CN105070970A - Method for preparing lithium ion battery anode material by using mixed waste alkaline battery - Google Patents
Method for preparing lithium ion battery anode material by using mixed waste alkaline battery Download PDFInfo
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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
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
- H01M4/36—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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The method comprises the steps of taking the anode materials of the waste alkaline zinc-manganese batteries and the waste lithium ion batteries as raw materials, dissolving the anode materials by nitric acid with certain concentration, and adding corresponding nitrate into a dissolving solution to adjust the ratio of cobalt ions, nickel ions and manganese ions. Using sodium hydroxide as precipitant, preparing nickel cobalt manganese hydroxide precursor by coprecipitation method, filtering, drying, mixing with a certain amount of lithium carbonate, and calcining in muffle furnace to obtain LiNi 1/3 Co 1/3 Mn 1/3 O 2 A ternary positive electrode material. Performing morphology and structure characterization on the obtained product by means of a spectrometer, an X-ray diffractometer, a scanning electron microscope and an energy spectrometer, preparing the product into a button cell, and performing electrochemical performance on the button cell by using a blue-ray analyzerAnd (5) line characterization. The results show that pH =8 was controlled at the precipitation reaction; the calcining temperature is 850 ℃; when the calcination time is 10 hours, the initial discharge capacity of the prepared new battery is 158.3mAhg –1 . The research not only can recycle the waste alkaline batteries of various types, but also can reduce the production cost of the battery anode material, and has better economic benefit and social benefit.
Description
Technical Field
The invention belongs to the technical field of recycling of solid wastes, and particularly relates to a method for preparing a lithium ion battery anode material by using a mixed waste alkaline battery.
Background
In recent years, lithium ion batteries are widely applied to various digital products, and have wide application prospects in the fields of electric vehicles, energy storage batteries and the like in the future. In order to meet the increasing demand of people for secondary batteries with high energy ratio and long cycle life, the preparation of a positive electrode material with excellent performance, safety and low price becomes a key in the commercialization process of lithium ion batteries.
Since the positive electrode material of the lithium ion battery is a key material for determining the performance of the lithium ion battery, the performance of the positive electrode material directly affects the discharge efficiency of the battery. For the Ni-Co-Mn ternary composite lithium ion battery anode material, the electrochemical performance is superior to that of any single LiNiO due to the synergistic effect of nickel, cobalt and manganese 2 、LiCoO 2 And LiMnO 2 The layered oxide has the advantages of the three components, has the characteristics of high specific capacity, stable cycle performance, good safety performance, relatively low cost and the like, and is considered to be the most potential lithium ion battery anode material. However, due to the scarcity of various metal resources in nature, the production cost of the cathode material in the preparation process is high.
However, for technical and economic reasons, the recovery rate of waste alkaline batteries (waste lithium cobalt oxide lithium ion batteries, waste alkaline zinc manganese batteries) is low, and a large amount of waste alkaline batteries are abandoned, thus causing great threat and pollution to the environment. However, the waste alkaline batteries contain a large amount of metal resources, if the comprehensive recycling of non-ferrous metal resources of the waste alkaline batteries, particularly cobalt, manganese and nickel, is realized, the shortage of non-ferrous metal resources in China can be effectively relieved, and huge economic benefits can be obtained, so that the waste alkaline batteries become a hot problem of social attention, and the waste alkaline batteries are also main power for promoting the development of the waste alkaline battery recycling industry.
At present, because different batteries contain different components, the recovery treatment of waste batteries with single model is often carried out at home and abroad, and the single property of the treatment process seriously limits the recovery efficiency of mixed waste batteries with various models. In order to overcome the defects, the ternary lithium ion battery anode material is prepared by mainly taking the mixed waste alkaline battery (waste lithium cobalt oxide lithium ion battery and waste alkaline zinc-manganese battery) anode material as a raw material, so that the waste alkaline batteries with different models can be recycled, the great waste of resources and serious environmental pollution are avoided, the production cost of the battery anode material is reduced, and the ternary lithium ion battery anode material has better economic benefit and social benefit.
