CN110838601A - Dry repairing method for failed lithium ion battery positive active material and material obtained by repairing - Google Patents

Dry repairing method for failed lithium ion battery positive active material and material obtained by repairing Download PDF

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CN110838601A
CN110838601A CN201911121828.1A CN201911121828A CN110838601A CN 110838601 A CN110838601 A CN 110838601A CN 201911121828 A CN201911121828 A CN 201911121828A CN 110838601 A CN110838601 A CN 110838601A
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ion battery
lithium ion
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不公告发明人
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Wuhan Ruijite 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4242—Regeneration of electrolyte or reactants
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • 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
    • 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
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    • Y02W30/84—Recycling of batteries or fuel cells

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Abstract

The invention belongs to the technical field of waste lithium ion battery recovery, and particularly relates to a dry method repairing method of a failed lithium ion battery positive active material and a lithium ion battery positive active material obtained by repairing. The repairing method comprises the following steps: 1) separating the failed lithium ion battery anode material from the aluminum current collector to obtain a lithium ion battery anode recycled material; 2) crushing the lithium ion battery anode recycled material to obtain lithium ion battery anode recycled material powder; 3) carrying out hydro-thermal treatment on the lithium ion battery anode recycled material powder in a lithium supplement agent; 4) and washing and drying the recovered material powder of the lithium ion battery anode, and calcining to obtain the repaired lithium ion battery anode active material. The inventor of the invention finds that the hydrothermal treatment in the step 3) can ensure that the morphology and the crystal structure of the failed lithium ion battery anode material after the lithium supplement calcination are recovered, and can also obviously reduce the time of the lithium supplement calcination.

