CN108682849A - A kind of preparation method for mixing aluminium cobalt acid lithium - Google Patents
A kind of preparation method for mixing aluminium cobalt acid lithium Download PDFInfo
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- CN108682849A CN108682849A CN201810490923.8A CN201810490923A CN108682849A CN 108682849 A CN108682849 A CN 108682849A CN 201810490923 A CN201810490923 A CN 201810490923A CN 108682849 A CN108682849 A CN 108682849A
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
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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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- 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
Abstract
The invention discloses a kind of preparation methods for mixing aluminium cobalt acid lithium, belong to technical field of lithium ion.For this method using certain density cobalt and lithium mixed solution as cobalt, lithium source, sodium carbonate liquor is precipitating reagent, and ammonia spirit is complexing agent, and hydrazine hydrate solution is reducing agent, and aluminium salt ethanol solution is dopant, goes out cobalt carbonate and carbonic acid lithium mixture using Moist chemical synthesis.During the reaction, participation reaction in reaction kettle is added in doped solution by disperseing liquid feeding mode；After synthesis under the conditions of certain pH value, cobalt carbonate is oxidized to hydroxy cobalt oxide using certain density hydrogen peroxide solution, then mixture is washed, is dry, is calcined under certain condition, obtains mixing aluminium cobalt acid lithium product, production efficiency is high；And the aluminium cobalt acid lithium product of mixing for using that the method for the present invention prepares mixes aluminum amount for 0.2 0.4%, and aluminium element is uniformly distributed, laser particle size is 5 15 μm, Zhen Shi Mi Du≤2.0g/cm3, 0.2 0.6m of specific surface area2/ g, in blocky or spherical pattern.
Description
Technical field
It is specifically a kind of to mix aluminium cobalt for anode material for lithium-ion batteries the invention belongs to technical field of lithium ion
The preparation method of sour lithium.
Background technology
Cobalt acid lithium is the main positive electrode in current commercial Li-ion battery.But cobalt acid lithium actual specific capacity only has
140mAh/g or so, only its theoretical capacity（274mAh/g）50% or so；And the anti-over-charging performance of cobalt acid lithium is poor, compared with
Specific capacity reduces rapidly under high charge voltage.Research has shown that, is improving anode material for lithium-ion batteries performance, especially cyclicity
Energy aspect, doping is one of most efficient method, can not only improve the stability of ionic lattice, but also can increase substantially
The cycle performance of material.
Chinese invention patent（200710065340.2）Disclose a kind of " super large grain size and high-density lithium cobalt oxide and its preparation
Method ", specifically will be by cobalt compound, lithium compound, or is mixed simultaneously with a small amount of doping element compound, high temperature sintering 3-
30h forms block sintered product, obtains cobalt acid lithium powder body material using crushing and classification, this method production technology need to be through length
The batch mixing of time and sintering, low production efficiency, high energy consumption.Chinese invention patent（201210011485.5）Disclose that " one kind is mixed
The preparation process of the spherical lithium cobalt of miscellaneous Ti, Mg, Al ", specifically by cobalt salt mixed solution and ammonium bicarbonate soln precipitation reaction,
Spherical cobaltous carbonate obtains cobaltosic oxide after primary roasting, cobaltosic oxide with lithium source through after baking obtain doping Ti, Mg,
The problem of Al spherical lithium cobalts, that there is also roasting times is long for the production method, high energy consumption.
In view of the above technical problems, the Chinese invention patent of 107863526 A of Publication No. CN discloses a kind of " doping
The preparation method of cobalt acid lithium ", this method goes out the sediment of doped chemical by Moist chemical synthesis, then cobalt hydroxide is oxidized to hydroxyl
Cobalt oxide obtains doping cobalt acid lithium product finally by calcining.But this method is in the preparation for mixing aluminium cobalt acid lithium, aluminium salt
Fast with alkaline reaction speed, there are aluminium and lithium, cobalt to precipitate non-uniform problem.In addition, the compound of cobalt is very easy to oxidation, oxygen
Cobalt compound after change can interfere the fast-growth of synthetic product, and therefore, there is also the relatively low problems of production efficiency for this method.
