Regeneration process of waste ternary positive electrode material based on solid proton source treatment

Abstract

The application discloses a kind of based on solid proton source processing waste ternary positive electrode material regeneration process, comprising the following steps: (1) waste ternary positive electrode material is mixed with solid proton source grinding, then heat treatment, after proton exchange, the precursor of defect state is obtained;The solid proton source is the substance that can provide proton in the process of heat treatment;(2) the precursor of defect state after proton exchange is mixed with lithium source, target transition metal element source grinding, then calcination treatment, and the regenerated lithium-rich layered positive electrode material is obtained.The application solves the technical problems that spinel phase is difficult to be effectively removed in the existing waste NCM523 regeneration technology, and the element supplementing efficiency is low, can significantly improve the electrochemical performance of regenerated material, has higher discharge specific capacity, excellent cycle stability and good rate performance, and can be widely used in lithium ion battery and next-generation high-energy-density energy storage system.

Description

Technical Field

[0001] This invention relates to the field of lithium-ion battery cathode material recycling technology, and in particular to a waste ternary cathode material regeneration process based on solid proton source treatment. Background Technology

[0002] With the rapid development of new energy vehicles and portable electronic devices, the global installed capacity of lithium-ion batteries has continued to grow rapidly, resulting in a sharp increase in the number of waste batteries. Among them, NCM523 (LiNi) batteries are particularly problematic. 0.5 Co 0.2 Mn 0.3 O2) Ternary cathode materials once held a large market share due to their good balance between cost and performance. However, during long-term cycling, these materials suffer from transition metal leaching and Li... + / Ni 2+ Factors such as cation mixing and surface reconstruction can easily transform the layered structure into a spinel phase (such as LiMn2O4) and a rock salt phase, leading to the Li... + The diffusion channels are blocked, and the material structure deteriorates severely.

[0003] In recent years, direct regeneration technology for waste ternary cathode materials has gradually become a research hotspot, including hydrothermal lithium replenishment, molten salt regeneration, and solid-phase lithium replenishment. Although these methods can restore the material structure to some extent, their effects are not ideal for waste NCM523 black powder that has already formed a spinel phase. The spinel phase has a dense structure and is thermodynamically stable, making it difficult for conventional lithium replenishment processes to effectively destroy its phase structure. This leads to obstructed diffusion of subsequently added Mn and Li elements, making it difficult to achieve uniform incorporation. Ultimately, the regenerated material has an impure crystal structure, uneven element distribution, and poor electrochemical performance.

[0004] While existing technologies have reported methods for surface coating or bulk doping using phosphates and boron compounds (such as phosphate coating to improve cycle stability and boron doping to stabilize the crystal lattice), these methods primarily focus on modifying newly prepared materials or are directly applied to the post-processing of fresh powders. They cannot address the spinel phase already formed in waste NCM523. Patent application CN115498298A discloses a method for regenerating waste ternary cathode materials. This method first activates the material by mixing it with liquid acid, followed by lithium replenishment and other operations. This results in a more compact atomic arrangement, reducing the interatomic spacing and refining the grains, thereby improving the crystallinity of the material. However, this method also fails to destroy the spinel phase already formed in waste NCM523. Summary of the Invention

[0005] The main objective of this invention is to provide a regeneration process for waste ternary cathode materials based on solid proton source treatment, aiming to solve the technical problems of spinel phase being difficult to remove effectively and element replenishment efficiency in existing waste NCM523 regeneration technologies.

[0006] To achieve the above objectives, this invention provides a process for regenerating waste ternary cathode materials based on solid proton source treatment, comprising the following steps: (1) Waste ternary cathode material is ground and mixed with a solid proton source, and then heat-treated to obtain a defect-state precursor after proton exchange; the solid proton source is a substance that can provide protons during the heat treatment process; (2) The defective precursor after proton exchange is ground and mixed with the lithium source and the target transition metal element source, and then calcined to obtain the regenerated lithium-rich layered cathode material.

[0007] Furthermore, the waste ternary cathode material is waste NCM523 black powder containing a spinel phase.

[0008] Furthermore, the solid proton source is selected from any one or more of ammonium dihydrogen phosphate, boric acid, ammonium metaphosphate, ammonium polyphosphate, ammonium bisulfate, ammonium sulfate, oxalic acid, citric acid, and tartaric acid in any proportion; even further, the solid proton source is selected from ammonium dihydrogen phosphate and / or boric acid.

