Preparation method for recycling lithium cobalt nickel manganese oxide battery from quaternary ammonium carboxyl-containing hydroxyl additive

Abstract

The invention provides a preparation method for recovering a lithium cobalt nickel manganese oxide battery by using a quaternary ammonium carboxyl-containing hydroxyl assistant, which comprises the following steps: initiating copolymerization of a quaternary ammonium salt monomer and a bisphenol A derivative by potassium persulfate to generate a branched polymer containing quaternary ammonium groups, hydroxyl and ester groups, and meeting the coordination requirements of multiple metal ions.

Description

Technical Field

[0001] This invention belongs to the field of lithium battery recycling technology, specifically relating to a method for recycling aluminum foil, a cathode material of waste lithium-ion batteries containing nickel-cobalt-manganese oxide. Background Technology

[0002] In 2023, global sales of new energy vehicles exceeded 20 million units, corresponding to a demand of over 800 GWh for ternary lithium batteries (NCM / NCA). China, as the largest producer and consumer, accounted for over 65% of this production. With the 5-8 year lifespan of lithium batteries approaching, it is projected that by 2025, the global volume of scrapped ternary lithium batteries will exceed 1.5 million tons, with China's annual scrapping volume exceeding 800,000 tons. In the cathode materials of ternary lithium batteries, precious metals such as cobalt, nickel, and manganese account for over 50%, while lithium, although present in lower amounts (approximately 3-5%), has significant recycling value as a strategic resource.

[0003] For example, patent CN119812547A discloses a method for recycling and regenerating waste lithium battery cathode materials, relating to the field of lithium battery cathode material technology. In preparing lithium battery cathode materials, this invention first discharges and disassembles waste lithium iron phosphate batteries, then circulates and soaks the current collector in hot and cold water to separate it. After calcination, lithium ions are selectively leached out using sulfuric acid-hydrogen peroxide to recover and obtain recycled lithium carbonate; a ternary precursor of lithium carbonate is prepared using a co-precipitation method. For example, patent CN119433208A discloses a method for selectively and sequentially separating valuable metals from waste ternary lithium battery cathode materials. This invention involves heating and mixing choline chloride, malonic acid, and water to obtain a eutectic solvent. This solvent is then mixed with the waste ternary lithium battery cathode material for nickel separation. The resulting leachate is then mixed with an oxalic acid aqueous solution for cobalt separation. The resulting leachate residue is then mixed with an inorganic strong alkaline solution for manganese separation. Finally, the leachate contains lithium. The method provided by this invention can selectively and sequentially separate valuable metals from waste ternary lithium battery cathode materials.

[0004] Existing lithium nickel cobalt manganese oxide cathode material technology often suffers from problems such as complex processes, high reagent consumption, and serious pollution. It also has drawbacks such as difficult separation, low recovery rate, and poor electrochemical performance of the product. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing lithium cobalt nickel manganese oxide batteries containing quaternary ammonium carboxyl hydroxyl additives. Through innovative additive design and microwave-assisted processing, the following technical objectives are achieved: 1. Increase the leaching rates of cobalt, nickel, and manganese to over 95%, and the lithium leaching rate to 98%, which is 10-15% higher than the traditional wet process; 2. Shorten the reaction time to 3-4 hours, reducing energy consumption by more than 30%; 3. Achieve gradient separation of lithium, cobalt, nickel, and manganese, with each metal precipitate having a purity of ≥98%, meeting the requirements for battery-grade materials; 4. Reduce the amount of strong acid used by 50%, lower wastewater treatment costs, and achieve green recycling.

