CN116588928A - Regeneration and repair method for waste graphite layer structure - Google Patents
Regeneration and repair method for waste graphite layer structure Download PDFInfo
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- CN116588928A CN116588928A CN202310434459.1A CN202310434459A CN116588928A CN 116588928 A CN116588928 A CN 116588928A CN 202310434459 A CN202310434459 A CN 202310434459A CN 116588928 A CN116588928 A CN 116588928A
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- acid
- graphite
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- waste
- graphite layer
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 80
- 239000010439 graphite Substances 0.000 title claims abstract description 80
- 239000002699 waste material Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000008929 regeneration Effects 0.000 title claims abstract description 8
- 238000011069 regeneration method Methods 0.000 title claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004327 boric acid Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002696 manganese Chemical class 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 230000001172 regenerating effect Effects 0.000 claims description 13
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical group Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 235000002867 manganese chloride Nutrition 0.000 claims description 6
- 239000011565 manganese chloride Substances 0.000 claims description 6
- 229940099607 manganese chloride Drugs 0.000 claims description 6
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 21
- 239000010926 waste battery Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011366 tin-based material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
-
- 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
Abstract
The invention relates to the field of battery recovery, in particular to a regeneration and repair method of a waste graphite layer structure. The method comprises the steps of mixing graphite waste, manganese salt and/or nickel salt, boric acid and alcohol reagent after acid washing and impurity removal, drying, and then heating at high temperature and impurity removal. The method provided by the invention can be used for efficiently recycling the electrode graphite powder in the waste lithium ion battery, and the recycled graphite has an excellent layer structure, so that the electrochemical performance of the regenerated graphite is effectively improved.
Description
Technical Field
The invention belongs to the field of battery recovery, and particularly relates to a regeneration and repair method of a waste graphite layer structure.
Background
With the rapid development of new energy automobile industry, china becomes the first major new energy automobile producing and selling country in the world. The installed amount of the power battery is also rising year by year while the new energy automobile industry is rapidly developed. The service life of the power battery is generally 5-8 years, and after the battery capacity is reduced to below 80%, the service requirement of the new energy automobile cannot be effectively met. Estimated to 2025, the total amount of retired power batteries in China can reach 78 ten thousand tons.
The invention discloses a method for preparing a high-capacity negative electrode material by utilizing recycled graphite, which comprises the steps of mixing a silicon-based/tin-based material with a carbon source with cohesiveness, and performing liquid-phase mixing and high-temperature carbonization to achieve an ideal carbon coating effect on the silicon-based or tin-based material to obtain the high-capacity negative electrode material. However, there is currently little research on the graphite recovery process in waste batteries, some of which are mentioned only as by-products, and the literature is mainly focused on improving the purity of the recovered graphite, while there is little research on the layer structure of the recovered graphite. The industrially recovered graphite can only meet the requirements of preparing low-value materials at present, but cannot meet the performance requirements of high-value materials such as battery-grade graphite. At present, the waste graphite recycled in the waste battery negative electrode material in the field has large interlayer spacing and poor electrochemical performance, so that a person skilled in the art needs to provide a method for recycling graphite with an excellent layer structure in the waste lithium battery negative electrode material.
Disclosure of Invention
In order to solve the technical problems, the invention provides a regeneration and repair method for a waste graphite layer structure.
In a first aspect, the method for regenerating and repairing the waste graphite layer structure provided by the invention comprises the steps of mixing graphite waste subjected to acid washing and impurity removal, manganese salt and/or nickel salt, boric acid and alcohol reagents, drying, and then heating at high temperature and removing impurities. The invention utilizes the magnetic element manganese or nickel and boric acid to calcine and repair the waste graphite layer structure at high temperature, thereby improving the electrochemical performance of the regenerated graphite. The invention can realize the efficient recovery of high-purity electrode graphite powder in waste lithium ion batteries, and the recovered graphite has the characteristics of excellent layer structure, good graphite layer spacing of the regenerated graphite, high graphite purity, wide application range and the like, and has excellent electrochemical performance.