[0009] Furthermore, the amount of the solid proton source is 0.5 to 2.0 wt% of the mass of the waste ternary cathode material, and more preferably 1 wt%.

[0010] The target transition metal element of this invention is selected from any one or more of Mn, Ni, Co, Fe, Ti, Al, Mg, Zr, Mo, and W.

[0011] Furthermore, the lithium source is composed of LiNO3 and LiOH·H2O in a molar ratio of 3:2.

[0012] Furthermore, the target transition metal element source is MnCO3, and the amounts of MnCO3, LiNO3, and LiOH·H2O added are 1.173640g, 1.04560g, and 0.42436g, respectively, based on 1g of waste ternary cathode material.

[0013] Furthermore, the heat treatment temperature is 350~450℃, and the time is 2~4 hours, preferably 400℃ for 3 hours. The heat treatment temperature of 400℃ can avoid abnormal grain growth and energy waste caused by traditional high-temperature long-term calcination.

[0014] Furthermore, the calcination treatment temperature is 850~950℃, and the time is 10~14h, with an alternative of 900℃ and 12h.

[0015] The present invention also provides a recycled lithium-rich layered cathode material, which is prepared according to the above process.

[0016] The present invention also provides a lithium-ion battery, wherein the positive electrode material of the lithium-ion battery uses the above-mentioned recycled lithium-rich layered positive electrode material.

[0017] The design principle of this invention is : Taking waste NCM523 black powder containing spinel phase as an example: First, in step (1), the treatment with a solid proton source selectively eliminates the deactivated phases (spinel phase, rock salt phase, and other reconstructed structures) formed by cyclic aging in the material, and constructs abundant lattice defects and ion diffusion channels within the crystal. Solid proton sources, such as ammonium dihydrogen phosphate and boric acid, release protons (H+) upon thermal decomposition. + Ammonium dihydrogen phosphate decomposes to produce NH3 and H3PO4, and boric acid decomposes to release H2O. + And a small amount of B2O3, H + Proton-lithium ion exchange reaction occurs with the spinel phase in waste NCM523: H + + LiMn2O4→ HMn2O4+ Li + (Escape or redistribution), Li in spinel structure + H + Partial substitution, accompanied by Mn 3+ / Mn 4+ Oxidation state changes and lattice oxygen escape successfully disrupt the cubic close-packed structure of the spinel phase, while simultaneously introducing numerous defects (controllable lattice defects, vacancies, and active sites) into the original layered structure, placing the precursor in a defective state. These defects can significantly reduce the subsequent Li... + and Mn 4+ The diffusion barrier provides a rapid ion transport channel for the subsequent addition of elements, solving the technical problems of low efficiency and poor phase purity in traditional direct solid-state lithium replenishment methods. Furthermore, the trace amounts of boron provided by boric acid can enter the crystal lattice and play a mild doping stabilizing role, further enhancing the structural stability of the material.

[0018] Subsequently, in step (2), a eutectic molten salt system is used to supplement lithium and target transition metal elements. The material's crystal structure is then reconstructed through high-temperature calcination to obtain a regenerated lithium-rich layered cathode material. During the high-temperature calcination process, the pre-manufactured lattice defects act as a "highway" for ion diffusion, significantly increasing the efficiency of Mn. 4+ and Li +The migration rate allows the added elements to uniformly enter the lattice, achieving an ordered reconstruction from a spinel / layered mixed phase to a pure lithium-rich layered structure. Furthermore, the molar ratio of LiNO3 to LiOH·H2O is strictly controlled at 3:2, allowing them to form a low-melting-point eutectic molten salt system during heating (the eutectic molten salt is liquid at high temperatures, significantly reducing the melting point of the Li source and promoting Li...). + The deep embedding of defect-state NCM lattices significantly reduces the melting temperature of lithium salts, promotes liquid-phase assisted sintering and uniform lithium incorporation, and the lattice defects created, combined with the liquid-phase environment provided by the eutectic molten salt, achieve a uniform atomic-scale distribution of Mn and Li. Furthermore, these rapid channels improve solid-state reaction efficiency, enabling structural upgrades to be completed in a single high-temperature calcination step.

[0019] The ammonium dihydrogen phosphate (MDH) route and the boric acid route can be flexibly selected according to actual needs. The MDH route may introduce trace amounts of phosphorus to play an auxiliary stabilizing role while breaking down the spinel phase; the boric acid route can achieve a light doping of boron, further improving the high-temperature structural stability of the material.

