CN104319391A - Preparation method of high-nickel, low-cobalt and low-manganese ternary positive electrode material precursor for lithium battery - Google Patents
Preparation method of high-nickel, low-cobalt and low-manganese ternary positive electrode material precursor for lithium battery Download PDFInfo
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- CN104319391A CN104319391A CN201410524111.2A CN201410524111A CN104319391A CN 104319391 A CN104319391 A CN 104319391A CN 201410524111 A CN201410524111 A CN 201410524111A CN 104319391 A CN104319391 A CN 104319391A
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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
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- 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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Abstract
The invention relates to a lithium battery preparation material, and provides a preparation method of a high-nickel, low-cobalt and low-manganese ternary positive electrode material precursor for a lithium battery. The shape and the appearance of nickel, cobalt and manganese hydroxide co-precipitated product can be precisely and conveniently controlled. A raw material solution is prepared from A, namely a nickel salt solution containing 80g/L of nickel, B, namely a mixed solution containing 60-90g/L of nickel, 10-30g/L of cobalt and 10-30g/L of manganese (prepared according to different proportions of x and y in nickel, cobalt and manganese hydroxide Ni(1-x-y)CoxMny(OH)2, wherein x is greater than or equal to 0.1 and smaller than or equal to 0.25, y is greater than or equal to 0.1 and smaller than or equal to 0.25, x+y is greater than or equal to 0.2 and smaller than or equal to 0.5), C, namely a solution containing 8mol/L of sodium hydroxide, and D, namely a solution containing a surface active dispersing agent. A preparation method comprises the steps of nickel hydroxide seed crystal cultivation, crystal particle maturing, slurry aging, precipitate filtering, washing and drying. Compared with the prior art, the preparation method has the advantages that ammonia water does not need to be added in the whole process including cultivation and confirmation of Ni(OH)2 crystals, so that high ammonia-nitrogen wastewater cannot be produced; the working procedure of treating the ammonia-nitrogen wastewater is omitted, so that the production cost is further lowered.
Description
Technical field
The present invention relates to lithium battery manufactured materials, particularly a kind of preparation method of presoma of ternary cathode material of lithium ion battery.
Background technology
Lithium ion battery is the green energy-storing battery of a new generation, has that voltage is high, energy density is large, the outstanding advantages such as good cycle, self discharge are little, memory-less effect, has been widely used in the electronic products such as mobile phone, notebook computer, energy storage.
Positive electrode is the crucial composition material of lithium ion battery, is cost accounting the best part in lithium ion battery.The lithium electricity positive electrode obtaining commercial applications at present mainly contains cobalt acid lithium (LiCoO
2), LiMn2O4 (LiMnO
2), lithium nickelate (LiNiO
2), nickel cobalt manganese (1:1:1,5:2:3 or 4:3:3) sour lithium, nickel cobalt lithium aluminate, LiFePO4 etc.Cobalt acid lithium is as one of the positive electrode of most extensive use, the market share is once up to more than 70%, but cobalt is a kind of rare resource, because of the factor such as raw material supply, cost price, the application of cobalt acid lithium faces more and more stern challenge, and the high performance substitution material of development and application has become common recognition in the industry.Nickel cobalt manganese (1:1:1,5:2:3,4:3:3) sour lithium ternary material, with the advantage of its higher energy density, high security and lower cost, has started to widely apply on some middle-end notebook computers.For the requirement to power vehicle flying power, nickel cobalt manganese (1:1:1,5:2:3,4:3:3) sour lithium ternary material introduced by the electrokinetic cell giant such as Japan and Korea S and is used as anode constituents to improve energy density, the Toyota Motor of such as Japan adopts nickel-cobalt-manganese ternary material, take into account cost and energy density advantage, lithium ion battery used for electric vehicle has been produced in batches.Therefore, cobalt nickel lithium manganate ternary material thinks most one of positive electrode having application prospect, and nickelic low cobalt low manganese (6:2:2 or 8:1:1) sour lithium, its energy density is higher, and bulk density is larger, has more application prospect in some field.