Disclosure of Invention
The invention provides a method for preparing a lithium ion battery anode material by using mixed waste alkaline batteries, which comprises the steps of dissolving the mixed waste alkaline battery anode material (waste lithium cobalt oxide lithium ion batteries and waste alkaline zinc-manganese batteries) by nitric acid as a raw material, preparing a precursor nickel-cobalt-manganese hydroxide ternary material by a coprecipitation method, mixing the precursor nickel-cobalt-manganese hydroxide ternary material with lithium carbonate, and sintering the mixture in a high-temperature furnace to obtain LiNi 1/3 Co 1/3 Mn 1/3 O 2 A ternary anode material of a lithium ion battery.
The technical scheme of the invention is as follows: a method for preparing a lithium ion battery anode material by using a mixed waste alkaline battery comprises the procedures of splitting the waste alkaline battery, separating the lithium battery anode material from an aluminum foil, dissolving, carrying out coprecipitation reaction and calcining, and is characterized in that:
(1) The positive and negative electrodes of the waste lithium ion battery are connected by a lead to enable the waste lithium ion battery to be self-discharged so as to prevent discharging or spontaneous combustion in the manual splitting process. Then, the aluminum foil and the positive electrode material were separated. For waste alkaline zinc-manganese batteries, a steel saw is used for sawing the battery collector, and the manganese-containing positive electrode material is manually separated.
(2) Putting the lithium battery anode material and the aluminum foil into NMP, performing ultrasonic treatment for 3min, filtering and drying. And obtaining the lithium ion battery anode active material.
(3) With 6mol L -1 The nitric acid solution contains 2.5 percent of hydrogen peroxide to dissolve the anode material of the mixed battery and is filtered. Thus obtaining the mixed filtrate of nickel, cobalt and manganese with certain concentration.
(4) Adjusting the molar ratio of nickel, cobalt and manganese in the solution to 1 by using nickel nitrate, cobalt nitrate and manganese nitrate, keeping the solution at 60 ℃ under the action of a constant-temperature magnetic stirrer, and slowly adding 2.5mol L of solution dropwise into the solution -1 Adjusting the pH value of the solution to 8, heating and evaporating the solution in a constant-temperature water bath at 70 ℃, continuously stirring until viscous sol is completely formed, drying the sol at 110 ℃ for 5 hours to form dry gel, grinding and crushing.
(5) Uniformly mixing the crushed sample with a certain amount of lithium carbonate, and calcining the mixture for 10 hours in a muffle furnace at the temperature of 850 ℃ to obtain LiNi 1/3 Co 1/3 Mn 1/3 O 2 A ternary cathode material of a lithium ion battery.
The invention utilizes the coprecipitation method to prepare the ternary anode material of the lithium ion battery, the prepared lithium ion battery anode material has excellent performance, the cost of raw materials is saved, and an effective method is provided for the recycling treatment of the mixed waste alkaline batteries.
Drawings
FIG. 1 shows a schematic view of aThe flow of the invention for preparing the lithium ion battery anode material by mixing the waste alkaline batteries is illustratedDrawing (A)，FIG. 2The invention prepares LiNi under the condition of different pH values 1/3 Co 1/3 Mn 1/3 O 2 IR of cathode MaterialDrawing (A)Spectra (a =5 b =6 c =7 d =8 e =9,FIG. 3Is the invention of different calcination temperatures to LiNi 1/3 Co 1/3 Mn 1/3 O 2 Influence of the preparation of the positive electrode material (a =650 ℃; b =750 ℃; c =850 ℃; d =950 ℃),FIG. 4Is the invention for LiNi with different calcination times 1/3 Co 1/3 Mn 1/3 O 2 Effect of positive electrode material preparation (a =7h, b =8h, c =9h,FIG. 5The invention is in LiNi 1/3 Co 1/3 Mn 1/3 O 2 Scanning electron microscope picture and EDS energy spectrum of anode materialDrawing (A)，FIG. 6The charge-discharge curve and the cycle performance curve of the battery prepared by the ternary cathode material are newly prepared at 2.8-4.6V.
Detailed Description
The present invention is further described below with reference to examples. It should be noted that the present invention is not limited to the following embodiments.
Example 1
And optimizing the dissolving condition of the mixed waste alkaline battery.
