CN111370799A - Pretreatment method for failure lithium ion battery anode material - Google Patents

Pretreatment method for failure lithium ion battery anode material Download PDF

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CN111370799A
CN111370799A CN201911394857.5A CN201911394857A CN111370799A CN 111370799 A CN111370799 A CN 111370799A CN 201911394857 A CN201911394857 A CN 201911394857A CN 111370799 A CN111370799 A CN 111370799A
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Wuhan Ruijiete 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
    • H01M10/54—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
    • 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
    • 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
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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    • 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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Abstract

A pretreatment method for a failed lithium ion battery anode material comprises the following steps: s1, weighing lithium salt, and adding water to prepare a lithium salt solution with the concentration of more than or equal to 0.1 mol/L; wherein, the lithium salt is inorganic lithium salt; s2, testing the lithium deficiency ratio x of the failed positive electrode material, and mixing the lithium salt solution of S1 with the failed positive electrode material to obtain a mixture; wherein the molar ratio of lithium in the lithium salt solution to the positive electrode material is more than or equal to the lithium deficiency ratio x of the failed positive electrode material; s3 placing the mixture of S2 in a high-pressure hydrothermal kettleHydrothermal reaction was carried out, and Li of the mixture in the pot was monitored+The concentration is not reduced continuously until the reaction is finished; wherein the hydrothermal reaction temperature is more than or equal to 100 ℃; and S4, cooling, filtering to remove the solvent, washing with water to remove the residual lithium salt, and drying to obtain the lithium-supplemented cathode material. The method can improve the regeneration efficiency and performance index of the recycled material, has good repeatability, high resource utilization rate, simple and efficient working procedures and very high social and economic values.

