preparing method
CN101770868A (en) * 2009-01-06 2010-07-07 中国科学院化学研究所 Compound of metal/metal oxide and preparation method and application thereof
CN101659447A (en) * 2009-09-27 2010-03-03 武汉理工大学 Method for synthesizing manganese oxide nano-particles in one step
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Publication number Priority date Publication date Assignee Title
CN105047906A (en) * 2015-08-21 2015-11-11 湖南杉杉新材料有限公司 Lithium-cobalt composite oxide cathode material and preparation method thereof
CN105047906B (en) * 2015-08-21 2018-04-03 湖南杉杉能源科技股份有限公司 Lithium cobalt positive polar material and preparation method thereof
CN107863526A (en) * 2017-10-23 2018-03-30 兰州金川新材料科技股份有限公司 A kind of preparation method for adulterating cobalt acid lithium
CN107863525A (en) * 2017-10-23 2018-03-30 兰州金川新材料科技股份有限公司 A kind of preparation method of grade doping cobalt acid lithium

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