Invention content
The purpose of the invention is to overcome the shortcomings of above-mentioned prior art, provide that a kind of production efficiency is high, product quality
The good preparation method for mixing aluminium cobalt acid lithium.
The purpose of the present invention is what is be achieved through the following technical solutions：Using certain density cobalt and lithium mixed solution as cobalt,
Lithium source, sodium carbonate liquor are precipitating reagent, and ammonia spirit is complexing agent, and hydrazine hydrate solution is reducing agent, aluminium salt ethanol solution
For dopant, Moist chemical synthesis goes out cobalt carbonate and carbonic acid lithium mixture under certain condition.During the reaction, by disperseing liquid feeding
Doped solution is added in reaction kettle and participates in reacting by mode；After synthesis under the conditions of certain pH value, utilization is certain density
Cobalt carbonate is oxidized to hydroxy cobalt oxide by hydrogen peroxide solution, then washs mixture, is dry, calcining under certain condition, obtaining
To mixing aluminium cobalt acid lithium product.Specifically include following steps：
A, the preparation of solution
Using cobalt salt, lithium salts as raw material, it is 1 to keep lithium, cobalt molar ratio:1.1-1.4 is configured to cobalt, lithium concentration is 1-2mol/L
Lithium cobalt mixed solution be solution A；The sodium carbonate liquor that compound concentration is 1-2mol/L is B solution, and sodium carbonate is dense in B solution
Degree is identical as the concentration of cobalt in solution A；Compound concentration is the ammonia spirit of 5-10mol/L, and 5- is added in every liter of ammonia spirit
The hydrazine hydrate solution that 20mL volume fractions are 30% is C solution；The aluminium salt ethanol solution that compound concentration is 2-4g/L is D molten
Liquid；The hydrogen peroxide solution that compound concentration is 5-10mol/L is E solution；The sodium hydroxide solution that compound concentration is 2-6mol/L is F
Solution；
B, synthetic reaction
So that solution A, B solution and C solution cocurrent is entered reaction kettle, while solution D is added, in the stirring of 200-500r/min
Under reacted, obtain the mixture of cobalt carbonate and lithium carbonate；
C, oxidation reaction
E solution and F solution are added in the mixture of cobalt carbonate and lithium carbonate, is carried out under the stirring of 200-500r/min
Reaction, makes cobalt carbonate be changed into hydroxy cobalt oxide；Wherein, reaction temperature is 70-80 DEG C, reaction time 1-2h, E solution addition
It is 0.5-0.6 times of solution A addition, is 10-11 by adjusting solution D flow control solution ph；
D, it is filtered, washed and dries
After oxidation reaction, material in reaction kettle is filtered, 80-100 DEG C of deionized water pulping and washing, 100-400 DEG C
Lower drying obtains mixing aluminium cobalt acid lithium presoma；
E, it calcines
The calcining of aluminium cobalt acid lithium presoma will be mixed, obtains mixing aluminium cobalt acid lithium product.
As the further preferred of technical solution of the present invention, above-mentioned cobalt salt is one kind in cobaltous sulfate, cobalt nitrate, cobalt chloride
Or several mixtures, lithium salts are the mixture of one or both of lithium nitrate, lithium chloride, aluminium salt ethanol solution is three
The ethanol solution of aluminium chloride or aluminum nitrate.
In synthetic reaction process, a concentration of 5-10g/L of ammonia spirit is controlled, reaction temperature is 70-80 DEG C, solution A flow velocity
For 200L/h, B solution flow velocity is 320-340L/h, and C solution flow velocity is adjusted according to ammonia spirit concentration, and solution D flow velocity is 20L/
H, reaction time 80-100h.