About the preparation of nickel cobalt manganese hydroxide and the bibliographical information of aspect of performance more, mostly adopt the method for liquid phase synthesis.As CN1547277A discloses a kind of method preparing nickel cobalt manganese hydroxide precursor, the method comprises makes mixed solution by soluble nickel salt, cobalt salt and manganese salt, at 20-90 degree temperature, strong base solution (as potassium hydroxide, NaOH, lithium hydroxide) is added drop-wise in above-mentioned salting liquid under agitation, until solution PH is greater than 9, be precipitated thing, then sediment is spent deionized water, filtration, the solids obtained is nickel cobalt manganese hydroxide, can be directly used in and prepare nickle cobalt lithium manganate tertiary cathode material.With powder or sheet-like particle that the nickel cobalt manganese hydroxide precursor that the method obtains is irregular shape, bulk density is low.Well known to a person skilled in the art and be, the low meeting of bulk density causes the specific capacity of positive electrode low, and battery performance is poor, therefore wishes to prepare the nickel cobalt manganese hydroxide be made up of the spheric granules of rule, to improve the bulk density of ternary material.
CN1622371A discloses a kind of preparation method of high density spherical nickel-cobalt manganese hydroxide, under the method is included in 40-65 degree temperature, be the mixed aqueous solution of the nickel salt of 0.6-3 mol/L, cobalt salt and manganese salt by total concentration of metal ions, the sodium hydrate aqueous solution of 2-10 mol/L, the ammonia spirit pump of 2-10 mol/L be input in the reactor that band stirs respectively continuously, and control NH
3the pH value of/(Ni+Co+Mn)=0.2-1.0 (mol ratio) and reactant liquor is 10-12, obtain solid matter, then be separated by gained solid and spend deionized water to the pH value of washings and be less than 8, the product after washing obtains spherical nickel-cobalt manganese hydroxide in drier after drying.
CN1966410A discloses a kind of preparation method of nickel cobalt manganese hydroxide, under the method is included in 5-40 degree temperature (substantially need not additionally heating condition under), in the reactor that band stirs, the mixed solution A containing nickel salt, cobalt salt and manganese salt and the solution B containing highly basic NaOH are carried out precipitation reaction in the device by band gauge is injected into containing ammoniacal liquor end liquid C, obtain solid matter, then be separated by gained solid and spend deionized water, the product after washing obtains spherical nickel-cobalt manganese hydroxide in drier after drying.
Although spherical nickel-cobalt manganese hydroxide all may be obtained by above-mentioned two kinds of methods, but process cannot accurately control, product sphericity cannot ensure, and all employ ammoniacal liquor in two kinds of methods, cause severe operational environment, ammonia nitrogen ion is contained, the problems such as nitrogen-containing wastewater processing cost increasing in mother liquor after sediment is separated.
Summary of the invention
The object of the invention is the shortcoming in order to overcome in various nickel cobalt manganese hydroxide preparation method of the prior art, there is provided a kind of operating environment good, accurately, conveniently can control the preparation method of the low manganese hydroxide of nickelic low cobalt of nickel cobalt manganese hydroxide coprecipitated product pattern.
Technical problem of the present invention is solved mainly through following technical proposals:
A lithium battery preparation method for the low manganese ternary anode material precursor of nickelic low cobalt, comprises the following steps:
(1) material solution preparation: the nickel salt solution of nickeliferous 80 grams per liters of solution A, the nickeliferous 60-90 grams per liter of solution B, containing cobalt 10-30 grams per liter, containing the mixed solution of manganese 10-30 grams per liter (according to nickel hydroxide cobalt manganese Ni
1-x-yco
xmn
y(OH)
2, 0.1≤x≤0.25,0.1≤y≤0.25, x, y ratio difference configuration in 0.2≤x+y≤0.5), solution C is containing NaOH 8mol/L solution, and solution D is containing surface active dispersing agent solution.