Description

Dry repairing method for failed lithium ion battery positive active material and material obtained by repairing
Technical Field
The invention belongs to the technical field of waste lithium ion battery recovery, and particularly relates to a dry method repairing method of a failed lithium ion battery anode active material and a lithium ion battery anode active material obtained by repairing.
Background
Ternary nickel cobalt manganeseThe battery anode material is LiNi1-x-yCoxMnyO2The proportion of the lithium battery anode material with the general formula is 424, 333, 523, 811 and the like, and the proportion of the lithium battery anode material with the general formula is commonly seen in the industry. The ternary cathode material is a lithium battery cathode material with a layered structure, and has the characteristics of high specific capacity, stable cycle performance, relatively low cost, good safety performance and the like.
The world ternary positive electrode material manufacturers mainly focus on the south-japanese korean, which accounts for about 50% of the global market share. In 2016, the yield of the lithium battery anode material in China is 16.16 ten thousand tons, which is increased by 43 percent on a par with the same ratio. The yield of the ternary cathode material is 5.43 ten thousand tons, and the yield is increased by 49 percent on a same scale. From the production value, the production value of the lithium battery cathode material in 2016 exceeds 200 billion yuan, and is increased by more than 54% compared with that in 2015. Wherein, the market scale of the domestic ternary anode material is increased by over 70 percent in the same ratio, and the market scale is close to 80 hundred million yuan.
With the increasing market share of the ternary cathode material and the continuous increase of the global cobalt price, the recovery of the ternary cathode material has great economic value. At present, the main method for industrially treating the waste lithium ion batteries is to crush and separate the waste lithium ion batteries to obtain ternary positive electrode powder, then remove impurities from the obtained ternary positive electrode powder by a pyrogenic process or a wet leaching process, and finally carry out overall recovery or separation recovery by coprecipitation or extraction separation and other modes. However, the traditional pyrogenic recovery process has the problems of high energy consumption and low recovery rate, and the wet treatment has the problems of low metal separation rate, high cost, complex process, serious environmental pollution and the like although the recovery rate is higher.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a dry method repairing method of a failed lithium ion battery positive electrode active material and the lithium ion battery positive electrode active material obtained by repairing. The method has the characteristics of good repeatability, high resource utilization rate, simple process and high efficiency.
The technical scheme provided by the invention is as follows:
a dry method repairing method of a failure lithium ion battery anode active material comprises the following steps:
1) separating the failed lithium ion battery anode material from the aluminum current collector to obtain a lithium ion battery anode recycled material;
2) crushing the lithium ion battery anode recycled material obtained in the step 1) to obtain lithium ion battery anode recycled material powder;
3) carrying out hydrothermal treatment on the lithium ion battery anode recycled material powder obtained in the step 2) in a lithium supplement agent;
4) and (3) washing and drying the lithium ion battery anode recycled material powder subjected to the hydrothermal treatment in the step 3), and then calcining to obtain the repaired lithium ion battery anode active material.
In the prior art, although a technical scheme for repairing a failed lithium ion battery positive electrode material and a lithium supplement agent by calcining is disclosed, according to a result of repeated experiments, the failed lithium ion battery positive electrode material and the lithium supplement agent are directly calcined, so that the shape and the crystal structure of the failed lithium ion battery positive electrode material cannot be recovered.
Based on the technical scheme, the inventor of the invention finds that the morphology and the crystal structure of the failed lithium ion battery anode material after lithium supplement calcination can be recovered through the hydrothermal treatment in the step 3), and the time for lithium supplement calcination can be remarkably reduced.
Specifically, the lithium supplement agent is a mixed aqueous solution of at least two of lithium hydroxide, lithium sulfate, lithium acetate, lithium nitrate and lithium lactate.
In the technical scheme, each lithium supplement agent does not generate other side reactions, and the economic value is higher.
Specifically, the lithium supplement agent is a mixed aqueous solution of lithium hydroxide and lithium sulfate, the concentration of the lithium hydroxide is 2-5 mol/L, and the concentration of the lithium sulfate is 1-4 mol/L.
Specifically, the molar ratio of the lithium supplement agent to the lithium ion battery anode recycled material powder is 0.1-0.3: 1.
In the technical scheme, the lithium supplement agent consisting of the two lithium sources does not have other advantages in side reaction, and has higher economic value.
Based on the lithium supplement agent, the reaction is as follows:
Figure BDA0002275659220000031
specifically, the conditions of the hydrothermal treatment in the step 3) are as follows: the pressure is 1.5-3 MPa; the temperature is 750-950 ℃; the time is 10-12 h.
Specifically, the calcination conditions in step 4) are as follows: the calcination temperature is 700-800 ℃; the heating rate is 5 ℃/min; the heat preservation time can be 4-6 h.
Based on the technical scheme, the crystal form of the lithium battery anode recycled material can be recovered, and compared with the conventional dry sintering lithium supplement, the sintering temperature is reduced, and the sintering time is reduced.
Specifically, in step 1), the failed lithium ion battery positive electrode material is failed lithium cobaltate, a failed NCM ternary material 111, a failed NCM ternary material 523, a failed NCM ternary material 622, or a failed NCM ternary material 811.
Based on the technical scheme, the lithium ion battery anode material can be suitable for various types of lithium ion battery anode materials.
Specifically, in the step 1), the failed lithium ion battery positive electrode material and the aluminum current collector are crushed and then dissolved in NMP or DMF, and filter residue is obtained after filtration, namely the lithium ion battery positive electrode recycling material.
Specifically, in the step 2), the particle size of the lithium ion battery anode recycled material powder is less than or equal to 0.5 μm.
The invention also provides the lithium ion battery anode active material obtained by repairing the failed lithium ion battery anode active material according to the dry repairing method of the failed lithium ion battery anode active material.
Based on the technical scheme, the first charge capacity of the repaired ternary cathode material can reach 150mAh/g, and the coulombic efficiency can reach 85%.
Compared with the recovery and repair process of the ternary cathode material applied in the industry at present, the process technology has the following advantages:
1. the technology can obtain the battery-grade ternary cathode material by simply repairing the ternary cathode powder obtained by disassembly, and the cathode material can be directly used for manufacturing the lithium ion battery;
2. in the production process of the process, any organic solvent and acid-base substance are not added, so that waste liquid and waste residue are not generated basically, the waste water and waste residue treatment process is not required to be added, and the process is environment-friendly and economical;
3. the process can be used for manufacturing the lithium ion battery after directly supplementing lithium and sintering and repairing the recycled ternary material, has the advantages of good appearance and crystal line preservation, high recovery rate, economy, reasonableness and the like, provides a new way for recycling the waste lithium battery, and realizes efficient recycling of the waste lithium battery.
Drawings
FIG. 1 is a SEM photograph of the results of treatment with NCM523 before and after repair regeneration in example 1.
FIG. 2 is an XRD contrast before and after treatment with NCM523, before and after repair regeneration in example 1.
FIG. 3 is a graph comparing the charge and discharge curves of NCM 5231C before and after repair regeneration in example 1.
FIG. 4 is a graph comparing the charge and discharge curves of the NCM523 magnification before and after the repair regeneration in example 1.
FIG. 5 is a comparative plot of the charge-discharge cycle curves of NCM 5231C before and after repair regeneration in example 1.
Fig. 6 is a comparative graph of charge and discharge cycle curves of the respective materials in comparative example 1.
Fig. 7 is a system diagram of a mechanical separation system of an aluminum current collector and a positive electrode material.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
The dry repairing method of the failed lithium ion battery positive electrode active material comprises the following steps:
1) crushing a failed lithium ion battery positive electrode material and an aluminum current collector, dissolving the crushed materials in NMP, and filtering to obtain filter residue, namely a lithium ion battery positive electrode recycling material, wherein the failed lithium ion battery positive electrode material is a failed NCM ternary material 523;
2) drying the lithium ion battery anode recycled material obtained in the step 1), and then putting the dried lithium ion battery anode recycled material into a ball mill for crushing to obtain lithium ion battery anode recycled material powder, wherein the particle size of the lithium ion battery anode recycled material powder is less than 0.5 mu m;
3) carrying out hydrothermal treatment on the lithium ion battery anode recycled material powder obtained in the step 2) in a lithium supplement agent by using an autoclave, wherein the lithium supplement agent is a mixed aqueous solution of lithium hydroxide and lithium sulfate, the concentration of the lithium hydroxide is 3mol/L, the concentration of the lithium sulfate is 2mol/L, and the conditions of the hydrothermal treatment are as follows: the pressure is 2, the temperature is 815 ℃, the time is 11h, and the dosage ratio of the lithium ion battery anode recycled material powder to the lithium supplement agent is 1:0.25 (the amount of the substance n);
