Recovery method for waste ternary battery

Abstract

Disclosed herein is a recovery method for a waste ternary battery, belonging to the technical field of material recovery. The method comprises: disassembling a waste ternary battery to obtain an electrode sheet; then carrying out vacuum impurity removal, and separating and recovering an active substance; and finally, by means of a specific restoration means, restoring and regenerating the active substance. The method not only can effectively avoid using treatment reagents, such as strong acid and strong base, of high contamination rates and high cost rates, but also involves mild processing conditions and can be implemented in atmospheric-pressure states, and a restored and regenerated positive electrode material has a low impurity content and excellent electrochemical performance.

Description

A recycling method for waste ternary batteries Technical Field

[0001] This article relates to the field of material recycling technology, and in particular to a method for recycling waste ternary batteries. Background Art

[0002] Since used ternary batteries contain a lot of metal elements such as lithium, nickel, and manganese, if they are not recycled in time, not only will these metal resources be wasted, but also environmental pollution will be caused. At present, there are three main methods for recycling used ternary batteries: pyrometallurgical recycling, wet extraction recycling, and direct recycling. Pyrometallurgical recycling uses a high-temperature smelting process to directly burn used ternary batteries, and then chemically separate the recyclable elements. This method is simple to operate, but it consumes a lot of energy and has a low degree of recovery. Wet extraction recycling uses used ternary batteries to extract and recover different materials in sections using different extractants. Although it can achieve a high recovery level and relatively low energy consumption, the operation process is very complicated, involves many types of extraction reagents, and may also generate new sources of pollution. Direct recovery uses physical means to separate physical screening and then conduct special recycling. The materials recovered by this method have high impurities and unstable quality.

[0003] Summary of the Invention

[0004] The purpose of this article is to overcome the shortcomings of the above-mentioned existing technologies and provide a method for recycling waste ternary batteries. This method first disassembles the waste ternary batteries to obtain pole pieces, then performs vacuum removal of impurities, and then separates and recovers the active substances. Finally, the active substances are repaired and regenerated by specific repair means. This method can not only effectively avoid the use of high-pollution and high-cost treatment reagents such as strong acids and strong alkalis, but also has mild processing conditions and can be achieved under normal pressure. The positive electrode material obtained by repair and regeneration has a low impurity content and excellent electrochemical performance.

[0005] To achieve the above objectives, the technical solutions adopted in this paper are:

[0006] A method for recycling waste ternary batteries comprises the following steps:

[0007] Disassemble the waste ternary battery to obtain the positive electrode sheet;

[0008] calcining the positive electrode sheet at 100-200° C. for 0.5-2 h under a vacuum degree of -0.1-0.2 MPa to obtain a pretreated positive electrode sheet;

[0009] The pretreated positive electrode sheet is placed in an organic extract and ultrasonically stirred at 80-150°C for 0.5-1 hour. The resulting suspension is allowed to stand for solid-liquid separation. The resulting solid is ultrasonically stirred under the same conditions for three times. The resulting precipitate is washed, solid-liquid separated, dried, and crushed to obtain the isolated active substance.

[0010] The separated active material is tested for lithium content and the amount of lithium deficiency is determined. The separated active material is then crushed in water, and an organic lithium salt or its derivative is added according to the amount of lithium deficiency. An additive is then added and mixed. The resulting mixture is stirred and reacted at 80 to 100° C. for 1 to 4 hours. Water is added in real time during the reaction to maintain a constant water level. After the reaction is complete, the separated solid is dried and crushed to obtain the repaired active material. The additive is a mixture of ascorbic acid and hydrogen peroxide, and the volume percentage concentration of the additive in the mixture is 0.1 to 0.5 vol%.

[0011] The repaired active material is mixed with an inorganic lithium source and calcined at 750-900° C. for 3-6 hours in air or oxygen atmosphere to obtain a repaired and regenerated positive electrode material.