The liquid feeding mode of solution D is solution D charging line to be divided into 6-9 tiny pipelines, each thin liquid-feeding tube is said
Liquid mouth is fixed to middle part or the tail portion dispersion liquid feeding of reaction kettle stirrer paddle.
Calcination process is, in confined conditions, with 800-1000 DEG C of temperature calcination 10-20h.
Compared with the prior art, the advantageous effect of technical solution of the present invention is：
1. the compound of cobalt is very easy to oxidation, the cobalt compound after oxidation can prevent the quick of synthetic product
Growth, causes the laser particle size of final products to be not easy to grow up, the present invention mixes the preparation method of aluminium cobalt acid lithium, passes through addition
The hydrazine hydrate that volume fraction is 30% is reducing agent, cobalt compound can be prevented to aoxidize, and then promotes the fast growth of product, is carried
High efficiency.
2. mix aluminium cobalt acid lithium presoma with Co deposited synthesis, due to Al (OH)3Solubility product constant at normal temperatures is remote
Much smaller than CoCO3Solubility product constant, and Al3+It is difficult that complex reaction occurs with ammonium hydroxide, leads to Al in solution3+Settling rate it is remote
Far faster than Co2+, cause that Al elements are unevenly distributed in presoma and granular precursor is difficult to grow up.The present invention uses aluminium salt is molten
In method of the absolute ethyl alcohol as dopant solution, after ethanol solution need are miscible with water, aluminium salt could participate in reacting, and slow down
Al3+Settling rate, solve due to Al (OH)3Solubility product constant is too small and reacts violent, and aluminium cannot be asked with what cobalt was co-precipitated
Topic；And by the way that aluminium salt ethanol solution charging line is divided into 6-9 small sized pipeline, each thin charging line liquid outlet is fixed
In the middle part of to stirring blade or tail portion disperses the method for liquid feeding, makes Al in building-up process3+Reaction kettle can be rapidly and uniformly distributed to
Middle participation reaction ensure that and prepare being uniformly distributed for aluminium element in product.
3, the aluminium cobalt acid lithium product of mixing that the method for the present invention is prepared is used to mix aluminum amount for 0.2-0.4%, and aluminium element uniformly divides
Cloth, laser particle size are 5-15 μm, Zhen Shi Mi Du≤2.0g/cm3, specific surface area 0.2-0.6m2/ g, in blocky or spherical pattern.
Description of the drawings
Fig. 1 is the testing result of the product synthesized using method in the embodiment of the present invention 1；
Fig. 2 is the testing result of the product synthesized using method in the embodiment of the present invention 2；
Fig. 3 is the testing result of the product synthesized using method in the embodiment of the present invention 3.
Specific implementation mode
The preparation method that aluminium cobalt acid lithium is mixed the present invention by specific embodiment below in conjunction with the accompanying drawings is made further specifically
It is bright.
Embodiment 1
Preparation cobalt chloride concentration is 1mol/L, the mixed solution of a concentration of 1.1mol/L of lithium chloride is solution A；Compound concentration is
The sodium carbonate liquor of 1mol/L is B solution；Compound concentration is the ammonia spirit of 5mol/L, and 5mL is added in every liter of ammonia spirit
The hydrazine hydrate solution that volume fraction is 30% is C solution；The alchlor ethanol solution that compound concentration is 2g/L is solution D；It prepares
The hydrogen peroxide solution of a concentration of 5mol/L is E solution；The sodium hydroxide solution that compound concentration is 2mol/L is F solution.
When synthetic reaction starts, solution A, B solution and C solution cocurrent is made to enter reaction kettle, while by solution D charging line
It is divided into 6-9 tiny pipelines, each thin charging line liquid outlet is fixed to middle part or the portion of reaction kettle stirrer paddle
It dissipates and solution D is added, reacted under the stirring of 200r/min, a concentration of 5g/L of ammonia spirit is controlled in reaction process,
70 DEG C of reaction temperature, solution A flow velocity 200L/h, B solution flow velocity be 320L/h, C solution flow velocity 40L/h, solution D flow velocity 20L/h,
Reaction time 80h obtains the mixture of cobalt carbonate and lithium carbonate.