Preferably, the regeneration and repair method of the waste graphite layer structure comprises the following steps:
1) Acid washing and impurity removal: carrying out acid washing and impurity removal on graphite waste in a mixed solution of an acid washing solvent and a hydrogen peroxide reagent, and filtering and washing to obtain acid-washed graphite;
2) Mixing: mixing the acid-washed graphite, manganese salt and/or nickel salt, boric acid and alcohol reagent;
3) And (3) drying: stirring and drying the mixture obtained in the step 2);
4) And (3) high-temperature heating: heating the dried material in the step 3) at a high temperature;
5) Dilute acid or deionized water to remove impurities: and (3) treating the graphite subjected to the high-temperature heating in the step 4) by using a dilute acid solvent or deionized water.
Preferably, in the step 1), the acid washing reagent is sulfuric acid or methanesulfonic acid, the concentration of the acid washing reagent is 0.5-5 mol/L, the hydrogen peroxide reagent is 30% hydrogen peroxide, and the dosage of the hydrogen peroxide reagent is 5-15 vol%; and/or the treatment temperature is 50-90 ℃; and/or the treatment time is 0.5-2.5 h; the liquid-solid ratio is 50-200: 1ml/g.
Preferably, in the step 2), the manganese salt is manganese chloride or manganese sulfate, and the nickel salt is nickel chloride; more preferably, the manganese salt is manganese chloride.
Further preferably, in the step 2), the mol ratio of the acid-washed graphite, the manganese salt and the boric acid is 1-5:1:1, preferably 1.5-2:1:1; the alcohol reagent is preferably an alcohol with a concentration of more than 90%.
In the invention, experimental researches have unexpectedly found that when the preferred acid-washed graphite, manganese salt, boric acid and alcohol with the molar mass ratio and the concentration of more than 90% are adopted, the acid-washed graphite layer structure is closer to commercial graphite with excellent performance, and the acid-washed graphite layer structure shows more excellent electrochemical performance.
Further preferably, in the step 3), the temperature of stirring and drying is 60-90 ℃ and the drying time is 3-5 h.
Further preferably, in the step 4), the heating atmosphere is argon, the heating temperature is 500-1200 ℃, and the heating time is 3-6 hours; preferably, the heating temperature is 700-1000 ℃, the heating time is 4-6 h, and the heating is performed under argon atmosphere.
Further preferably, in the step 5), the diluted acid solvent is diluted hydrochloric acid or deionized water, and the concentration of the diluted acid solvent is 0.05-0.1 mol/L.
Further preferably, in the step 5), the reaction temperature is 30-90 ℃, the liquid-solid ratio is 50-100:1 ml/g, and the reaction time is 1-2 h.
According to the invention, through optimizing and adjusting the molar mass ratio of graphite to boric acid to manganese salt, the conditions of heating atmosphere and the like, the mixed treatment of manganese salt and boric acid can obviously improve the graphite layer structure after high-temperature heating, so that the regenerated graphite has a better regenerated graphite layer-to-layer interval range and shows more excellent electrochemical performance.
In a second aspect, the invention provides an application of the regeneration repair method of the waste graphite layer structure in regenerating and repairing the waste graphite layer structure in waste materials of waste lithium ion batteries, preferably an application in recycling high-purity electrode graphite powder in negative materials of the waste lithium ion batteries; preferably, the recycled graphite layer spacing is preferably close to 3.36nm, and the recycled graphite exhibits more excellent electrochemical performance as the recycled graphite layer spacing of the present invention reaches 3.359nm.
The invention has the advantages that: the method for regenerating and repairing the waste graphite layer structure provides a new idea for treating the waste batteries, and is beneficial to realizing resource circulation. The method has the advantages of simplicity, high efficiency, mild conditions and the like, can realize the high-efficiency recovery of the high-purity electrode graphite powder in the waste lithium ion battery, improves the electrochemical performance recovered in the waste battery negative electrode material, and the recovered graphite has an excellent layer structure, meets the performance requirements of high-value graphite materials, and can improve the electrochemical performance of the regenerated graphite.