[0020] The beneficial effects of this invention are reflected in: : 1. The entire process of this invention consists of only four main steps: grinding, low-temperature pretreatment, mixing, and high-temperature calcination. It eliminates the need for wet processes such as acid leaching and extraction, as well as expensive organic complexing agents or special atmosphere protection. The process is simple and efficient, significantly reducing recycling costs and environmental burden. Compared to traditional wet recycling, co-precipitation resynthesis, or surface coating modification processes, this invention features a simpler process, lower energy consumption, lower equipment requirements, and is more environmentally friendly. It is suitable for large-scale industrial production, achieving direct regeneration and upgrading without completely decomposing the original crystal structure. It maximizes the preservation of valuable transition metal resources in waste materials, realizing the high-value transformation from waste NCM materials to high-performance lithium-rich manganese-based materials or other high-value-added cathode materials, thus possessing significant resource recycling and economic value.

[0021] 2. Significantly improves the electrochemical performance of recycled materials, with high discharge specific capacity, excellent cycle stability and good rate performance, and can be widely used in lithium-ion batteries and next-generation high-energy-density energy storage systems.

[0022] 3. This invention effectively solves the problem of difficult removal of spinel phase in waste NCM523. The recycled material has a pure phase layered structure with no obvious impurities. The product is directly upgraded from low-lithium, low-capacity NCM523 to high-lithium, high-capacity lithium-rich material with higher theoretical capacity and better working voltage platform. 4. The regenerated lithium-rich layered cathode material obtained by calcination in this invention can be directly used for cathode slurry coating, electrode preparation and coin cell or soft pack battery assembly after thorough grinding and sieving, without the need for additional coating or modification treatment. Attached Figure Description

[0023] Figure 1 SEM image of discarded NCM523 black powder.

[0024] Figure 2 This is a SEM image of P-NCM obtained in Example 1.

[0025] Figure 3 This is a SEM image of the defective precursor powder after proton exchange prepared in Example 2.

[0026] Figure 4 This is a SEM image of D-NCM-1 obtained in Comparative Example 1.

[0027] Figure 5 This is a SEM image of D-NCM-2 obtained in Comparative Example 2.

[0028] Figure 6 This is a SEM image of D-NCM-3 obtained in Comparative Example 3.

[0029] Figure 7 The first charge-discharge curves for LR-NCM-1, LR-NCM-2, and D-NCM-1 are shown.

[0030] Figure 8 Cyclic capacity curves for LR-NCM-1, LR-NCM-2, and D-NCM-1. Detailed Implementation

[0031] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.

[0032] Unless otherwise specified, the raw materials, reagents or devices used in the following embodiments can be obtained from conventional commercial sources or by existing known methods; unless otherwise specified, the methods used in the embodiments of the present invention are methods mastered by those skilled in the art.

[0033] The waste NCM523 black powder used in the following embodiments and comparative examples was derived from retired industrial batteries, obtained through pre-disassembly, alkaline washing, and preliminary crushing. The chemical formula of each element was determined by ICP testing. 0.97176 Ni 0.50736 Co 0.21356 Mn 0.30632 O2, whose typical composition is similar to LiNi 0.5 Co 0.2 Mn 0.3 O2 has been generated, and spinel phase LiMn2O4-type impurities and lithium loss have occurred.

[0034] Example 1 Lithium-rich layered cathode material prepared based on proton exchange regeneration of waste NCM523 black powder using ammonium dihydrogen phosphate. (1) Take 1.000 g of waste NCM523 black powder and 0.010 g of ammonium dihydrogen phosphate (NH4H2PO4, accounting for 1.0 wt% of waste NCM523 black powder) and place them together in an agate mortar. Mix and grind them at room temperature for 30 min so that the two powders can reach molecular level contact. The ground mixed powder was spread evenly in a corundum crucible and placed in a muffle furnace. The temperature was raised to 400 ℃ at a rate of 5 ℃ / min, held for 3 h, and then naturally cooled to room temperature to obtain the proton-exchanged defect state precursor powder, denoted as P-NCM.