[0012] In the recycling method of waste ternary batteries described in this article, compared with the existing method of directly soaking the positive electrode sheet in strong acid and strong alkali, the positive electrode sheet is first treated by a low-temperature vacuum impurity removal method. This treatment can not only effectively accelerate the rapid volatilization of the residual electrolyte in the positive electrode sheet, but also quickly inactivate the binder (such as PVDF, etc.) contained in the positive electrode sheet. Subsequently, under the action of the organic extract, the active material in the positive electrode sheet can be separated from impurities such as the binder at a temperature of only 80 to 150 ° C, thereby obtaining an active material with higher purity. Subsequently, in order to repair the active material with lithium, an organic lithium salt is used when introducing a lithium salt. The applicant has found through experiments that, compared with inorganic lithium salts, using an organic lithium salt or its derivative as a lithium source for lithium replenishment can promote the volatilization of impurity ions during subsequent high-temperature solid-phase calcination, thereby improving the purity of the recovered positive electrode material. On the other hand, when performing the lithium replenishment reaction, a specific additive needs to be introduced. The additive can effectively improve the redox kinetics of the relithiation of the active material, reduce the energy barrier of the reaction, and thus effectively reduce the conditions required for the reaction. Therefore, the lithium replenishment stage can react directly at normal pressure, effectively reducing energy consumption. Finally, the repaired active material is mixed with an inorganic lithium source (used to supplement the lithium loss during calcination) and calcined at high temperature to fix the crystal phase, thereby obtaining a repaired and regenerated ternary positive electrode material. The material has high purity and high electrochemical activity and can be directly used to re-prepare the positive electrode sheet of the ternary battery.

[0013] In one embodiment, the positive electrode material in the waste ternary battery is a nickel-cobalt-manganese positive electrode material, and the molar ratio of nickel, cobalt and manganese in the positive electrode material is (1-8): (1-2): (1-4).

[0014] In the recycling method of waste ternary batteries described in this article, the processing object can be any of the commonly used NCM111, NCM424, NCM523, NCM622 or NCM811 system batteries, as long as they are normally retired and have not been damaged or significantly expanded.

[0015] In one embodiment, when the pretreated positive electrode sheet is placed in an organic extract for ultrasonic stirring treatment, the solid-liquid ratio of the pretreated positive electrode sheet to the organic extract is 1:(2-4); the organic extract is at least one of pyrrolidone, N,N-dimethylformamide, and dimethyl sulfoxide; the frequency of the ultrasonic stirring treatment is 20-25kHz, the power is 30-35kW, and the stirring speed is 60-12r / min.

[0016] Due to the previous vacuum decontamination stage, most of the electrolyte in the positive electrode sheet has been removed, and the remaining inorganic binder is also inactivated during the heating process. It only needs to be effectively separated from the active substance by ultrasonic-assisted low-heat treatment in a conventional organic extract.

[0017] In one embodiment, the suspension after ultrasonic stirring is allowed to stand for 2 to 4 hours.

[0018] In one embodiment, the separated active material is tested for lithium content using an inductively coupled plasma emission spectrometer, the detected lithium deficiency amount is x, where the unit of x is mol, and the molar ratio of the lithium element in the organic lithium salt to the lithium element in the separated active material is ≥x.

[0019] In one embodiment, the stirring rate of the mixed solution containing the separation active substance, the organic lithium salt and the additive during the stirring reaction is 200-600 r / min.

[0020] Furthermore, the organic lithium salt is at least one of lithium acetate, lithium lactate, LiCF3SO3, and LiN(SO2CF3)2.

[0021] In one embodiment, the mass ratio of ascorbic acid to hydrogen peroxide in the additive is 1-9.

[0022] Through experimental research, it was found that when the two are within this ratio range, the energy level of the lithium replenishment reaction of the active substance is reduced to the greatest extent, which can further improve the degree of lithium replenishment.

[0023] In one embodiment, the water content of the repaired active substance is ≤1 wt %, and the average particle size is 8-12 μm.

[0024] In one embodiment, the inorganic lithium salt is lithium carbonate, and the molar ratio of the repaired active substance to the lithium carbonate is 1:0.01 to 0.05.

[0025] In one embodiment, the heating rate during the calcination of the repaired active material and the inorganic lithium source is 2-5° C. / min.