Drawings
In order to more clearly illustrate the embodiments of the present invention and the technical solutions of the prior art, the following description will briefly explain the embodiments or the drawings needed in the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
Figure 1 is an XRD pattern (right image is a partial enlargement of left image) of the product obtained in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention are clearly and completely described below. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods. The examples are not intended to identify the particular technology or conditions, and are either conventional or are carried out according to the technology or conditions described in the literature in this field or are carried out according to the product specifications. The reagents and instruments used, etc. are not identified to the manufacturer and are conventional products available for purchase by regular vendors.
In the embodiment of the invention, the used waste battery is a waste lithium ion battery with the model INR18650P manufactured by Chaowei company. The waste graphite raw material is obtained by manual disassembly and crushing.
In the embodiment of the invention, the graphite layer structure test is carried out according to the GB/T24533-2019 method. The XRD test device used an X-ray diffractometer (XRD-7000).
In the embodiment of the invention, 70% methane sulfonic acid (aqueous solution) and concentrated sulfuric acid are purchased from Tongguangjingyi; 30% hydrogen peroxide (aqueous solution) was purchased from the national drug group; boric acid and manganese chloride were purchased from Beijing Yili Fine chemicals Co.
In the embodiment of the invention, the negative electrode plate of the waste battery is calcined at 500 ℃, and the graphite of the negative electrode powder and the copper of the current collector are separated after the calcination.
The invention will be further illustrated with reference to examples.
Example 1
Disassembling the waste batteries, and stripping the batteries and the negative electrode powder after high-temperature calcination. And removing impurities by using a mixed solution of 1.5mol/L methanesulfonic acid and 10vol% of 30% hydrogen peroxide at 90 ℃ under the conditions that the liquid-solid ratio is 50:1ml/g and the pickling time is 1.5h, and drying in vacuum to obtain the pickled graphite.
Fully mixing the pickled graphite, the manganese chloride and the boric acid with the molar ratio of 1.5:1:1, placing the mixture into 15ml of 95% alcohol, and stirring and drying at 90 ℃ until the alcohol is completely volatilized. And then taking out the dried sample, and placing the dried material in a tubular furnace in an argon atmosphere for heating and calcining at 700 ℃ for 4 hours. The calcined acid-washed graphite is subjected to simple impurity removal by deionized water under the conditions of 60 ℃ and liquid-solid ratio of 100:1ml/g and reaction time of 1h, and the impurity removal is followed by drying to obtain the regenerated graphite, wherein the interlayer spacing of the regenerated graphite is 3.359nm. The XRD pattern of the product obtained in this example is shown in FIG. 1.
Example 2
Disassembling the waste batteries, and stripping the batteries and the negative electrode powder after high-temperature calcination. And (3) removing impurities by using a mixed solution of 2mol/L methanesulfonic acid and 10vol% of 30% hydrogen peroxide at 90 ℃ under the conditions that the liquid-solid ratio is 50:1ml/g and the pickling time is 1.5h, and drying in vacuum to obtain the pickled graphite.
Fully mixing the graphite, the nickel chloride and the boric acid which are subjected to acid washing in a molar ratio of 2:1:1, putting the mixture into 20ml of 95% alcohol, and stirring and drying at 90 ℃ until the alcohol is completely volatilized. And then taking out the dried sample, and placing the dried material in a tubular furnace in an argon atmosphere for heating and calcining at 700 ℃ for 4 hours. The calcined waste negative electrode graphite is simply decontaminated by using 0.05mol/L hydrochloric acid solution at 60 ℃ under the conditions that the liquid-solid ratio is 100:1ml/g and the reaction time is 1h, and the waste negative electrode graphite is dried after decontaminating, so that the regenerated graphite with the interlayer spacing of 3.346nm is obtained.