After synthetic reaction, E solution and F solution, control reaction temperature are added in the mixture of cobalt carbonate and lithium carbonate
Degree is 70 DEG C, and E solution additions are 0.5 times of solution A addition, is 10 by adjusting solution D flow control solution ph,
1h is reacted under the stirring of 500r/min, cobalt carbonate is made to be oxidized to hydroxy cobalt oxide.
After above-mentioned oxidation reaction, material in reaction kettle is filtered, 80 DEG C of deionized water pulping and washings, 100 DEG C
Lower drying obtains mixing aluminium cobalt acid lithium presoma.
Aluminium cobalt acid lithium presoma will be mixed and calcine 20h under confined conditions in be not passed through oxidizing gas 800 DEG C, obtain mixing aluminium
Cobalt acid lithium product, product index are as shown in Figure 1.Prepare mix aluminium cobalt acid lithium product mix aluminum amount be 0.2%, 10 μ of laser particle size
M or so, Zhen Shi Mi Du≤2.0g/cm3, it is in bulk morphologies.
Embodiment 2
Preparation cobalt sulfate concentration is 1.5mol/L, the mixed solution of a concentration of 1.8mol/L of lithium nitrate is solution A；Compound concentration is
The sodium carbonate liquor of 1.5mol/L is B solution；Compound concentration is the ammonia spirit of 8mol/L, and is added in every liter of ammonia spirit
The hydrazine hydrate solution that 15mL volume fractions are 30% is C solution；The aluminum nitrate ethanol solution that compound concentration is 3g/L is solution D；Match
The hydrogen peroxide solution for making a concentration of 8mol/L is E solution；The sodium hydroxide solution that compound concentration is 4mol/L is F solution.
When synthetic reaction starts, solution A, B solution and C solution cocurrent is made to enter reaction kettle, while by solution D charging line
It is divided into 8 tiny pipelines, each thin charging line liquid outlet is fixed to middle part or the tail portion dispersion of reaction kettle stirrer paddle
Solution D is added, is reacted under the stirring of 350r/min, a concentration of 8g/L of ammonia spirit is controlled in reaction process, instead
Answer 75 DEG C of temperature, solution A flow velocity 200L/h, B solution flow velocity is 330L/h, C solution flow velocity 60L/h, solution D flow velocity 20L/h, instead
90h between seasonable, obtains the mixture of cobalt carbonate and lithium carbonate.
After synthetic reaction, E solution and F solution, control reaction temperature are added in the mixture of cobalt carbonate and lithium carbonate
Degree is 75 DEG C, and E solution additions are 0.55 times of solution A addition, is by adjusting solution D flow control solution ph
10.5,1.5h is reacted under the stirring of 350r/min, cobalt carbonate is made to be oxidized to hydroxy cobalt oxide.
After above-mentioned oxidation reaction, material in reaction kettle is filtered, 90 DEG C of deionized water pulping and washings, 300 DEG C
Lower drying obtains mixing aluminium cobalt acid lithium presoma.
Aluminium cobalt acid lithium presoma will be mixed and calcine 15h under confined conditions in be not passed through oxidizing gas 900 DEG C, obtain mixing aluminium
Cobalt acid lithium product, product index are as shown in Figure 2.Prepare mix aluminium cobalt acid lithium product mix aluminum amount be 0.3%, 13 μ of laser particle size
M or so, Zhen Shi Mi Du≤2.0g/cm3, it is in bulk morphologies.