[0035] (2) Take 1.000 g of the above P-NCM powder, and place it together with 1.173640 g MnCO3 (analytical grade), 1.04560 g LiNO3 (analytical grade) and 0.42436 g LiOH·H2O (analytical grade) in an agate mortar. Mix and grind at room temperature for 30 min to ensure uniform mixing. The mixed powder was transferred to a tube furnace and heated to 900 °C at a rate of 5 °C / min in an Ar / O2 (95:5 volume ratio) mixed atmosphere at a flow rate of 50 mL / min. After holding at this temperature for 12 h, the mixture was allowed to cool naturally to room temperature. The powder was then ground for 30 min and passed through a 200-mesh sieve to obtain a regenerated lithium-rich layered cathode material. ICP analysis showed the chemical formula to be Li. 1.2 Ni 0.2 Mn 0.515 Co 0.085 O2, denoted as LR-NCM-1.

[0036] Example 2-10 Lithium-rich layered cathode materials prepared by regenerating waste NCM523 black powder using other solid proton sources. The preparation methods of Examples 2-10 are basically the same as those of Example 1, except that in Examples 2-10, the ammonium dihydrogen phosphate in step (1) of Example 1 is replaced with equal masses of boric acid (H3BO3), phosphoric acid (H3PO4), ammonium metaphosphate (NH4PO3), and ammonium polyphosphate (NH4PO3). n Ammonium bisulfate (NH4HSO4), ammonium sulfate ((NH4)2SO4), oxalic acid (H2C2O4), citric acid (C6H8O7), and tartaric acid (C4H6O6) are listed in Table 1.

[0037] Comparative Example 1 Direct lithium supplementation for cathode material preparation without proton exchange regeneration of waste NCM523 black powder The preparation method of this comparative example is basically the same as that of Example 1, except that step (1) is omitted and the P-NCM powder in step (2) is replaced with an equal mass of waste NCM523 black powder. The regenerated cathode material obtained in this comparative example is denoted as D-NCM-1.

[0038] Comparative Example 2 Direct lithium supplementation for cathode material preparation without heat treatment to regenerate waste NCM523 black powder The preparation method of this comparative example is basically the same as that of Example 1, except that the operation of "spreading the ground mixed powder evenly in a corundum crucible, placing it in a muffle furnace, heating it to 400 ℃ at a heating rate of 5 ℃ / min, holding it at that temperature for 3 h and then naturally cooling it to room temperature" in step (1) is omitted, and the P-NCM powder in step (2) is replaced by an equal mass of the mixed powder of waste NCM523 black powder and ammonium dihydrogen phosphate after grinding. The regenerated cathode material obtained in this comparative example is denoted as D-NCM-2.

[0039] Comparative Example 3 Acid activation and regeneration of waste NCM523 black powder to prepare lithium-rich layered cathode materials (1) Prepare a tartaric acid solution with pH 5.0, add 1.000 g of waste NCM523 black powder, stir at 30°C for 2 h, then separate the solid and liquid, wash the obtained solid with water and dry it to obtain activated NCM523; (2) This step is basically the same as step (2) in Example 1, except that the P-NCM powder is replaced with an equal mass of the above-mentioned activated NCM523. The regenerated cathode material prepared in this comparative example is denoted as D-NCM-3.

[0040] Experimental Example 1 Structural analysis of materials before and after recycling SEM image of discarded NCM523 black powder as shown Figure 1 As shown, the SEM image of P-NCM is as follows: Figure 2 As shown, the waste NCM523 black powder exhibits obvious microcracks (delithiation and oxygen loss due to Li-Li degradation). + / Ni 2+ The mixed arrangement induces the formation of disordered spinel impurities in a layered structure, and the severe mismatch between the two phase lattices leads to accumulated stress and the generation of a large number of microcracks, indicating the presence of spinel impurities in the material. However, the P-NCM obtained after ammonium dihydrogen phosphate treatment has a smooth and flat particle surface and exhibits a layered structure, indicating that the irreversible reconstruction is blocked after material regeneration, no spinel impurities are generated, there is no local stress concentration inside the particles, and the morphology can maintain a smooth and flat shape. This shows that the spinel phase on the material surface is broken by the proton exchange reaction of ammonium dihydrogen phosphate.

[0041] Similarly, see Figure 3The SEM image of the proton-exchanged defect-state precursor powder obtained in Example 2 also shows this structural change.

[0042] Figure 4 The image shows the SEM image of D-NCM-1 prepared in Comparative Example 1. It can be seen that without the proton exchange treatment of ammonium dihydrogen phosphate, the problem of the spinel phase in the material cannot be solved, and the material still has some microcracks, making it impossible to completely repair the material.