Description

Pretreatment method for failure lithium ion battery anode material
Technical Field
The invention relates to a method for recycling, repairing and regenerating a retired lithium ion battery material, in particular to a method for pretreating a failed lithium ion battery anode material, and belongs to the field of waste lithium ion battery recycling and resource recycling.
Background
In recent years, the demand for lithium ion batteries has proliferated in the rapidly growing consumer electronics, electric vehicles and energy storage markets, bringing along a large number of retired batteries. According to statistics, the cumulative waste lithium battery in 2018 in China reaches 12.08GWH, and the cumulative scrap amount reaches about 17.25 ten thousand tons. If a common garbage disposal method is adopted, metals such as cobalt, nickel, lithium, manganese and the like, inorganic compounds and organic compounds in the garbage disposal method can cause serious pollution. And the high-price rare metals such as lithium, cobalt, nickel and the like can avoid environmental pollution through effective recovery treatment, can be about a large amount of production cost for battery manufacturers, and has very high economic value. In view of the huge amount, environmental protection and precious resources, the recovery of waste lithium batteries is very necessary and has become a research hotspot around the world.
The existing recovery method of the failure lithium ion battery anode material mainly comprises pyrometallurgy and hydrometallurgy. The pyrometallurgy is mainly to disassemble the battery and then directly calcine the battery at high temperature to obtain metal oxide or metal alloy, and the method has high energy consumption and causes environmental pollution; the hydrometallurgy mainly comprises the steps of dissolution, extraction, separation, precipitation and the like to obtain various elements or compounds, the method has complex working procedures, and acid and alkali are used in the process to pollute the environment.
Compared with the recovery process, the other simple and green treatment, recovery and regeneration method is used, namely, the waste materials are not decomposed and element separated, but lithium is directly supplemented and synthesized into the materials which can be used by the battery.
Aiming at a failure positive electrode material lacking lithium, the existing lithium supplement technology is mainly lithium preparation sintering, and the method is used for sintering at the material phase forming temperature (700 ℃) by preparing lithium salt and the failure material in a proper proportion so as to achieve the purposes of lithium supplement and capacity recovery. The method is convenient and quick, but the lithium supplementing effect is not ideal, and the Li/Me ratio is not more than 90% after lithium supplementation.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a pretreatment method of a failed lithium ion battery anode material, which is used for supplementing lithium to the failed lithium ion battery anode material caused by working conditions such as circulation, high temperature and multiplying power by a hydrothermal method, and is beneficial to improving the regeneration efficiency and performance index of a recycled material; meanwhile, the method has the advantages of good repeatability, high resource utilization rate, simple and efficient process and very high social and economic values.
In order to achieve the above technical object, the present invention adopts the following technical solutions.
A pretreatment method for a failed lithium ion battery anode material comprises the following steps:
s1 weighing lithium salt, adding water to prepare lithium salt solution with concentration more than or equal to 0.1 mol/L.
Wherein the lithium salt is inorganic lithium salt, more preferably LiOH and Li2CO3、Li2SO4One or more of (a) and (b).
Preferably, the concentration of the lithium salt solution is 1 to 5mol/L, preferably 2 to 5 mol/L.
S2 testing the lithium deficiency ratio x of the failed positive electrode material, and mixing the lithium salt solution of S1 with the failed positive electrode material to obtain a mixture.
And the molar ratio of lithium in the lithium salt solution to the failed positive electrode material is more than or equal to the lithium deficiency ratio x of the failed positive electrode material.
More preferably, the molar ratio of lithium in the lithium salt solution to the spent positive electrode material is 2 to 20 times, and more preferably 2 to 5 times, the lithium deficiency ratio x of the spent positive electrode material.
The failure positive electrode material is layered LiMeO2Wherein Me is one or more of Ni, Co or Mn;
or the anode material is olivine LiMePO4Wherein Me is one or a mixture of two of Fe or Mn.
Specifically, the failure positive electrode material is a failure positive electrode material of a capacity fading battery caused by working conditions such as circulation, high temperature and multiplying power.
S3 hydrothermal reaction of the mixture S2 in a high-pressure hydrothermal kettle, and monitoring Li of the mixture in the kettle+And (4) until the concentration does not continuously decrease, finishing the reaction.
Wherein the hydrothermal reaction temperature is more than or equal to 100 ℃.
Specifically, Li of the mixture in the kettle is monitored by a pH meter or acid-base titration+And (4) concentration.
And after the S4S 3 reaction is finished, cooling, filtering to remove the solvent, washing with water to remove residual lithium salt, and drying to obtain the lithium-supplement cathode material.
After washing with water, the pH was tested and when the pH was <9.0, it indicated that the washing was sufficient.
Preferably, the drying temperature is 50-300 ℃, preferably 130-200 ℃, and the drying time is 0.5-5h, preferably 2-5h, and the drying is completed when the weight is not reduced any more.
By adopting the scheme, the invention achieves the following technical effects.
According to the pretreatment method of the invalid lithium ion battery anode material, the invalid anode material of the capacity fading battery caused by working conditions such as circulation, high temperature and multiplying power is supplemented with lithium by a hydrothermal method, so that the regeneration efficiency and performance index of a recycled material are improved; meanwhile, the method has the advantages of good repeatability, high resource utilization rate, simple and efficient process and very high social and economic values.