Embodiment 3
Prepare a concentration of 2mol/L of cobalt nitrate, the mixed solution of a concentration of 2mol/L of lithium chloride is solution A；Compound concentration is
The sodium carbonate liquor of 2mol/L is B solution；Compound concentration is the ammonia spirit of 10mol/L, and is added in every liter of ammonia spirit
The hydrazine hydrate solution that 20mL volume fractions are 30% is C solution；The alchlor ethanol solution that compound concentration is 4g/L is solution D；
The hydrogen peroxide solution that compound concentration is 10mol/L is E solution；The sodium hydroxide solution that compound concentration is 6mol/L is F solution.
When synthetic reaction starts, solution A, B solution and C solution cocurrent is made to enter reaction kettle, while by solution D charging line
It is divided into 9 tiny pipelines, each thin charging line liquid outlet is fixed to middle part or the tail portion dispersion of reaction kettle stirrer paddle
Solution D is added, is reacted under the stirring of 500r/min, a concentration of 10g/L of ammonia spirit is controlled in reaction process, instead
Answer 80 DEG C of temperature, solution A flow velocity 200L/h, B solution flow velocity is 340L/h, C solution flow velocity 80L/h, solution D flow velocity 20L/h, instead
100h between seasonable, obtains the mixture of cobalt carbonate and lithium carbonate.
After synthetic reaction, E solution and F solution, control reaction temperature are added in the mixture of cobalt carbonate and lithium carbonate
Degree is 80 DEG C, and E solution additions are 0.6 times of solution A addition, is 11 by adjusting solution D flow control solution ph,
2h is reacted under the stirring of 200r/min, cobalt carbonate is made to be oxidized to hydroxy cobalt oxide.
After above-mentioned oxidation reaction, material in reaction kettle is filtered, 100 DEG C of deionized water pulping and washings, 400 DEG C
Lower drying obtains mixing aluminium cobalt acid lithium presoma.
Aluminium cobalt acid lithium presoma will be mixed and calcine 20h under confined conditions in be not passed through oxidizing gas 1000 DEG C, mixed
Aluminium cobalt acid lithium product, product index are as shown in Figure 3.Prepare mix aluminium cobalt acid lithium product mix aluminum amount be 0.4%, laser particle size 8
μm or so, Zhen Shi Mi Du≤2.0g/cm3, it is in bulk morphologies.
Claims (6)
1. a kind of preparation method for mixing aluminium cobalt acid lithium, is characterized in that, this approach includes the following steps：
A, the preparation of solution
Using cobalt salt, lithium salts as raw material, it is 1 to keep lithium, cobalt molar ratio:1.1-1.4 is configured to cobalt, lithium concentration is 1-2mol/L
Lithium cobalt mixed solution be solution A；The sodium carbonate liquor that compound concentration is 1-2mol/L is B solution, and sodium carbonate is dense in B solution
Degree is identical as the concentration of cobalt in solution A；Compound concentration is the ammonia spirit of 5-10mol/L, and 5- is added in every liter of ammonia spirit
The hydrazine hydrate solution that 20mL volume fractions are 30% is C solution；The aluminium salt ethanol solution that compound concentration is 2-4g/L is D molten
Liquid；The hydrogen peroxide solution that compound concentration is 5-10mol/L is E solution；The sodium hydroxide solution that compound concentration is 2-6mol/L is F
Solution；
B, synthetic reaction
So that solution A, B solution and C solution cocurrent is entered reaction kettle, while solution D is added, in the stirring of 200-500r/min
Under reacted, obtain the mixture of cobalt carbonate and lithium carbonate；
C, oxidation reaction
E solution and F solution are added in the mixture of cobalt carbonate and lithium carbonate, is carried out under the stirring of 200-500r/min
Reaction, makes cobalt carbonate be changed into hydroxy cobalt oxide；Wherein, reaction temperature is 70-80 DEG C, reaction time 1-2h, E solution addition
It is 0.5-0.6 times of solution A addition, is 10-11 by adjusting solution D flow control solution ph；
D, it is filtered, washed and dries
After oxidation reaction, material in reaction kettle is filtered, 80-100 DEG C of deionized water pulping and washing, 100-400 DEG C
Lower drying obtains mixing aluminium cobalt acid lithium presoma；
E, it calcines
The calcining of aluminium cobalt acid lithium presoma will be mixed, obtains mixing aluminium cobalt acid lithium product.