[0043] Figure 5 The image shows the SEM image of D-NCM-2 prepared in Comparative Example 2. It can be seen that the material obtained by grinding and mixing without muffle furnace heating cannot solve the spinel phase problem. The material still has some microcracks and cannot be completely repaired.

[0044] Figure 6 The image shows the SEM image of D-NCM-3 prepared in Comparative Example 3. It can be seen that the material obtained by acid activation treatment also has microcracks and cannot solve the problem of spinel phase.

[0045] Experimental Example 2 Charge and discharge testing of materials The cathode materials prepared in the above embodiments and comparative examples were subjected to constant current charge-discharge tests under the same conditions. The test methods and results are as follows: The cathode material to be tested was mixed with Super P conductive carbon black and PVDF binder at a mass ratio of 85:10:5, and an appropriate amount of NMP was added to prepare a slurry. The slurry was then uniformly coated onto an aluminum foil current collector and vacuum dried at 80℃ for 12 h. The slurry was then cut into 12 mm diameter electrode sheets (active material loading 2.0 mg / cm²). 2 ).

[0046] Assemble CR2032 button half-cells in an argon glove box: the positive electrode is the above-mentioned electrode, the negative electrode is a lithium metal sheet, the separator is Celgard 2400, and the electrolyte is 1 M LiPF6 dissolved in EC:DMC:EMC (1:1:1 volume ratio) containing 2 wt% VC additive.

[0047] Constant current charge-discharge tests were performed using the Newway BTS battery testing system in the voltage range of 2.0–4.8 V. The results are shown in Table 1. Additionally, for the sake of brevity, Figure 6 and Figure 7 Only the test results of LR-NCM-1, LR-NCM-2 (the regenerated lithium-rich layered cathode material prepared in Example 2) and D-NCM-1 are shown.

[0048] Table 1

[0049] The results above show that: The cathode material prepared in Example 1 achieved a first-cycle discharge capacity of 286.19 mAh / g at 1C rate, with an initial coulombic efficiency of 76.19%; the cathode material prepared in Example 2 achieved a first-cycle discharge capacity of 274.45 mAh / g at 1C rate, with an initial coulombic efficiency of 84.23%. Cathode materials prepared using other solid proton sources such as phosphoric acid also exhibited good charge-discharge performance.

[0050] In contrast, the initial capacity of D-NCM-1 in Comparative Example 1 was only 220.88 mAh / g, with an initial coulombic efficiency of 65.55%. Compared to Example 1, the performance was significantly reduced. Similarly, D-NCM-2 in Comparative Example 2 and D-NCM-3 in Comparative Example 3 also failed to achieve the same effect as Example 1.

[0051] Experimental Example 3 Scale-up experiment The cathode material was prepared by scaling up the formulation of Example 1 by 10 times (10 g NCM523), using a planetary ball mill instead of manual grinding (300 rpm, 60 min), with all other conditions unchanged. The properties of the obtained cathode material were basically consistent with those of Example 1, demonstrating that this process has good scale-up feasibility.

[0052] Experiment Example 4 Post-cycle material regeneration verification The LR-NCM-1 material prepared in Example 1 was used to assemble a battery. After 100 cycles, the positive electrode powder was disassembled and recycled. The regeneration process of Example 1 was used again. The resulting secondary regenerated material could still maintain more than 90% of the initial capacity, demonstrating excellent regeneration cycle performance.

[0053] Experimental Example 5 Effect of different amounts of solid proton source added on material properties Based on Example 1, the amount of ammonium dihydrogen phosphate added in step (1) was changed to 0.005 g (0.5 wt%), 0.015 g (1.5 wt%) and 0.020 g (2.0 wt%) respectively. Other conditions were the same as in Example 1. The prepared regenerated lithium-rich layered cathode material was subjected to charge-discharge tests (same as in Experiment 2). The results are shown in Table 2 below.

[0054] Table 2

[0055] The results showed that an addition of 1 wt% was the optimal condition. If the addition was too small, the protons provided would not be sufficient to completely break down the spinel phase and repair the microcracks, resulting in a decrease in the electrochemical performance of the battery; if the addition was too large, it would provide excessive protons, leading to corrosion of the material structure and a decrease in the electrochemical performance of the material.

[0056] Experimental Example 6 Effect of different heat treatment temperatures on material properties Based on Example 1, the heat treatment holding temperature in step (1) was adjusted to 350 ℃ and 450 ℃ respectively, while other conditions remained unchanged. The resulting regenerated lithium-rich layered cathode material was subjected to charge-discharge tests (same as in Example 2), and the results are shown in Table 3 below.