(2) nickel hydroxide crystal seed is cultivated: stir in heatable reactor at a band, inject the deionized water of certain volume, add through the solution C calculated and measure (keeping reaction end of a period PH 10) and be uniformly mixed containing the solution D (volume ratio 0.01-0.05%) of a certain amount of dispersant, add through the solution A (crystal seed Ni amount/(Ni+Co+Mn)=0.05-0.1) calculated and measure after abundant mixing at normal temperatures fast, be swift in response and carry out, produce solid sediment, mixing speed keeps more than 500rpm to maintain 1-2h, after in sample analysis suspended matter, nickel hydroxide crystal seed D50 laser particle size reaches 1-1.5 micron, crystal seed cultivation stage is complete.
(3) crystal grain is ripe: after seed size D50 reaches 1-1.5 micron index, slurry temperature in reactor is risen to 60 degree or more (according to nickelic low cobalt low manganese hydroxide crystal grain size determination reaction temperatures), mixing speed drops to 300-320rpm, open the valve of solution B and solution C and stream adds in reactor and reacts, in maintenance reactor, solution PH is between 10-10.5, the particle of nickel cobalt manganese hydroxide crystal is constantly grown up, and after the requirement index that solids D50 granularity reaches 5-10 micron, valve-off stops reinforced.
(4) slip ageing: mixing speed adjusts to 200rpm, keeps digestion time 6h-8h, makes the further homogenization of the particle in slip.
(5) sediment filters, washs: filtered by above-mentioned slip with filter, more constantly wash with deionized water, until wash water PH is less than 8, wash complete.
(6) drying precipitate: the sediment after above-mentioned washing carries out drying at the temperature of 200-300 degree, obtains tap density and is greater than 1.8g/cm
3, the lithium battery ternary anode material precursor that laser particle size (D50) 5 ~ 10um is spherical-low manganese hydroxide product of nickelic low cobalt.
The preparation method that a kind of operating environment provided by the invention is good, conveniently can control the low manganese hydroxide of nickelic low cobalt of nickel cobalt manganese hydroxide coprecipitated product pattern, compared with the conventional method, has following distinguishing feature:
(1), in the incubation step of nickel hydroxide crystal grain, be conducive to, under the condition that nickel hydroxide molecule formed, first cultivating and producing the spherical little crystal grain of nickel hydroxide.
(2) have employed the interpolation of surface active dispersing agent, be conducive to opening of loose agglomerated particle thing, be conducive to the generation of tiny crystal grains.
(3) the stage of recognition of molecule, after nickel hydroxide molecule is formed, sample presentation analyzes D50 granular laser particle size, guarantees to enter the next stage after nickel hydroxide molecule D50 reaches 1-1.5 micron again.
(4) difference of process reaction temperature: crystal grain cultivation stage adopts normal temperature, is conducive to nickel hydroxide molecule that is less, more sphericity and generates; The temperature of grain growth stage employing 60 degree or more, can improve reaction speed, also can control the granularity of the low manganese hydroxide of the nickelic low cobalt of end of a period.The reaction temperature that stage is different, is more conducive to the physical characteristic required for precisely control product.
(5) the present invention and prior art significantly do not need to add ammoniacal liquor unlike, whole process, can not produce high ammonia-nitrogen wastewater, eliminate the operation of process nitrogen-containing wastewater, reduce further production cost.
(6) nickel salt solution in solution A, solution B described in process of the present invention can be nickelous sulfate, nickel chloride or nickel nitrate solution; Cobalt salt solution can be cobaltous sulfate, cobalt chloride or cobalt nitrate solution; Manganese salt solution can be manganese sulfate, manganese chloride or manganese nitrate solution.
(7) in the present invention, solution C can be highly basic NaOH, potassium hydroxide.
(8) solution D is the solution of pbz polymer modifier dispersant.
Accompanying drawing explanation
Fig. 1 is nickel hydroxide cobalt manganese product scanning electron microscope (SEM) photograph in the present invention.