2. a kind of preparation method for mixing aluminium cobalt acid lithium according to claim 1, it is characterised in that：In step a, the cobalt salt
For the mixture of one or more of cobaltous sulfate, cobalt nitrate, cobalt chloride, lithium salts is lithium nitrate, one kind in lithium chloride or two
The mixture of kind, aluminium salt ethanol solution are the ethanol solution of alchlor or aluminum nitrate.
3. a kind of preparation method for mixing aluminium cobalt acid lithium according to claim 1, it is characterised in that：The synthetic reaction process
In, a concentration of 5-10g/L of ammonia spirit is controlled, reaction temperature is 70-80 DEG C, and solution A flow velocity is 200L/h, and B solution flow velocity is
320-340L/h, C solution flow velocity are adjusted according to ammonia spirit concentration, and solution D flow velocity is 20L/h, reaction time 80-100h.
4. according to a kind of preparation method for mixing aluminium cobalt acid lithium of claim 1-3 any one of them, it is characterised in that：In step b,
The liquid feeding mode of the solution D is that solution D charging line is divided into 6-9 tiny pipelines, each thin charging line liquid outlet
It is fixed to middle part or the tail portion dispersion liquid feeding of reaction kettle stirrer paddle.
5. according to a kind of preparation method for mixing aluminium cobalt acid lithium of claim 1-3 any one of them, it is characterised in that：The calcining
Process is, in confined conditions, with 800-1000 DEG C of temperature calcination 10-20h.
6. a kind of preparation method for mixing aluminium cobalt acid lithium according to claim 4, it is characterised in that：The calcination process is,
In confined conditions, with 800-1000 DEG C of temperature calcination 10-20h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111176046A (en) * | 2018-11-12 | 2020-05-19 | 中国科学院上海硅酸盐研究所 | Lithium cobaltate film and preparation method and application thereof |
| CN113233516A (en) * | 2021-05-28 | 2021-08-10 | 金川集团股份有限公司 | Preparation method of single crystal small-granularity cobaltosic oxide |
| CN114604881A (en) * | 2022-03-24 | 2022-06-10 | 昆明理工大学 | Preparation method of hydroxyl nano-alumina with controllable hydroxyl content |
| WO2024055522A1 (en) * | 2022-09-16 | 2024-03-21 | 广东邦普循环科技有限公司 | Surface-coated and modified cobaltosic oxide, and preparation method therefor and use thereof |
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| CN203061158U (en) * | 2013-02-01 | 2013-07-17 | 赤峰博恩药业有限公司 | Dispersive liquid-adding device of reaction kettle |
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| 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 |
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| CN203061158U (en) * | 2013-02-01 | 2013-07-17 | 赤峰博恩药业有限公司 | Dispersive liquid-adding device of reaction kettle |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111176046A (en) * | 2018-11-12 | 2020-05-19 | 中国科学院上海硅酸盐研究所 | Lithium cobaltate film and preparation method and application thereof |
| CN113233516A (en) * | 2021-05-28 | 2021-08-10 | 金川集团股份有限公司 | Preparation method of single crystal small-granularity cobaltosic oxide |
| CN114604881A (en) * | 2022-03-24 | 2022-06-10 | 昆明理工大学 | Preparation method of hydroxyl nano-alumina with controllable hydroxyl content |
| CN114604881B (en) * | 2022-03-24 | 2022-11-25 | 昆明理工大学 | Preparation method of hydroxyl nano-alumina with controllable hydroxyl content |
| WO2024055522A1 (en) * | 2022-09-16 | 2024-03-21 | 广东邦普循环科技有限公司 | Surface-coated and modified cobaltosic oxide, and preparation method therefor and use thereof |
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