[0057] Table 3

[0058] The results show that a heat treatment holding temperature of 400 °C is the optimal condition, and the resulting product exhibits the best electrochemical performance. Too low a temperature leads to insufficient proton exchange, while too high a temperature easily results in excessive oxidation of the transition metal.

[0059] Experimental Example 7 Effect of different heat treatment times on material properties Based on Example 1, the heat treatment holding time in step (1) was adjusted to 2 h and 4 h, while other conditions remained unchanged. The resulting regenerated lithium-rich layered cathode material was subjected to charge-discharge tests (same as in Example 2), and the results are shown in Table 4 below.

[0060] Table 4

[0061] The results showed that a heat treatment holding time of 3 h was the optimal condition, yielding products with the best electrochemical performance. Too short a holding time resulted in insufficient proton exchange, while too long a holding time easily led to excessive oxidation of the transition metals.

[0062] Experimental Example 8 Effect of different calcination temperatures on material properties Based on Example 1, the calcination temperature of step (2) was set to 850 ℃ and 950 ℃ respectively, and other conditions were the same as in Example 1. The obtained regenerated lithium-rich layered cathode material was subjected to charge-discharge test (same as in Experiment 2), and the results are shown in Table 5 below.

[0063] Table 5

[0064] Experimental Example 9 Effect of different calcination times on material properties Based on Example 1, the calcination holding time in step (2) was set to 10 h and 14 h, while other conditions were the same as in Example 1. The obtained recycled lithium-rich layered cathode material was subjected to charge-discharge tests (same as in Experiment 2), and the results are shown in Table 6 below.

[0065] Table 6

[0066] The results showed that the product obtained by incubation at 900 ℃ for 12 h had the best electrochemical performance.

[0067] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A regeneration process of waste ternary cathode material based on solid proton source treatment, characterized in that, Includes the following steps: (1) Waste ternary cathode material is ground and mixed with a solid proton source, and then heat-treated to obtain a defect-state precursor after proton exchange; the solid proton source is a substance that can provide protons during the heat treatment process; (2) The defective precursor after proton exchange is ground and mixed with the lithium source and the target transition metal element source, and then calcined to obtain the regenerated lithium-rich layered cathode material.

2. The waste ternary cathode material regeneration process based on solid proton source treatment as described in claim 1, characterized in that, The waste ternary cathode material is waste NCM523 black powder containing spinel phase.

3. The waste ternary cathode material regeneration process based on solid proton source treatment as described in claim 1 or 2, characterized in that, The solid proton source is selected from any one or more of ammonium dihydrogen phosphate, boric acid, phosphoric acid, ammonium metaphosphate, ammonium polyphosphate, ammonium bisulfate, ammonium sulfate, oxalic acid, citric acid, and tartaric acid in any proportion; the amount of the solid proton source is 0.5 to 2.0 wt% of the mass of the waste ternary cathode material.

4. The waste ternary cathode material regeneration process based on solid proton source treatment as described in claim 3, characterized in that, The solid proton source is selected from ammonium dihydrogen phosphate and / or boric acid.

5. The waste ternary cathode material regeneration process based on solid proton source treatment as described in claim 1 or 2, characterized in that, The lithium source is composed of LiNO3 and LiOH·H2O in a molar ratio of 3:

2.

6. The waste ternary cathode material regeneration process based on solid proton source treatment as described in claim 5, characterized in that, The target transition metal element source is MnCO3. The amounts of MnCO3, LiNO3, and LiOH·H2O added are 1.173640g, 1.04560g, and 0.42436g, respectively, based on 1g of waste ternary cathode material.

7. The waste ternary cathode material regeneration process based on solid proton source treatment as described in claim 1 or 2, characterized in that, The heat treatment temperature is 350~450℃, and the time is 2~4h.

8. The waste ternary cathode material regeneration process based on solid proton source treatment as described in claim 1 or 2, characterized in that, The calcination temperature is 850~950℃ and the time is 10~14h.

9. A recycled lithium-rich layered cathode material, characterized in that, Prepared according to the process described in any one of claims 1 to 8.

10. A lithium-ion battery, characterized in that, The positive electrode material of the lithium-ion battery uses the recycled lithium-rich layered positive electrode material as described in claim 9.

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