4) washing and drying the lithium ion battery anode recycled material powder subjected to hydrothermal treatment in the step 3), and then calcining, wherein the calcining conditions are as follows: the calcination temperature is 750 ℃; the heating rate is 5 ℃/min; the heat preservation time can be 5 hours, and the repaired lithium ion battery anode active material 1 is obtained.
The repaired anode material is measured, the first charge capacity is 150mAh/g, and the coulombic efficiency is 85%.
FIG. 1 is a SEM photograph of the NCM523 treated before and after the repair/regeneration in example 1. In the figure, from left to right, new materials, waste failure materials and regenerated materials are sequentially adopted, and it can be seen from the figure that the appearance of the NCM523 is more regular and uniform before repair after repair by the repair method of the invention.
As shown in FIG. 2, the XRD patterns before and after the NCM523 treatment before and after the repairing regeneration of example 1 are sequentially from top to bottom, namely, regenerated materials, waste failure materials and new materials, and as can be seen from the XRD patterns, the characteristic peaks of all samples are completely the same as the patterns of the commercial fresh ternary cathode materials before and after the repairing by the repairing method of the invention, the impurity phase does not exist, the diffraction peak is strong and sharp, the half peak width is narrow, the crystal crystallinity is good, and the value is α -NaFeO2Hexagonal layered structure, different in diffraction peak intensity ratio and splitting degree of the peak of each sampleAnd moreover, the repaired and regenerated materials have high strength ratio I (003)/I (104), which indicates that the materials have a good laminated structure.
FIG. 3 is a graph showing the charge and discharge curves of NCM 5231C before and after the repair regeneration in example 1. In the figure, the charging part is sequentially waste failure, regenerated material and new material from top to bottom; the discharge part is made of new materials, regenerated materials and waste failure sequentially from top to bottom. The graph shows that the discharge specific capacity of the repaired material is not greatly different from that of the commercial fresh anode ternary material, and most of the specific capacity can be recovered.
As shown in fig. 4, it is a graph of the charge and discharge rate of NCM523 before and after the repair regeneration in example 1. In the figure, new materials, recycled materials, and waste failures are sequentially formed from top to bottom. It can be seen from the figure that the specific capacity of the repaired ternary cathode material at each multiplying power is greatly improved compared with that of the abandoned failed ternary cathode material.
FIG. 5 is a graph showing the charge-discharge cycle of NCM 5231C before and after the repair regeneration in example 1. In the figure, new materials, recycled materials, and waste failures are sequentially formed from top to bottom. It can be seen from the figure that the cycle performance of the repaired ternary cathode material is greatly improved compared with the performance of the abandoned failed ternary cathode material.
Example 2
The dry repairing method of the failed lithium ion battery positive electrode active material comprises the following steps:
1) crushing a failed lithium ion battery positive electrode material and an aluminum current collector, dissolving the crushed materials in DMF, and filtering to obtain filter residue, namely a lithium ion battery positive electrode recycling material, wherein the failed lithium ion battery positive electrode material is a failed NCM ternary material 622;
2) drying the lithium ion battery anode recycled material obtained in the step 1), and then putting the dried lithium ion battery anode recycled material into a ball mill for crushing to obtain lithium ion battery anode recycled material powder, wherein the particle size of the lithium ion battery anode recycled material powder is less than 0.5 mu m;
3) carrying out hydrothermal treatment on the lithium ion battery anode recycled material powder obtained in the step 2) in a lithium supplement agent by using an autoclave, wherein the lithium supplement agent is a mixed aqueous solution of lithium hydroxide and lithium sulfate, the concentration of the lithium hydroxide is 4mol/L, the concentration of the lithium sulfate is 3mol/L, and the conditions of the hydrothermal treatment are as follows: the pressure is 2.5, the temperature is 880 ℃, the time is 11.5h, and the dosage ratio of the lithium ion battery anode recycled material powder to the lithium supplement agent is 1:0.15 (the amount of the substance n);
4) washing and drying the lithium ion battery anode recycled material powder subjected to hydrothermal treatment in the step 3), and then calcining, wherein the calcining conditions are as follows: the calcining temperature is 800 ℃; the heating rate is 5 ℃/min; the heat preservation time can be 6h, and the repaired lithium ion battery anode active material 1 is obtained.
The repaired anode material is measured, the first charge capacity is 165mAh/g, and the coulombic efficiency is 86%.
Example 3
The dry repairing method of the failed lithium ion battery positive electrode active material comprises the following steps:
1) crushing a failed lithium ion battery positive electrode material and an aluminum current collector, dissolving the crushed materials in NMP, and filtering to obtain filter residue, namely a lithium ion battery positive electrode recycling material, wherein the failed lithium ion battery positive electrode material is a failed NCM ternary material 111;
2) drying the lithium ion battery anode recycled material obtained in the step 1), and then putting the dried lithium ion battery anode recycled material into a ball mill for crushing to obtain lithium ion battery anode recycled material powder, wherein the particle size of the lithium ion battery anode recycled material powder is less than 0.5 mu m;
3) carrying out hydrothermal treatment on the lithium ion battery anode recycled material powder obtained in the step 2) in a lithium supplement agent by using an autoclave, wherein the lithium supplement agent is a mixed aqueous solution of lithium hydroxide and lithium sulfate, the concentration of the lithium hydroxide is 5mol/L, the concentration of the lithium sulfate is 4mol/L, and the conditions of the hydrothermal treatment are as follows: the pressure is 3, the temperature is 950 ℃, the time is 12 hours, and the dosage ratio of the lithium ion battery anode recycled material powder to the lithium supplement agent is 1:0.1 (the amount of the substance n);
4) washing and drying the lithium ion battery anode recycled material powder subjected to hydrothermal treatment in the step 3), and then calcining, wherein the calcining conditions are as follows: the calcination temperature is 750 ℃; the heating rate is 5 ℃/min; the heat preservation time can be 5 hours, and the repaired lithium ion battery anode active material 1 is obtained.
The repaired anode material is measured, the first charge capacity is 145mAh/g, and the coulombic efficiency is 87%.
Comparative example 1
And (4) reproducing by adopting a method disclosed by a direct high-temperature calcination paper to obtain the lithium ion battery cathode material 4.
The following measurements were made on the performance of the lithium ion battery positive electrode material 4, and the actual results are shown in fig. 6:
in the figure, the new material, the calcined material and the waste material are sequentially used from top to bottom. It can be seen that, in the direct high-temperature calcination method, the difference between the specific capacity of the waste spent ternary material and the specific capacity of the material after high-temperature calcination is not large, which indicates that the effect of the direct calcination method is almost not good.
The mechanical separation of the aluminum current collector from the positive electrode material can adopt a technical solution provided by the following contents, as shown in fig. 7, which is a system diagram of a mechanical separation system of the aluminum current collector from the positive electrode material:
1. discharging the recovered lithium ion battery, removing electrolyte, and crushing the anode of the lithium ion battery to 10-30um by a crusher;
2. the method comprises the following steps of introducing crushed materials into an airflow separator for separation, feeding heavy materials obtained after separation into a first vibrating screen from a heavy material outlet for screening, and feeding light materials obtained after separation into a cyclone separator from a light material outlet, wherein the first vibrating screen is provided with two layers of screens, the aperture of the heavy materials is 50 meshes and 325 meshes from top to bottom, the 50 meshes of the screen are mainly aluminum foil particles, the 325 meshes of the screen are materials with the particle size of 50-325 meshes and are separated anode materials, and the undersize of the last layer is materials with the particle size of less than 325 meshes and are separated anode materials;
3. the sorted materials are further sorted by a cyclone separator, the heavy materials obtained after sorting are sent into a second vibrating screen from a heavy material outlet to be screened, the light materials obtained after sorting are sent into a pulse dust collector from a light material outlet to be dedusted, wherein the second vibrating screen is provided with three layers of screens, the aperture of the third vibrating screen is 50 meshes, 100 meshes and 325 meshes from top to bottom, the 50 meshes are mainly aluminum foil particles and other mixed impurities, the 100 meshes are materials with the particle size of 50-100 meshes, the materials are separated anode materials, the 325 meshes are materials with the particle size of 100-325 meshes, the materials are separated anode materials, and the materials with the particle size of less than 325 meshes are sieved below the last layer;
4. combining oversize materials of the first vibrating screen and oversize materials of the second vibrating screen to obtain aluminum foil particles and other impurity materials; and combining undersize of the first vibrating screen and undersize of the first vibrating screen to obtain the available positive electrode material.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (9)