For the waste lithium ion battery, firstly, the positive electrode and the negative electrode are connected by a lead to enable the waste lithium ion battery to be self-discharged so as to prevent discharging or spontaneous combustion in the manual splitting process. Then, the positive electrode material containing aluminum foil was separated. When the separation conditions of the anode material and the aluminum foil are optimized, water, carbon tetrachloride, dichloromethane and NMP are respectively selected as ultrasonic solvents, and the result shows that the anode material and the aluminum foil can be completely separated by using NMP as the ultrasonic solvent and carrying out ultrasonic treatment for 3min in ultrasonic waves no matter what type and brand of lithium cobaltate anode material is. And (5) filtering and drying. And obtaining the lithium ion battery anode active material. For waste alkaline zinc-manganese batteries, a steel saw is used for sawing the battery collector, and the manganese-containing positive electrode material is manually separated. Then mixing the two battery anode materials, and using 6mol L -1 The nitric acid solution contains 2.5 percent of hydrogen peroxide to dissolve the anode material of the mixed battery and is filtered. Obtaining a nickel, cobalt and manganese mixed solution with a certain concentration, and filtering to obtain a mixed ion filtering solution. Schematic flow of lithium ion battery anode material prepared from mixed waste alkaline batteriesAs shown in figure 1As shown.
Example 2
Preparation of LiNi under different pH values 1/3 Co 1/3 Mn 1/3 O 2 IR of cathode MaterialDrawing (A)Spectra.
When different gelling agents or sinks are usedThe starches form gels because of their polarity, polar moment, and acquisition of reactive ions. The exchange reaction in the sol will be affected differently. When only water is used as solvent, the precursor does not contain active substances capable of undergoing polycondensation reaction, and the crosslinking among products is realized only by heating, stirring and evaporating the solvent, so that the products approach to form gel through hydrogen bond connection. When absolute ethyl alcohol or ethylene glycol is used as a solvent, citric acid is added as a gelling agent to form gel, and the reason for forming the gel is that the citric acid and the solvent have stronger polymerization reaction and quickly form a continuous three-dimensional network structure. The experiment takes water as solvent, naOH as precipitator,FIG. 2 is a schematic view of a display deviceIs LiNi for controlling reactions with different pH values 1/3 Co 1/3 Mn 1/3 O 2 The infrared spectrum obtained after calcination at a high temperature of 800 ℃ for 8hDrawing (A)A spectrum; byFIG. 2It can be seen that a, bDrawing (A)Because the solvent water is excessive, the formed coprecipitation may contain intramolecular crystal water, OH stretching vibration absorption peaks are obvious, c and d show that OH completely generates coprecipitation, and e and f along with the increase of pH valueDrawing (A)Showing an excess of OH after complete reaction. It was also found that the pH value was 625cm at different pH values -1 Can completely generate the nanocrystalline nickel cobalt lithium manganese oxide anode material. By comparison, dDrawing (A)At 625cm -1 The time peak is sharp and has no impurity peak. When pH =8, the nanocrystalline lithium nickel cobalt manganese oxide positive electrode material was completely produced.
Example 3
Different calcination temperature vs LiNi 1/3 Co 1/3 Mn 1/3 O 2 Influence of the preparation of the positive electrode material.
ByFIG. 3As can be seen, XRD in the case of calcination of a, b, dDrawing (A)The spectra have all hetero peaks, and the crystallinity is better under the condition of calcining c; this result indicates that the calcination temperature is gradually increased and the crystal grains are gradually formed, but when the calcination temperature is too high, the micropores may shrink and the agglomeration phenomenon may occur, and when the calcination temperature is too low, the precursor may not be completely decomposed. In combination, the degree of crystallinity at 850 ℃ is strong, and no impurity peak exists.
Example 4
Different calcination times for LiNi 1/3 Co 1/3 Mn 1/3 O 2 The influence of (c).
FIG. 4Display LiNi 1/3 Co 1/3 Mn 1/3 O 2 XRD of anode material calcined at 850 ℃ for 7h to 11hDrawing (A)The spectrum, with increasing calcination time, shows that the impurity peak near 2 θ =30 ° gradually weakens, while the two sets of diffraction peaks (006)/(012) and (108)/(110) become sharper and more clearly split, indicating LiNi with increasing calcination time 1/3 Co 1/3 Mn 1/3 O 2 The degree of crystallization of the positive electrode material is higher. From the viewpoint of energy saving, the final calcination time was determined to be 10 hours.