Embodiment
Below technical scheme of the present invention is described in further detail.
A lithium battery preparation method for the low manganese ternary anode material precursor of nickelic low cobalt,
Execution mode comprises the following steps:
Preparation raw material solution, the nickel salt solution of nickeliferous 80 grams per liters of solution A, the nickeliferous 60-90 grams per liter of solution B, containing cobalt 10-30 grams per liter, containing the mixed solution of manganese 10-30 grams per liter (according to nickel hydroxide cobalt manganese Ni
1-x-yco
xmn
y(OH)
2, 0.1≤x≤0.25,0.1≤y≤0.25, x, y ratio difference configuration in 0.2≤x+y≤0.5), solution C is containing NaOH 8mol/L solution, and solution D is containing surface active dispersing agent solution.
Stir in heatable reactor at a band, inject the deionized water of certain volume, add through the solution C calculated and measure (keeping reaction end of a period PH 10) and be uniformly mixed containing the solution D (volume ratio 0.01-0.05%) of a certain amount of dispersant, add through the solution A (crystal seed Ni amount/(Ni+Co+Mn)=0.05-0.1) calculated and measure after abundant mixing at normal temperatures fast, be swift in response and carry out, produce solid sediment, mixing speed keeps more than 500rpm to maintain 1-2h, after in sample analysis suspended matter, nickel hydroxide crystal seed D50 laser particle size reaches 1-1.5 micron, crystal seed cultivation stage is complete.After seed size D50 reaches 1-1.5 micron index, slurry temperature in reactor is risen to 60 degree or more (according to nickelic low cobalt low manganese hydroxide crystal grain size determination reaction temperatures), mixing speed drops to 300-320rpm, open the valve of solution B and solution C and stream adds in reactor and reacts, in maintenance reactor, solution PH is between 10-10.5, the particle of nickel cobalt manganese hydroxide crystal is constantly grown up, and after the requirement index that solids D50 granularity reaches 5-10 micron, valve-off stops reinforced.
Mixing speed adjusts to 200rpm, keeps digestion time 6h-8h, makes the further homogenization of the particle in slip.With filter, above-mentioned slip is filtered, more constantly wash with deionized water, until wash water PH is less than 8, wash complete.Sediment after washing is carried out drying at the temperature of 200-300 degree, obtains tap density and be greater than 1.8g/cm
3, the lithium battery ternary anode material precursor that laser particle size (D50) 5 ~ 10um is spherical-low manganese hydroxide product of nickelic low cobalt.
The present embodiment is the execution mode of example of the present invention; for those skilled in the art; on the basis that the invention discloses application process and principle; be easy to make various types of improvement or distortion; and the structure be not limited only to described by the above-mentioned embodiment of the present invention, therefore previously described mode is preferred version, and does not have restrictive meaning; every equivalence done according to the present invention changes and amendment, all in the scope protection range of claims of the present invention.