1. A dry method repairing method for a failed lithium ion battery positive electrode active material is characterized by comprising the following steps:
1) separating the failed lithium ion battery anode material from the aluminum current collector to obtain a lithium ion battery anode recycled material;
2) crushing the lithium ion battery anode recycled material obtained in the step 1) to obtain lithium ion battery anode recycled material powder;
3) carrying out hydrothermal treatment on the lithium ion battery anode recycled material powder obtained in the step 2) in a lithium supplement agent;
4) and (3) washing and drying the lithium ion battery anode recycled material powder subjected to the hydrothermal treatment in the step 3), and then calcining to obtain the repaired lithium ion battery anode active material.
2. The dry method repair method for the failed lithium ion battery positive electrode active material according to claim 1, characterized in that: the lithium supplementing agent is a mixed aqueous solution of at least two of lithium hydroxide, lithium carbonate, lithium sulfate, lithium acetate or lithium nitrate and lithium lactate.
3. The dry method repair method for the failed lithium ion battery positive electrode active material according to claim 2, characterized in that:
the lithium supplement agent is a mixed aqueous solution of lithium hydroxide and lithium sulfate, the concentration of the lithium hydroxide is 2-5 mol/L, and the concentration of the lithium sulfate is 1-4 mol/L;
the molar ratio of the lithium supplement agent to the lithium ion battery anode recycled material powder is 0.1-0.3: 1.
4. The dry method for repairing a failed lithium ion battery positive electrode active material according to claim 3, wherein the hydrothermal treatment in step 3) is performed under the following conditions: the pressure is 1.5-3 MPa; the temperature is 750-950 ℃; the time is 10-12 h.
5. The dry method repair method for the failed lithium ion battery positive electrode active material according to claim 4, characterized in that the calcination in step 4) is performed under the following conditions: the calcination temperature is 700-800 ℃; the heating rate is 5 ℃/min; the heat preservation time can be 4-6 h.
6. The dry method repair method for the failed lithium ion battery positive electrode active material according to any one of claims 1 to 5, characterized in that: in step 1), the failed lithium ion battery positive electrode material is failed lithium cobaltate, a failed NCM ternary material 111, a failed NCM ternary material 523, a failed NCM ternary material 622, or a failed NCM ternary material 811.
7. The dry method repair method for the failed lithium ion battery positive electrode active material according to any one of claims 1 to 5, characterized in that: in the step 1), crushing the failed lithium ion battery positive electrode material and the aluminum current collector, dissolving the crushed materials in NMP or DMF, and filtering to obtain filter residue, namely the lithium ion battery positive electrode recycled material.
8. The dry method repair method for the failed lithium ion battery positive electrode active material according to any one of claims 1 to 5, characterized in that: in the step 2), the particle size of the lithium ion battery anode recycled material powder is less than or equal to 0.5 μm.
9. The lithium ion battery positive active material obtained by repairing the failed lithium ion battery positive active material according to any one of claims 1 to 8 by the dry repairing method.
CN201911121828.1A 2019-11-15 2019-11-15 Dry repairing method for failed lithium ion battery positive active material and material obtained by repairing Pending CN110838601A (en)