Drawings
FIG. 1 is a graph comparing the lithium element contents of the positive electrode material before and after lithium replenishment in example 1;
FIG. 2 is an XRD contrast of the positive electrode material before and after lithium replenishment in example 1;
FIG. 3 is a graph comparing the lithium element contents of the positive electrode material before and after lithium replenishment in example 2;
FIG. 4 is a comparison of the specific discharge capacity of coin cells at 0.1C prepared from the positive electrode materials before and after lithium replenishment in example 3;
fig. 5 is an XRD comparison pattern of the positive electrode materials after lithium supplementation of example 4 and comparative experimental example;
fig. 6 is a comparison of the specific discharge capacity of coin cells 0.1C prepared from the positive electrode materials of example 4 and comparative examples after lithium supplementation.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a pretreatment method of a failure lithium ion battery anode material, which comprises the following steps:
s1 weighing lithium salt, adding water to prepare lithium salt solution with concentration more than or equal to 0.1 mol/L.
Wherein the lithium salt is inorganic lithium salt, more preferably LiOH and Li2CO3、Li2SO4One or more of (a) and (b).
Preferably, the concentration of the lithium salt solution is 1 to 5mol/L, preferably 2 to 5 mol/L.
S2 testing the lithium deficiency ratio x of the failed positive electrode material, and mixing the lithium salt solution of S1 with the failed positive electrode material to obtain a mixture.
And the molar ratio of lithium in the lithium salt solution to the failed positive electrode material is more than or equal to the lithium deficiency ratio x of the failed positive electrode material.
More preferably, the molar ratio of lithium in the lithium salt solution to the spent positive electrode material is 2 to 20 times, and more preferably 2 to 5 times, the lithium deficiency ratio x of the spent positive electrode material.
The failure positive electrode material is layered LiMeO2Wherein Me is one or more of Ni, Co or Mn;
or the anode material is olivine LiMePO4Wherein Me is one or a mixture of two of Fe or Mn.
Specifically, the failure positive electrode material is a failure positive electrode material of a capacity fading battery caused by working conditions such as circulation, high temperature and multiplying power.
S3 hydrothermal reaction of the mixture S2 in a high-pressure hydrothermal kettle, and monitoring Li of the mixture in the kettle+And (4) until the concentration does not continuously decrease, finishing the reaction.
Wherein the hydrothermal reaction temperature is more than or equal to 100 ℃.
Specifically, Li of the mixture in the kettle is monitored by a pH meter or acid-base titration+And (4) concentration.
And after the S4S 3 reaction is finished, cooling, filtering to remove the solvent, washing with water to remove residual lithium salt, and drying to obtain the lithium-supplement cathode material.
After washing with water, the pH was tested and when the pH was <9.0, it indicated that the washing was sufficient.
Preferably, the drying temperature is 50-300 ℃, the drying time is 0.5-5h, preferably 2-5h, and the drying is finished when the weight is not reduced any more.
Example 1
A pretreatment method for a failed lithium ion battery anode material comprises the following steps:
s1 LiOH 7.66g is weighed in a beaker by an electronic balance, 80ml of distilled water is added by a pipette, and the solution is dissolved by magnetic stirring for 20min to prepare 4mol/L lithium salt solution.
S2 test for failed positive electrode material NCM523 (LiNi) with ICP0.5Co0.2Mn0.3O2) The Li/Me ratio in this example was found to be 0.81, and the lithium deficiency ratio was 0.19. Weighing 25.0g of the failed positive electrode material, adding a lithium salt solution of S1 to enable the molar ratio of lithium in the lithium salt solution to the failed positive electrode material to be 3.5, namely 17 times of the lithium deficiency ratio x, and magnetically stirring for 10min to obtain a mixture.
S3 transferring the mixture of S2 to a high-pressure hydrothermal kettle with a tetrafluoro lining, carrying out hydrothermal reaction at 200 ℃, and monitoring Li of the mixture in the kettle by a pH meter or acid-base titration in the process+When the concentration is not reduced any more, the hydrothermal reaction is finished for 8 h.
S4 was cooled to 50 ℃, the autoclave was opened, filtered, washed 3 times with distilled water, and the PH of the filtrate was measured using a precision PH paper, which in this example was 7.6, and washed sufficiently with water.
And then, placing the washed material in a forced air drying oven, and drying for 2h at 130 ℃ to obtain the lithium-supplement anode material.
The Li/Me of the positive electrode material after lithium supplement in this example is measured by ICP is 1.06, and the Li/Me test results of the positive electrode material before and after lithium supplement are shown in fig. 1, from which it can be seen that lithium element in the failed positive electrode material has been completely supplemented by the method in this example.
The X-ray diffraction analysis of the positive electrode material before and after lithium supplementation in this example showed that the crystal phase of the material was unchanged, but the crystallinity was higher and the impurity phase was reduced, as shown in fig. 2.
Example 2
A pretreatment method for a failed lithium ion battery anode material comprises the following steps:
s1 weighing 22.17g of Li by using electronic balance2CO3In a beaker, 60ml of distilled water was added by a pipette and dissolved by magnetic stirring for 10min to prepare a 5mol/L lithium salt solution.