[0026] Compared with the existing technology, the beneficial effects of this article are:

[0027] This article provides a method for recycling waste ternary batteries. The method first disassembles the waste ternary batteries to obtain electrodes, then performs vacuum removal, separates and recovers the active substances, and finally repairs and regenerates the active substances through specific repair means. This method can not only effectively avoid the use of high-pollution and high-cost treatment reagents such as strong acids and strong alkalis, but also has mild processing conditions and can be achieved under normal pressure. The positive electrode material obtained by repair and regeneration has low impurity content and excellent electrochemical performance. After being assembled into a lithium-ion battery, the reversible specific capacity reaches 155-170mAh / g, and the first efficiency reaches more than 85%, indicating that the recycled product is comparable to new ternary positive electrode materials, and is in line with the integrated industrial system of recycling, repair and regeneration, and application of waste ternary batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] FIG1 is a scanning electron microscope image of the separated active substance (a) and the repaired and regenerated positive electrode material (b) obtained in Example 2 described herein.

[0029] FIG2 is a graph showing the XRD test comparison results of the separated active substance and repaired regenerated positive electrode material obtained in Example 2 described herein and the pure new material. DETAILED DESCRIPTION

[0030] To better illustrate the purpose, technical solutions and advantages of this article, this article will be further described below with reference to the accompanying drawings and specific embodiments.

[0031] Unless otherwise specified, the materials used in the examples and comparative examples can be obtained through commercial channels.

[0032] The lithium iron phosphate scraps used in the various embodiments and comparative examples herein are all commercially recycled ternary batteries, all of which are normal retired products without any damage, bulging, or expansion. In addition to the current collector aluminum foil, active material, conductive agent, and binder, the positive electrode sheets do not contain too many additional impurities.

[0033] Example 1

[0034] An embodiment of the method for recycling waste ternary batteries described herein includes the following steps:

[0035] (1) Dismantling the waste NCM523 (i.e., the active material of the positive electrode material is nickel-cobalt-manganese ternary material, and the molar ratio of the three elements is 5:2:3) ternary battery under argon atmosphere to obtain the positive electrode sheet;

[0036] (2) calcining the positive electrode sheet at 150° C. for 2 h under a vacuum of −0.1 MPa to obtain a pretreated positive electrode sheet;

[0037] (3) The pretreated positive electrode sheet was placed in a reactor containing an organic extract of pyrrolidone at a solid-liquid ratio of 1:2, and then ultrasonically stirred at 80°C for 1 hour, with an ultrasonic frequency of 24 kHz, a power of 32 kW, and a stirring rate of 120 r / min. The resulting suspension was allowed to stand for 4 hours before solid-liquid separation. The resulting solid was ultrasonically stirred under the same conditions for three times. The resulting precipitate was washed, solid-liquid separated, dried, and crushed to obtain the isolated active substance.

[0038] (4) The separated active material was tested for lithium content using an inductively coupled plasma spectrometer and the lithium deficiency was determined to be 0.2 mol. The separated active material was then crushed in water and a 2 mol / L lithium acetate aqueous solution was added at a solid-liquid ratio of 1:2 according to the lithium deficiency, and then 0.1 vol% of an additive (a mixture of ascorbic acid and hydrogen peroxide at a mass ratio of 3:1) was added and mixed. The resulting mixture was stirred at 100° C. at a rate of 200 r / min for 4 h. Water was added in real time during the reaction to maintain a constant water level. After the reaction was complete, the separated solid was dried to a moisture content of ≤1 wt% and crushed to an average particle size of 8 μm to obtain the repaired active material.

[0039] (5) The repaired active material was mixed with 1 mol% inorganic lithium source lithium carbonate and heated to 810°C at a rate of 2°C / min in an air atmosphere and calcined for 3 h to obtain a repaired and regenerated positive electrode material.