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CN112670603A (en) * 2020-09-08 2021-04-16 华中科技大学 Method for repairing regenerated failed ternary material by physical method multi-medium cooperation
CN112713267A (en) * 2020-12-31 2021-04-27 中南大学 Lithium cobaltate composite material and preparation method and application thereof
CN112838205A (en) * 2021-01-11 2021-05-25 厦门厦钨新能源材料股份有限公司 Method for recovering fine powder of lithium ion battery cathode material
CN113582251A (en) * 2021-07-27 2021-11-02 上海纳米技术及应用国家工程研究中心有限公司 Method for recycling and regenerating anode material
CN114447465A (en) * 2022-01-14 2022-05-06 清华大学深圳国际研究生院 Method and material for synergistically regenerating anode material and cathode material of lithium ion battery and application of material
CN114597534A (en) * 2022-03-29 2022-06-07 西安交通大学 Method for in-situ repairing of waste ternary lithium battery cathode material through supercritical water
CN115724474A (en) * 2022-11-16 2023-03-03 清华大学深圳国际研究生院 Repairing method of failed layered positive electrode material, positive electrode material and application of positive electrode material
CN112670602B (en) * 2020-09-08 2023-07-25 华中科技大学 Regeneration and repair treatment method for ternary positive electrode material of lithium ion battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102017277A (en) * 2008-02-22 2011-04-13 S·E·斯鲁普 Reintroduction of lithium into recycled battery materials
CN106688135A (en) * 2014-08-06 2017-05-17 史蒂文·E·斯卢普 Recycling positive-electrode material of a lithium-ion battery
CN107069078A (en) * 2017-03-24 2017-08-18 中航锂电（洛阳）有限公司 A kind of recovery method of electrodes of lithium-ion batteries material
WO2019136397A1 (en) * 2018-01-05 2019-07-11 The Regents Of The University Of California Systems and methods for regeneration of lithium cathode materials