Claims (1)
1. a lithium battery preparation method for the low manganese ternary anode material precursor of nickelic low cobalt, comprises the following steps:
(1) material solution preparation: the nickel salt solution of nickeliferous 80 grams per liters of solution A, the nickeliferous 60-90 grams per liter of solution B, containing cobalt 10-30 grams per liter, mixed solution containing manganese 10-30 grams per liter, described mixed solution configuration proportion is according to nickel hydroxide cobalt manganese Ni
1-x-yco
xmn
y(OH)
2, 0.1≤x≤0.25,0.1≤y≤0.25, x, y ratio difference configuration in 0.2≤x+y≤0.5, solution C is containing NaOH 8mol/L solution, and solution D is containing surface active dispersing agent solution;
(2) nickel hydroxide crystal seed is cultivated: stir in heatable reactor at a band, inject the deionized water of certain volume, add the solution C through calculating and measure and be uniformly mixed containing the solution D of a certain amount of dispersant, its maintenance reaction end of a period of described solution C PH 10, its volume ratio 0.01-0.05% of described solution D, both add through the solution A calculated and measure at normal temperatures fast after fully mixing, its crystal seed Ni amount/(Ni+Co+Mn)=0.05-0.1, be swift in response and carry out, produce solid sediment, mixing speed keeps more than 500rpm to maintain 1-2h, after in sample analysis suspended matter, nickel hydroxide crystal seed D50 laser particle size reaches 1-1.5 micron, crystal seed cultivation stage is complete,
(3) crystal grain is ripe: after seed size D50 reaches 1-1.5 micron index, slurry temperature in reactor is risen to 60 degree or more, mixing speed drops to 300-320rpm, open the valve of solution B and solution C and stream adds in reactor and reacts, in maintenance reactor, solution PH is between 10-10.5, the particle of nickel cobalt manganese hydroxide crystal is constantly grown up, and after the requirement index that solids D50 granularity reaches 5-10 micron, valve-off stops reinforced;
(4) slip ageing: mixing speed adjusts to 200rpm, keeps digestion time 6h-8h, makes the further homogenization of the particle in slip;
(5) sediment filters, washs: filtered by above-mentioned slip with filter, more constantly wash with deionized water, until wash water PH is less than 8, wash complete;
(6) drying precipitate: the sediment after aforementioned washing carries out drying at the temperature of 200-300 degree, obtains tap density and is greater than 1.8g/cm
3, the lithium battery ternary anode material precursor that laser particle size (D50) 5 ~ 10um is spherical-low manganese hydroxide product of nickelic low cobalt.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104701524A (en) * | 2015-03-03 | 2015-06-10 | 中南大学 | Method for directly preparing nickel-cobalt-manganese ternary cathode material precursor from nickel electrolyte |
| CN105329955A (en) * | 2015-12-01 | 2016-02-17 | 韶关中弘金属实业有限公司 | Production process for spherical nickel hydroxide |
| CN105375078A (en) * | 2015-10-23 | 2016-03-02 | 赣州市芯隆新能源材料有限公司 | Method for circularly preparing spherical lithium nickel cobalt manganese oxide by lithium-ion battery positive plate |
| CN105609755A (en) * | 2016-02-29 | 2016-05-25 | 深圳市贝特瑞新能源材料股份有限公司 | Preparation method for positive electrode active material, and positive electrode active material |
| CN106887585A (en) * | 2017-03-13 | 2017-06-23 | 成都育芽科技有限公司 | A kind of preparation method of new energy battery nickel-cobalt lithium manganate cathode material |
| CN107565124A (en) * | 2017-08-22 | 2018-01-09 | 山东精工电子科技有限公司 | A kind of precursor of nickel-cobalt-lithium-manganese-oxide and preparation method thereof |
| CN109888242A (en) * | 2019-03-12 | 2019-06-14 | 四川纳创时代新能源科技有限公司 | A kind of high-tap density cobalt nickel lithium manganate ternary material and preparation method thereof |
| CN110459763A (en) * | 2019-07-21 | 2019-11-15 | 浙江美都海创锂电科技有限公司 | A kind of fast preparation method of nickelic presoma |
| CN111403728A (en) * | 2019-11-11 | 2020-07-10 | 余姚市鑫和电池材料有限公司 | Preparation method of high-nickel low-cobalt co-precipitation magnesium-coated positive electrode material |