[0040] Example 2

[0041] An embodiment of the method for recycling waste ternary batteries described herein includes the following steps:

[0042] (1) Dismantling waste NCM111 (i.e., the active material of the positive electrode material is nickel-cobalt-manganese ternary material, and the molar ratio of the three elements is 1:1:1) ternary batteries under argon atmosphere to obtain positive electrode sheets;

[0043] (2) calcining the positive electrode sheet at 200°C for 0.5h under a vacuum degree of -0.1MPa to obtain a pretreated positive electrode sheet;

[0044] (3) The pretreated positive electrode sheet was placed in a reactor containing an organic extract of pyrrolidone at a solid-liquid ratio of 1:4, and then ultrasonically stirred at 150°C for 0.5h, with an ultrasonic frequency of 24kHz, a power of 32kW, and a stirring rate of 60r / min. The resulting suspension was allowed to stand for 2h before solid-liquid separation. The resulting solid was ultrasonically stirred under the same conditions for three times. The resulting precipitate was washed, solid-liquid separated, dried, and crushed to obtain the isolated active substance.

[0045] (4) The separated active material was tested for lithium content using an inductively coupled plasma spectrometer and the lithium deficiency was determined to be 0.4 mol. The separated active material was then crushed in water and a 4 mol / L lithium lactate aqueous solution was added according to the solid-liquid ratio of 1:2 based on the lithium deficiency. 0.2 vol% of an additive (a mixture of ascorbic acid and hydrogen peroxide in a mass ratio of 3:1) was then added and mixed. The resulting mixture was stirred at 80°C at a rate of 200 r / min for 4 h. Water was added during the reaction to maintain the water level constant. After the reaction was complete, the separated solid was dried to a moisture content of ≤1 wt% and crushed to an average particle size of 8 μm to obtain the repaired active material.

[0046] (5) The repaired active material was mixed with 5 mol% inorganic lithium source lithium carbonate and heated to 850°C at a rate of 5°C / min in an air atmosphere and calcined for 4 h to obtain a repaired and regenerated positive electrode material.

[0047] Example 3

[0048] An embodiment of the method for recycling waste ternary batteries described herein includes the following steps:

[0049] (1) Dismantling waste NCM622 (i.e., the active material of the positive electrode material is nickel-cobalt-manganese ternary material, and the molar ratio of the three elements is 6:2:2) ternary batteries under argon atmosphere to obtain positive electrode sheets;

[0050] (2) calcining the positive electrode sheet at 150° C. for 1 h under a vacuum degree of -0.1 MPa to obtain a pretreated positive electrode sheet;

[0051] (3) The pretreated positive electrode sheet was placed in a reactor containing an organic extract of pyrrolidone at a solid-liquid ratio of 1:4, and then ultrasonically stirred at 150°C for 0.5h, with an ultrasonic frequency of 24kHz, a power of 32kW, and a stirring rate of 60r / min. The resulting suspension was allowed to stand for 2h before solid-liquid separation. The resulting solid was ultrasonically stirred under the same conditions for three times. The resulting precipitate was washed, solid-liquid separated, dried, and crushed to obtain the isolated active substance.

[0052] (4) The separated active material was tested for lithium content using an inductively coupled plasma spectrometer and the lithium deficiency was determined to be 0.4 mol. The separated active material was then crushed in water and a 4 mol / L lithium lactate aqueous solution was added according to the solid-liquid ratio of 1:2 based on the lithium deficiency. 0.2 vol% of an additive (a mixture of ascorbic acid and hydrogen peroxide in a mass ratio of 3:1) was then added and mixed. The resulting mixture was stirred at 80°C at a rate of 200 r / min for 4 h. Water was added during the reaction to maintain the water level constant. After the reaction was complete, the separated solid was dried to a moisture content of ≤1 wt% and crushed to an average particle size of 10 μm to obtain the repaired active material.

[0053] (5) The repaired active material was mixed with 5 mol% inorganic lithium source lithium carbonate and heated to 830°C at a rate of 5°C / min in an air atmosphere and calcined for 3 h to obtain a repaired and regenerated positive electrode material.

[0054] Example 4

[0055] An embodiment of the method for recycling waste ternary batteries described herein differs from Example 1 only in that the additive is a mixture of ascorbic acid and hydrogen peroxide in a mass ratio of 1:3.

[0056] Example 5

[0057] An embodiment of the method for recycling waste ternary batteries described herein differs from Example 2 only in that the additive is a mixture of ascorbic acid and hydrogen peroxide in a mass ratio of 1:3.