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102017277A (en) * 2008-02-22 2011-04-13 S·E·斯鲁普 Reintroduction of lithium into recycled battery materials
CN106688135A (en) * 2014-08-06 2017-05-17 史蒂文·E·斯卢普 Recycling positive-electrode material of a lithium-ion battery
CN107069078A (en) * 2017-03-24 2017-08-18 中航锂电（洛阳）有限公司 A kind of recovery method of electrodes of lithium-ion batteries material
WO2019136397A1 (en) * 2018-01-05 2019-07-11 The Regents Of The University Of California Systems and methods for regeneration of lithium cathode materials

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112670603A (en) * 2020-09-08 2021-04-16 华中科技大学 Method for repairing regenerated failed ternary material by physical method multi-medium cooperation
CN112670602B (en) * 2020-09-08 2023-07-25 华中科技大学 Regeneration and repair treatment method for ternary positive electrode material of lithium ion battery
CN112670603B (en) * 2020-09-08 2023-07-25 华中科技大学 Method for cooperatively repairing and regenerating failure ternary material by using physical method and multielement medium
CN112713267A (en) * 2020-12-31 2021-04-27 中南大学 Lithium cobaltate composite material and preparation method and application thereof
CN112838205A (en) * 2021-01-11 2021-05-25 厦门厦钨新能源材料股份有限公司 Method for recovering fine powder of lithium ion battery cathode material
CN112838205B (en) * 2021-01-11 2021-11-30 厦门厦钨新能源材料股份有限公司 Method for recovering fine powder of lithium ion battery cathode material
CN113582251A (en) * 2021-07-27 2021-11-02 上海纳米技术及应用国家工程研究中心有限公司 Method for recycling and regenerating anode material
CN114447465A (en) * 2022-01-14 2022-05-06 清华大学深圳国际研究生院 Method and material for synergistically regenerating anode material and cathode material of lithium ion battery and application of material
CN114597534A (en) * 2022-03-29 2022-06-07 西安交通大学 Method for in-situ repairing of waste ternary lithium battery cathode material through supercritical water
CN115724474A (en) * 2022-11-16 2023-03-03 清华大学深圳国际研究生院 Repairing method of failed layered positive electrode material, positive electrode material and application of positive electrode material
CN115724474B (en) * 2022-11-16 2023-12-08 清华大学深圳国际研究生院 Repairing method of failed layered positive electrode material, positive electrode material and application of positive electrode material

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