S2 testing for failed positive electrode material LiCoO with ICP2The Li/Co ratio in this example was found to be 0.60 and the lithium deficiency ratio was 0.40. 56g of the failure positive electrode material is weighed, lithium salt solution of S1 is added to enable the molar ratio of lithium of the lithium salt solution to the failure positive electrode material to be 3, namely 7.5 times of the lithium deficiency ratio x, and magnetic stirring is carried out for 10min to obtain a mixture.
S3 transferring the mixture S2 to a high-pressure hydrothermal kettle with a tetrafluoro lining, carrying out hydrothermal reaction at 240 ℃, and monitoring Li of the mixture in the kettle by a pH meter or acid-base titration in the process+When the concentration is not reduced any more, the hydrothermal reaction is finished for 4 h.
S4 was cooled to 30 ℃, the autoclave was opened, filtered, washed 3 times with distilled water, and the PH of the filtrate was measured using a precision PH paper, which in this example was 8.2, and washed sufficiently with water.
And then, placing the washed material in a forced air drying oven, and drying for 1h at 150 ℃ to obtain the lithium-supplement cathode material.
The Li/Co of the positive electrode material obtained by the ICP test in this example was 0.99, and the Li/Co test results of the positive electrode material before and after lithium supplementation are shown in fig. 3, from which it can be seen that the lithium element in the failed positive electrode material was completely supplemented by the method in this example.
Example 3
A pretreatment method for a failed lithium ion battery anode material comprises the following steps:
s1, weighing 0.72g of LiOH in a beaker by using an electronic balance, adding 30ml of distilled water by using a transfer pipette, and magnetically stirring for 10min for dissolving to prepare 1mol/L lithium salt solution;
s2 LiFePO of failure anode material tested by ICP4The Li/Fe ratio was found to be 0.65 and the lithium deficiency ratio was found to be 0.35. Weighing 2.37g of the failed positive electrode material, adding a lithium salt solution of S1 to enable the molar ratio of lithium in the lithium salt solution to the failed positive electrode material to be 2, namely 5.7 times of the lithium deficiency ratio x, and magnetically stirring for 10min to obtain a mixture.
S3 transferring the mixture S2 to a high-pressure hydrothermal kettle with a tetrafluoro lining, carrying out hydrothermal reaction at 180 ℃, and monitoring Li in the mixture in the kettle by a pH meter or acid-base titration in the process+When the concentration is not reduced any more, the hydrothermal reaction is finished for 6 hours;
s4 was cooled to 50 ℃, the autoclave was opened, filtered, washed 3 times with distilled water, and the filtrate was tested for PH using a precision PH paper, which in this example was found to be 7.2, and washed thoroughly.
And then, placing the washed material in a forced air drying oven, and drying at 200 ℃ for 0.5h to obtain the lithium-supplement cathode material.
The lithium-supplemented cathode material obtained in this example was tested for Li/Fe of 1.03 using ICP. Further, the positive electrode material is made into a button cell, performance test is carried out, the test result is shown in fig. 4, the material capacity is recovered to a normal level, and the method of the embodiment is verified to be sufficient in lithium supplement.
Example 4
A pretreatment method for a failed lithium ion battery anode material comprises the following steps:
s1 LiOH 1.44g is weighed into a beaker by an electronic balance, 80ml of distilled water is added by a pipette, and the solution is dissolved by magnetic stirring for 20min to prepare a lithium salt solution of 2 mol/L.
S2 test for failed positive electrode material NCM111 (LiNi) with ICP1/3Co1/3Mn1/3O2) The Li/Me ratio in this example was found to be 0.70 and the lithium deficiency ratio was 0.30. Weighing 41.1g of the failure positive electrode material, adding a lithium salt solution of S1 to enable the molar ratio of lithium in the lithium salt solution to the failure positive electrode material to be 2, namely 6.7 times of the lithium deficiency ratio x, and magnetically stirring for 10min to obtain a mixture.
S3 transferring the mixture S2 to a high-pressure hydrothermal kettle with a tetrafluoro lining, carrying out hydrothermal reaction at 220 ℃, and monitoring Li of the mixture in the kettle by a pH meter or acid-base titration in the process+When the concentration is not reduced any more, the hydrothermal reaction is finished for 4 h.
S4 was cooled to 50 ℃, the autoclave was opened, filtered, washed 3 times with distilled water, and the PH of the filtrate was measured using a precision PH paper, which in this example was 7.8, and washed sufficiently with water.
And then, placing the washed material in a forced air drying oven, and drying at 200 ℃ for 0.5h to obtain the lithium-supplement cathode material.
The lithium-supplemented cathode material obtained in this example was tested for Li/Me of 1.08 using ICP.
The positive electrode material obtained by lithium supplementation in the embodiment was subjected to X-ray diffraction analysis, and performance tests were performed on the positive electrode material prepared as a button cell, with the test results shown in fig. 5 and 6.
Comparative examples
This comparative example is similar to example 4 except that after S4, the resulting material was sintered at a high temperature of 850 ℃ for 12 hours in a tube furnace in an oxygen atmosphere. The material Li/Me was further tested with ICP-1.06.
The positive electrode material for lithium supplement obtained in this comparative example was subjected to X-ray diffraction analysis, and the positive electrode material was made into a button cell, and performance tests were performed, and the test results are shown in fig. 5 and 6.
From fig. 4 and fig. 5, it can be seen that after lithium is supplemented by the hydrothermal lithium supplementation method of example 4, the structure and capacity of the cathode material are both restored to normal levels, which verifies that the hydrothermal lithium supplementation method is sufficient without a high-temperature sintering step.
The technical solution provided by the present invention is not limited by the above embodiments, and all technical solutions formed by utilizing the structure and the mode of the present invention through conversion and substitution are within the protection scope of the present invention.