Example 5
LiNi 1/3 Co 1/3 Mn 1/3 O 2 Scanning electron microscope picture and energy spectrum of anode materialDrawing (A)。
LiNi 1/3 Co 1/3 Mn 1/3 O 2 Scanning electron microscope picture and EDS energy spectrum of anode materialAs shown in figure 5As shown. As can be seen from the scanning electron microscope pictures, liNi 1/3 Co 1/3 Mn 1/3 O 2 The particle size of the anode material is about 0.1 micron, the particle surface is smooth, the dispersion is uniform, and the agglomeration phenomenon is basically avoided. From EDS energy spectrum analysis, liNi 1/3 Co 1/3 Mn 1/3 O 2 The main components of the positive electrode material are nickel, cobalt and manganese. Since the atomic mass number of lithium is less than 3 and the mass number of EDS should be greater than 4 in the analysis, it is possible to obtain a spectrumIn the figureThe presence of lithium atoms was not seen. Reacting the LiNi with a catalyst to obtain a mixture 1/3 Co 1/3 Mn 1/3 O 2 The positive electrode material is dissolved by acid, then the concentration of nickel, cobalt and manganese in the solution is detected by ICP-OES, and after analysis, the proportion of each element and the stoichiometric ratio of each element in the molecular formula are completely consistent.
Example 6
And newly preparing a battery charge-discharge curve and a cycle performance curve.
For systematic evaluation of LiNi 1/3 Co 1/3 Mn 1/3 O 2 Electrochemical Properties of the cathode Material, liNi 1/3 Co 1/3 Mn 1/3 O 2 The positive electrode material was prepared as a coin cell, and the 1 st, 2 nd, 3 rd, 10 th, 20 th, 30 th cycle charge/discharge curves of the cell were determined. At the same time, the rate capability and cycle performance of the battery are also determined, and the measurement result is obtainedAs shown in fig. 6As shown. In thatFIG. 6(A) In the discharge at 0.1C rate, the synthesized material has initial specific discharge capacity and coulombic efficiency of 160.2mAhg –1 And 99.9%, showing that the material exhibits excellent cycling performance and higher coulombic efficiency.FIG. 6(B) The battery shows the cycling performance at 2.8-4.6V voltage and different discharge rates of 0.2C,0.5C and 1C. The initial discharge capacity of the material is 158.3, 155.6 and 148mAhg respectively –1 The discharge capacities after 30 cycles were 140.2, 138.4 and 135.3mAhg, respectively –1 . Thus, the synthesized LiNi 1/3 Co 1/3 Mn 1/3 O 2 The positive electrode material has high discharge capacity, good rate capability and excellent cycle performance.
The foregoing embodiments have described the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.
Claims (2)
1. A process for preparing the positive electrode material of Li-ion battery from the waste mixed alkaline battery includes such steps as splitting the waste alkaline battery, separating the positive electrode material from Al foil, dissolving, co-deposition reaction and calciningThe method comprises the following steps: (1) The positive and negative electrodes of the waste lithium ion battery are connected by a lead to enable the waste lithium ion battery to be self-discharged so as to prevent discharging or spontaneous combustion in the manual splitting process. Then, the aluminum foil and the positive electrode material were separated. For waste alkaline zinc-manganese batteries, a steel saw is used for sawing the battery collector, and the manganese-containing positive electrode material is manually separated. (2) Putting the lithium battery anode material and aluminum foil into NMP, performing ultrasonic treatment for 3min, filtering and drying. And obtaining the lithium ion battery anode active material. (3) With 6mol L -1 The nitric acid solution contains 2.5 percent of hydrogen peroxide to dissolve the mixed battery anode material and is filtered. Thus obtaining the mixed filtrate of nickel, cobalt and manganese with certain concentration. (4) Adjusting the molar ratio of nickel, cobalt and manganese in the solution to be 1 by using nickel nitrate, cobalt nitrate and manganese nitrate, maintaining the solution at 60 ℃ under the action of a constant-temperature magnetic stirrer, slowly dropwise adding 2.5mol/l sodium hydroxide solution to adjust the pH value of the solution to be 8, heating and evaporating the solution in a constant-temperature water bath at 70 ℃ while continuously stirring until viscous sol is completely formed, drying the sol at 110 ℃ for 5 hours to form dry gel, grinding and crushing the dry gel. (5) Uniformly mixing the crushed sample with a certain amount of lithium carbonate, and calcining the mixture for 10 hours in a muffle furnace at the temperature of 850 ℃ to obtain LiNi 1/3 Co 1/3 Mn 1/3 O 2 A ternary anode material of a lithium ion battery.