[0058] Example 6

[0059] An embodiment of the method for recycling waste ternary batteries described herein differs from Example 3 only in that the additive is a mixture of ascorbic acid and hydrogen peroxide in a mass ratio of 1:3.

[0060] Comparative Example 1

[0061] A method for recycling waste ternary batteries, which differs from Example 1 only in that the additive is ascorbic acid.

[0062] Comparative Example 2

[0063] A method for recycling waste ternary batteries, which differs from Example 2 only in that the additive is ascorbic acid.

[0064] Comparative Example 3

[0065] A method for recycling waste ternary batteries, which differs from Example 3 only in that the additive is ascorbic acid.

[0066] Comparative Example 4

[0067] A method for recycling waste ternary batteries, which differs from Example 1 only in that the additive is hydrogen peroxide.

[0068] Comparative Example 5

[0069] A method for recycling waste ternary batteries, which differs from Example 2 only in that the additive is hydrogen peroxide.

[0070] Comparative Example 6

[0071] A method for recycling waste ternary batteries, which differs from Example 3 only in that the additive is hydrogen peroxide.

[0072] Comparative Example 7

[0073] A method for recycling waste ternary batteries, which differs from Example 1 only in that it comprises the following steps:

[0074] (1) Dismantle the waste NCM523 ternary battery under argon atmosphere to obtain the positive electrode sheet;

[0075] (2) Soaking the positive electrode sheet in a 0.5 mol / L phosphoric acid solution at a solid-liquid ratio of 1:3 for 1 hour while stirring the solution during the soaking process. The resulting precipitate was washed, solid-liquid separated, dried, and crushed to separate the active material.

[0076] (3) The separated active material was tested for lithium content using an inductively coupled plasma spectrometer and the lithium deficiency was determined to be 0.2 mol. The separated active material was then crushed in water and a 2 mol / L lithium acetate aqueous solution was added at a solid-liquid ratio of 1:2 according to the lithium deficiency, and then 0.1 vol% of an additive (a mixture of ascorbic acid and hydrogen peroxide at a mass ratio of 3:1) was added and mixed. The resulting mixture was stirred at 100° C. at a rate of 200 r / min for 4 h, and water was added in real time during the reaction to maintain a constant water level. After the reaction was complete, the separated solid was dried to a moisture content of ≤1 wt% and crushed to an average particle size of 8 μm to obtain the repaired active material.

[0077] (4) The repaired active material was mixed with 1 mol% inorganic lithium source lithium carbonate and heated to 810°C at a rate of 2°C / min in an air atmosphere and calcined for 3 h to obtain a repaired and regenerated positive electrode material.

[0078] Comparative Example 8

[0079] A method for recycling waste ternary batteries, which differs from Example 1 only in that the calcination temperature in step (2) is 80°C.

[0080] Comparative Example 9

[0081] A method for recycling waste ternary batteries, which differs from Example 1 only in that the calcination temperature in step (2) is 300°C.

[0082] Comparative Example 10

[0083] A method for recycling waste ternary batteries, which differs from Example 1 only in that the calcination temperature in step (2) is 80°C and is set at normal pressure.

[0084] Comparative Example 11

[0085] A method for recycling waste ternary batteries, which differs from Example 1 only in that the calcination temperature in step (2) is 300°C and is set at normal pressure.

[0086] Comparative Example 12

[0087] A method for recycling waste ternary batteries comprises the following steps:

[0088] (1) Dismantle the waste NCM523 ternary battery under argon atmosphere to obtain the positive electrode sheet;

[0089] (2) calcining the positive electrode sheet at 150° C. for 2 h under a vacuum of −0.1 MPa to obtain a pretreated positive electrode sheet;

[0090] (3) The pretreated positive electrode sheet was placed in a reactor containing an organic extract of pyrrolidone at a solid-liquid ratio of 1:2, and then ultrasonically stirred at 80°C for 1 hour, with an ultrasonic frequency of 24 kHz, a power of 32 kW, and a stirring rate of 120 r / min. The resulting suspension was allowed to stand for 4 hours before solid-liquid separation. The resulting solid was ultrasonically stirred under the same conditions for three times. The resulting precipitate was washed, solid-liquid separated, dried, and crushed to obtain the isolated active substance.