Example 3
Disassembling the waste batteries, and stripping the batteries and the negative electrode powder after high-temperature calcination. And removing impurities by using a mixed solution of 1.5mol/L methanesulfonic acid and 10vol% of 30% hydrogen peroxide at 90 ℃ under the conditions that the liquid-solid ratio is 50:1ml/g and the pickling time is 1.5h, and drying in vacuum to obtain the pickled graphite.
Fully mixing the pickled graphite, manganese chloride and boric acid with the molar ratio of 2:1:1, placing the mixture in 20ml of 95% alcohol, and stirring and drying at 90 ℃ until the alcohol is completely volatilized. And then taking out the dried sample, and placing the dried material in a tubular furnace in an argon atmosphere for heating and calcining at 700 ℃ for 4 hours. The calcined waste negative electrode graphite is simply decontaminated by using 0.05mol/L hydrochloric acid solution at 60 ℃ under the conditions that the liquid-solid ratio is 100:1ml/g and the reaction time is 1h, and the regenerated graphite interlayer spacing is 3.352nm after decontaminating and drying.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A regeneration and restoration method for a waste graphite layer structure is characterized by comprising the steps of mixing graphite waste subjected to acid washing and impurity removal, manganese salt and/or nickel salt, boric acid and alcohol reagents, drying, and then heating at high temperature and removing impurities.
2. The method for regenerating and repairing the waste graphite layer structure according to claim 1, which is characterized by comprising the following steps:
1) Acid washing and impurity removal: carrying out acid washing and impurity removal on graphite waste in a mixed solution of an acid washing solvent and a hydrogen peroxide reagent, and filtering and washing to obtain acid-washed graphite;
2) Mixing: mixing the acid-washed graphite, manganese salt and/or nickel salt, boric acid and alcohol reagent;
3) And (3) drying: stirring and drying the mixture obtained in the step 2);
4) And (3) high-temperature heating: heating the dried material in the step 3) at a high temperature;
5) Dilute acid or deionized water to remove impurities: and (3) treating the graphite subjected to the high-temperature heating in the step 4) by using a dilute acid solvent or deionized water.
3. The method for regenerating and repairing the waste graphite layer structure according to claim 2, wherein in the step 1), the acid washing reagent is sulfuric acid or methanesulfonic acid, the concentration of the acid washing reagent is 0.5-5 mol/L, the hydrogen peroxide reagent is 30% hydrogen peroxide, and the dosage of the hydrogen peroxide reagent is 5-15 vol%; and/or the treatment temperature is 50-90 ℃; and/or the treatment time is 0.5-2.5 h; the liquid-solid ratio is 50-200: 1ml/g.
4. The method for regenerating and repairing a waste graphite layer structure according to claim 2 or 3, wherein in the step 2), the manganese salt is manganese chloride or manganese sulfate, and the nickel salt is nickel chloride.
5. The method for regenerating and repairing a waste graphite layer structure according to claim 4, wherein in the step 2), the molar ratio of the acid-washed graphite to the manganese salt to the boric acid is 1-5:1:1.
6. The method for regenerating and repairing a waste graphite layer structure according to any one of claims 2 to 5, wherein in the step 3), the temperature of stirring and drying is 60 ℃ to 90 ℃ and the drying time is 3 to 5 hours.
7. The method for regenerating and repairing a waste graphite layer structure according to any one of claims 2 to 6, wherein in the step 4), the heating atmosphere is argon, the heating temperature is 500 to 1200 ℃, and the heating time is 3 to 6 hours.
8. The method for regenerating and repairing a waste graphite layer structure according to any one of claims 2 to 7, wherein in the step 5), the diluted acid solvent is diluted hydrochloric acid, and the concentration of the diluted acid solvent is 0.05 to 0.1mol/L.
9. The method for regenerating and repairing the waste graphite layer structure according to claim 8, wherein in the step 5), the reaction temperature is 30-90 ℃, the liquid-solid ratio is 50-100:1 ml/g, and the reaction time is 1-2 h.
10. Use of the method for regenerating and repairing a spent graphite layer structure according to any one of claims 1 to 9 in regenerating and repairing a spent graphite layer structure in a spent material of a spent lithium ion battery.
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