| CN111564625A (en) * | 2020-04-07 | 2020-08-21 | 江门市科恒实业股份有限公司 | Single crystal ternary positive electrode material and preparation method thereof |
| WO2021195524A1 (en) | 2020-03-27 | 2021-09-30 | Board Of Regents, The University Of Texas System | Low-cobalt and cobalt-free, high-energy cathode materials for lithium batteries |
| CN113479943A (en) * | 2021-07-01 | 2021-10-08 | 昆山宝创新能源科技有限公司 | Ternary cathode material precursor, preparation method thereof, automatic control feeding system and application |
| CN113748541A (en) * | 2019-09-26 | 2021-12-03 | 株式会社Lg化学 | Positive electrode active material precursor for secondary battery, method for preparing same, and method for preparing positive electrode active material |
| CN113860393A (en) * | 2021-09-22 | 2021-12-31 | 陕西红马科技有限公司 | Preparation method of amorphous nano single crystal material |
| CN116855759A (en) * | 2023-08-31 | 2023-10-10 | 赣州吉锐新能源科技股份有限公司 | High-nickel low-cobalt feed liquid deep cobalt removal process for retired battery |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104701524A (en) * | 2015-03-03 | 2015-06-10 | 中南大学 | Method for directly preparing nickel-cobalt-manganese ternary cathode material precursor from nickel electrolyte |
| CN105375078A (en) * | 2015-10-23 | 2016-03-02 | 赣州市芯隆新能源材料有限公司 | Method for circularly preparing spherical lithium nickel cobalt manganese oxide by lithium-ion battery positive plate |
| CN105329955A (en) * | 2015-12-01 | 2016-02-17 | 韶关中弘金属实业有限公司 | Production process for spherical nickel hydroxide |
| CN105609755A (en) * | 2016-02-29 | 2016-05-25 | 深圳市贝特瑞新能源材料股份有限公司 | Preparation method for positive electrode active material, and positive electrode active material |
| CN106887585A (en) * | 2017-03-13 | 2017-06-23 | 成都育芽科技有限公司 | A kind of preparation method of new energy battery nickel-cobalt lithium manganate cathode material |
| CN107565124A (en) * | 2017-08-22 | 2018-01-09 | 山东精工电子科技有限公司 | A kind of precursor of nickel-cobalt-lithium-manganese-oxide and preparation method thereof |
| CN107565124B (en) * | 2017-08-22 | 2022-10-25 | 山东精工电子科技有限公司 | Nickel cobalt lithium manganate precursor and preparation method thereof |
| CN109888242A (en) * | 2019-03-12 | 2019-06-14 | 四川纳创时代新能源科技有限公司 | A kind of high-tap density cobalt nickel lithium manganate ternary material and preparation method thereof |
| CN110459763A (en) * | 2019-07-21 | 2019-11-15 | 浙江美都海创锂电科技有限公司 | A kind of fast preparation method of nickelic presoma |
| CN113748541A (en) * | 2019-09-26 | 2021-12-03 | 株式会社Lg化学 | Positive electrode active material precursor for secondary battery, method for preparing same, and method for preparing positive electrode active material |
| CN111403728A (en) * | 2019-11-11 | 2020-07-10 | 余姚市鑫和电池材料有限公司 | Preparation method of high-nickel low-cobalt co-precipitation magnesium-coated positive electrode material |
| WO2021195524A1 (en) | 2020-03-27 | 2021-09-30 | Board Of Regents, The University Of Texas System | Low-cobalt and cobalt-free, high-energy cathode materials for lithium batteries |
| US11233239B2 (en) | 2020-03-27 | 2022-01-25 | Board Of Regents, The University Of Texas System | Low-cobalt and cobalt-free, high-energy cathode materials for lithium batteries |
| CN111564625A (en) * | 2020-04-07 | 2020-08-21 | 江门市科恒实业股份有限公司 | Single crystal ternary positive electrode material and preparation method thereof |
| CN113479943A (en) * | 2021-07-01 | 2021-10-08 | 昆山宝创新能源科技有限公司 | Ternary cathode material precursor, preparation method thereof, automatic control feeding system and application |
| CN113860393A (en) * | 2021-09-22 | 2021-12-31 | 陕西红马科技有限公司 | Preparation method of amorphous nano single crystal material |
| CN116855759A (en) * | 2023-08-31 | 2023-10-10 | 赣州吉锐新能源科技股份有限公司 | High-nickel low-cobalt feed liquid deep cobalt removal process for retired battery |
| CN116855759B (en) * | 2023-08-31 | 2023-11-17 | 赣州吉锐新能源科技股份有限公司 | High-nickel low-cobalt feed liquid deep cobalt removal process for retired battery |
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