[0091] (4) The separated active material was tested for lithium content using an inductively coupled plasma spectrometer and the lithium deficiency was determined to be 0.2 mol. The separated active material was then crushed in water and a 2 mol / L lithium acetate aqueous solution was added according to the solid-liquid ratio of 1:2 based on the lithium deficiency. The resulting mixture was ultrasonically treated at 100° C. (frequency 24 kHz, power 32 kW) and stirred at 200 r / min for 4 h. Water was added in real time during the reaction to maintain a constant water level. After the reaction was complete, the separated solid was dried to a moisture content of ≤1 wt% and crushed to an average particle size of 8 μm to obtain the repaired active material.

[0092] (5) The repaired active material was mixed with 1 mol% inorganic lithium source lithium carbonate and heated to 810°C at a rate of 2°C / min in an air atmosphere and calcined for 3 h to obtain a repaired and regenerated positive electrode material.

[0093] Comparative Example 13

[0094] A method for recycling waste ternary batteries comprises the following steps:

[0095] (1) Dismantle the waste NCM523 ternary battery under argon atmosphere to obtain the positive electrode sheet;

[0096] (2) calcining the positive electrode sheet at 150° C. for 2 h under a vacuum of −0.1 MPa to obtain a pretreated positive electrode sheet;

[0097] (3) The pretreated positive electrode sheet was placed in a reactor containing an organic extract of pyrrolidone at a solid-liquid ratio of 1:2, and then ultrasonically stirred at 80°C for 1 hour, with an ultrasonic frequency of 24 kHz, a power of 32 kW, and a stirring rate of 120 r / min. The resulting suspension was allowed to stand for 4 hours before solid-liquid separation. The resulting solid was ultrasonically stirred under the same conditions for three times. The resulting precipitate was washed, solid-liquid separated, dried, and crushed to obtain the isolated active substance.

[0098] (4) The separated active material was tested for lithium content using an inductively coupled plasma spectrometer and the lithium deficiency was determined to be 0.2. The separated active material was then crushed in water and a 2 mol / L lithium acetate aqueous solution was added according to the solid-liquid ratio of 1:2 based on the lithium deficiency. The resulting mixture was stirred at 100° C. at a rate of 200 r / min for 4 h. Water was added in real time during the reaction to maintain a constant water level. After the reaction was complete, the separated solid was dried to a moisture content of ≤1 wt% and crushed to an average particle size of 8 μm to obtain the repaired active material.

[0099] (5) The repaired active material was mixed with 1 mol% inorganic lithium source lithium carbonate and heated to 810°C at a rate of 2°C / min in an air atmosphere and calcined for 3 h to obtain a repaired and regenerated positive electrode material.

[0100] Comparative Example 14

[0101] A method for recycling waste ternary batteries, which differs from Example 1 only in that the lithium acetate aqueous solution is replaced by a lithium carbonate aqueous solution with an equal molar amount of lithium ions.

[0102] Effect Example 1

[0103] The liquid content and fluorine content of the separated active substances obtained by the recovery methods of the embodiments and comparative examples were statistically analyzed. The aluminum content of the finally prepared repaired and regenerated positive electrode materials was tested. Subsequently, commercial PVDF and conductive carbon black were mixed in a mass ratio of 8:1:1 and coated on aluminum foil to prepare pole pieces. Finally, commercial lithium sheets and commercial separators were used to assemble lithium-ion button cells. The first discharge specific capacity and the first charge-discharge efficiency were statistically analyzed under the current density conditions of 3-4.2 VV and 0.1 C (unit capacity is 160 mAh / g), where:

[0104] Liquid content (%) is the mass difference of the separated active substance after high-temperature drying at 200°C for 24 h / the mass of the separated active substance after drying × 100%;

[0105] The fluoride content (%) is the mass ratio of fluoride ions in the separated active substances, which is directly obtained by the fluoride ion selective electrode test method.

[0106] The results are shown in Table 1.