Claims (10)

1. A pretreatment method for a failed lithium ion battery anode material is characterized by comprising the following steps:
s1, weighing lithium salt, and adding water to prepare a lithium salt solution with the concentration of more than or equal to 0.1 mol/L;
wherein, the lithium salt is inorganic lithium salt;
s2, testing the lithium deficiency ratio x of the failed positive electrode material, and mixing the lithium salt solution of S1 with the failed positive electrode material to obtain a mixture;
wherein the molar ratio of lithium in the lithium salt solution to the positive electrode material is more than or equal to the lithium deficiency ratio x of the failed positive electrode material;
s3 hydrothermal reaction of the mixture S2 in a high-pressure hydrothermal kettle, and monitoring Li of the mixture in the kettle+The concentration is not reduced continuously until the reaction is finished;
wherein the hydrothermal reaction temperature is more than or equal to 100 ℃;
and after the S4S 3 reaction is finished, cooling, filtering to remove the solvent, washing with water to remove residual lithium salt, and drying to obtain the lithium-supplement cathode material.
2. The method of claim 1, wherein the method comprises the steps of: the lithium salt in S1 is LiOH or Li2CO3、Li2SO4One or more of (a) and (b).
3. The method of claim 1, wherein the method comprises the steps of:
the failure positive electrode material is layered LiMeO2Where Me is one or more of Ni, Co or MnMixing;
or the anode material is olivine LiMePO4Wherein Me is one or a mixture of two of Fe or Mn.
4. The method of claim 3, wherein the method comprises the steps of: the failure positive electrode material is a failure positive electrode material of a capacity fading battery caused by working conditions of circulation, high temperature and multiplying power.
5. The method of claim 3, wherein the method comprises the steps of:
in S4, wash with water to pH < 9.0.
6. The method of claim 3, wherein the method comprises the steps of: the drying temperature is 50-300 ℃.
7. The method of claim 1, wherein the method comprises the steps of: the concentration of lithium salt in S1 is 2-5 mol/L.
8. The method according to claim 1, wherein the method comprises the following steps: the molar ratio of lithium in the lithium salt solution in the S2 to the positive electrode material is 2-20 times of the lithium deficiency ratio x.
9. The method of claim 1, wherein the method comprises the steps of: the molar ratio of lithium in the lithium salt solution in the S2 to the positive electrode material is 2-5 times of the lithium deficiency ratio x.
10. The method of claim 1, wherein the method comprises the steps of: the temperature of the hydrothermal reaction is 180 ℃ and 240 ℃, and the reaction time is 4-8 h.
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Cited By (5)

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CN110729524A (en) * 2019-11-12 2020-01-24 上海纳米技术及应用国家工程研究中心有限公司 Method for repairing lithium ion battery anode material
CN112349989A (en) * 2020-11-05 2021-02-09 武汉大学 Method for repairing and regenerating waste lithium ion battery positive electrode active material and obtained regenerated positive electrode active material
CN112786987A (en) * 2021-02-10 2021-05-11 昆明理工大学 Regeneration method of retired lithium ion battery positive electrode material
CN113328161A (en) * 2021-05-14 2021-08-31 昆明理工大学 Method for preparing monocrystal-like ternary cathode material by regenerating waste lithium ion battery cathode material
CN117074398A (en) * 2023-10-12 2023-11-17 天津力神电池股份有限公司 Pre-lithiated material effectiveness detection method and pole piece pre-lithiated material detection method

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