2. The method for preparing the lithium ion battery anode material by using the mixed waste alkaline batteries according to claim 1, wherein the ternary lithium ion battery anode material is prepared by mainly using the mixed waste alkaline battery (waste lithium cobalt oxide lithium ion batteries, waste alkaline zinc manganese batteries) anode material as a raw material, so that the waste alkaline batteries of different types can be recycled, the great waste of resources and the serious environmental pollution are avoided, the production cost of the battery anode material is reduced, and the method has good economic benefits and social benefits.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106532170A (en) * | 2016-12-19 | 2017-03-22 | 重庆汉岳科技发展有限公司 | Resource recycling process for waste lithium batteries |
| CN106848474A (en) * | 2017-04-18 | 2017-06-13 | 中科过程（北京）科技有限公司 | A kind of method of high efficiente callback positive electrode material precursor and lithium carbonate from lithium ion cell anode waste |
| CN108878866A (en) * | 2018-06-28 | 2018-11-23 | 山东理工大学 | The method for preparing ternary material precursor using waste and old lithium ion battery tertiary cathode material and recycling lithium |
| CN109136571A (en) * | 2018-09-28 | 2019-01-04 | 中南大学 | Method for extracting valuable metals from lithium ion battery mixed manganese-rich waste leachate |
| CN109244580A (en) * | 2018-09-18 | 2019-01-18 | 余姚市鑫和电池材料有限公司 | A method of efficiently preparing ternary precursor |
| CN110336014A (en) * | 2019-07-12 | 2019-10-15 | 贵州红星电子材料有限公司 | A kind of preparation method of unformed nickel-cobalt-manganese ternary presoma |
| CN111170376A (en) * | 2020-01-15 | 2020-05-19 | 南开大学 | Positive electrode material precursor and preparation method thereof |
| CN112054265A (en) * | 2020-09-30 | 2020-12-08 | 合肥国轩高科动力能源有限公司 | Method for recycling and reusing anode material of waste ternary lithium ion battery |
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2015
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106532170A (en) * | 2016-12-19 | 2017-03-22 | 重庆汉岳科技发展有限公司 | Resource recycling process for waste lithium batteries |
| CN106848474A (en) * | 2017-04-18 | 2017-06-13 | 中科过程（北京）科技有限公司 | A kind of method of high efficiente callback positive electrode material precursor and lithium carbonate from lithium ion cell anode waste |
| CN106848474B (en) * | 2017-04-18 | 2021-07-09 | 中科过程（北京）科技有限公司 | Method for recovering positive electrode material and lithium carbonate from lithium ion battery positive electrode waste material |
| CN108878866A (en) * | 2018-06-28 | 2018-11-23 | 山东理工大学 | The method for preparing ternary material precursor using waste and old lithium ion battery tertiary cathode material and recycling lithium |
| CN108878866B (en) * | 2018-06-28 | 2020-11-17 | 山东理工大学 | Method for preparing ternary material precursor and recovering lithium by using ternary cathode material of waste lithium ion battery |
| CN109244580A (en) * | 2018-09-18 | 2019-01-18 | 余姚市鑫和电池材料有限公司 | A method of efficiently preparing ternary precursor |
| CN109136571A (en) * | 2018-09-28 | 2019-01-04 | 中南大学 | Method for extracting valuable metals from lithium ion battery mixed manganese-rich waste leachate |
| CN110336014A (en) * | 2019-07-12 | 2019-10-15 | 贵州红星电子材料有限公司 | A kind of preparation method of unformed nickel-cobalt-manganese ternary presoma |
| CN110336014B (en) * | 2019-07-12 | 2021-04-13 | 贵州红星电子材料有限公司 | Preparation method of amorphous nickel-cobalt-manganese ternary precursor |
| CN111170376A (en) * | 2020-01-15 | 2020-05-19 | 南开大学 | Positive electrode material precursor and preparation method thereof |
| CN112054265A (en) * | 2020-09-30 | 2020-12-08 | 合肥国轩高科动力能源有限公司 | Method for recycling and reusing anode material of waste ternary lithium ion battery |
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Application publication date: 20151118 |