[0107] Table 1

[0108] Scanning electron microscopy observations of the isolated active material and the repaired and regenerated material prepared by the method described in Example 2, as shown in Figures 1(a) and (b), show that the repaired and regenerated material prepared by the method described herein has a good and complete morphology and is very similar to the active material separated from the positive electrode sheet. Furthermore, XRD analysis of the two was performed and compared with pure new materials, as shown in Figure 2. It can be seen that the method described herein has a high degree of repair and regeneration of the isolated active material, and the prepared repaired and regenerated material has a high purity.

[0109] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this article and are not intended to limit the scope of protection of this article. Although this application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of this article may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of this article.

Claims

1. A method for recycling waste ternary batteries, characterized in that: The following steps are involved: Dismantle the waste ternary battery to obtain the positive electrode sheet; The positive electrode sheet is calcined at 100 to 200° C. for 0.5 to 2 hours under a vacuum degree of -0.1 to -0.2 MPa to obtain a pretreated positive electrode sheet; The pretreated positive electrode sheet is placed in an organic extract and subjected to ultrasonic stirring treatment at 80-150°C for 0.5-1h. The obtained suspension is allowed to stand for solid-liquid separation. The obtained solid is subjected to ultrasonic stirring treatment under the same conditions for three times. The obtained precipitate is washed, solid-liquid separated, dried, and crushed to obtain the separated active substance. The separated active substance is tested for lithium content and the amount of lithium deficiency is determined. The separated active substance is then crushed in water and an organic lithium salt or its derivative is added according to the amount of lithium deficiency. An additive is then added and mixed. The resulting mixed solution is stirred and reacted at 80 to 100° C. for 1 to 4 hours. Water is added in real time during the reaction to maintain a constant water level. After the reaction is complete, the separated solid is dried and crushed to obtain a repaired active substance. The additive is a mixture of ascorbic acid and hydrogen peroxide, and the volume percentage concentration of the additive in the mixed solution is 0.1 to 0.5 vol%. The repaired active material is mixed with an inorganic lithium source and calcined at 750-900°C for 3-6 hours in an air or oxygen atmosphere to obtain a repaired and regenerated positive electrode material.

2. The method for recycling waste ternary batteries as claimed in claim 1, characterized in that: The positive electrode material in the waste ternary battery is a nickel-cobalt-manganese positive electrode material, and the molar ratio of nickel, cobalt and manganese in the positive electrode material is (1-8): (1-2): (1-4).

3. The method for recycling waste ternary batteries as claimed in claim 1, characterized in that: When the pretreated positive electrode sheet is placed in an organic extract for ultrasonic stirring treatment, the solid-liquid ratio of the pretreated positive electrode sheet to the organic extract is 1:(2-4).

4. The method for recycling waste ternary batteries as claimed in claim 3, characterized in that: The organic extract is at least one of pyrrolidone, N,N-dimethylformamide and dimethyl sulfoxide.

5. The method for recycling waste ternary batteries as claimed in claim 1, characterized in that: The separated active substance is tested for lithium content by inductively coupled plasma emission spectrometer, the detected lithium deficiency is x, and the molar ratio of lithium element in the organic lithium salt to lithium element in the separated active substance is ≥x.

6. The method for recycling waste ternary batteries as claimed in claim 1, characterized in that: The organic lithium salt is at least one of lithium acetate, lithium lactate, LiCF3SO3, and LiN(SO2CF3)2.

7. The method for recycling waste ternary batteries as claimed in claim 1, characterized in that: The mass ratio of ascorbic acid to hydrogen peroxide in the additive is 1-9.

8. The method for recycling waste ternary batteries as claimed in claim 1, characterized in that: The water content of the repaired active substance is ≤1wt%, and the average particle size is 8-12μm.

9. The method for recycling waste ternary batteries as claimed in claim 1, characterized in that: The inorganic lithium salt is lithium carbonate, and the molar ratio of the repaired active substance to the lithium carbonate is 1:0.01-0.

05.

10. The method for recycling waste ternary batteries as claimed in claim 1, characterized in that: The heating rate when the repaired active material and the inorganic lithium source are mixed and calcined is 2-5°C / min.

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