[0006] The technical solution of this invention is: a method for preparing a lithium cobalt nickel manganese oxide battery containing a quaternary ammonium carboxyl hydroxyl additive, characterized by comprising the following steps: A. Raw material crushing and sieving: The waste NCM battery positive electrode sheet is crushed to a particle size ≤1mm. The current collectors such as aluminum foil are separated by a vibrating screen to obtain positive electrode active material powder. A certain mass of aluminum-containing positive electrode powder is mixed with an appropriate amount of sulfuric acid solution and added to a reaction vessel. The mixture is reacted at different temperatures for a period of time, and a nitric acid-EDTA mixed solution containing an appropriate amount of additives is added. The mixture is transferred to a microwave reaction vessel and heated for microwave-assisted reaction. After the reaction is completed, a clear leachate is obtained by plate and frame filtration. Na2CO3 solution and NH3·H2O are added to the leachate, and the pH is adjusted to obtain Li, Ni, Co, and Mn precipitates.

[0007] B. Calculate the leaching rates of nickel, cobalt, and manganese.

[0008] The concentrations of various metal ions in the leachate were determined using inductively coupled plasma optical emission spectrometry (ICP-OES), and the leaching rate was calculated using the following formula: Leaching rate (%) =

[0009] Where C is the concentration of metal ions in the leachate (mg / L), V is the volume of the leachate (L), M is the molar mass of the metal (g / mol), m is the mass of the cathode powder (g), and w is the mass fraction of the metal in the cathode (%).

[0010] As a preferred embodiment of the present invention, the feature is that in step A, the mass ratio of the lithium nickel cobalt manganese oxide positive electrode sheet to the sulfuric acid solution is 1-10:8-80.

[0011] As a preferred embodiment of the present invention, the reaction temperature in step A is 25-80°C and the reaction time is 1-5 hours.

[0012] As a preferred embodiment of the present invention, the additive amount in step A is 1%-10% of the total mass.

[0013] As a preferred embodiment of the present invention, the method for preparing the auxiliary agent in step A is as follows: In the presence of potassium persulfate initiator, 10-15 parts by weight of methacryloyloxyethyltrimethylammonium chloride, 11-14 parts by weight of hydroxyethyl acrylate and 6-10 parts by weight of bisphenol A propoxydiacrylate glycerol ester are dissolved in deionized water (solid content 20-30%), heated and reacted for a period of time, and spray-dried after the reaction is completed to obtain the branched polymer auxiliary. As a preferred embodiment of the present invention, the characteristic is that: in step A, the heating reaction temperature is 60-80℃.

[0014] As a preferred embodiment of the present invention, the characteristic is that: in step A, the heating reaction time is 2-5 hours.

[0015] As a preferred embodiment of the present invention, the feature is that: in step A, the dipotassium hydrogen phosphate-citric acid buffer solution of the auxiliary agent is subjected to a microwave-assisted reaction at 70-90°C.

[0016] As a preferred embodiment of the present invention, the microwave-assisted reaction time in step A is 3-4 hours.

[0017] As a preferred embodiment of the present invention, the feature is that: in step A, after the reaction is completed, a clear leachate is obtained by plate and frame filtration (pressure 0.4-0.6MPa) or centrifugation (speed 4000-6000rpm).

[0018] Lithium precipitation: Add Na₂CO₃ solution to the leachate to adjust the pH to 10.5-11.0, so that Li… + The precipitate is formed as Li2CO3, filtered, and dried at 60-90℃ for 3-6 hours to obtain battery-grade lithium carbonate.

[0019] The cobalt-nickel-manganese gradient precipitation method is as follows: Add NH3·H2O to the lithium-removed solution to adjust the pH to 8.5-9.0. Co 2+ With Co(OH) 2 Precipitation form, purity calculated; After filtration, continue adjusting the pH to 9.5-10.0, Ni 2+ Calculate the purity by precipitating Ni(OH)2. Finally, adjust the pH to 10.5-11.0, Mn 2+ The purity was calculated by precipitating the substance as Mn(OH)2.

[0020] I. Reaction Mechanism Synthesis and structural design of auxiliaries The branched polymer auxiliaries used in this invention are synthesized based on free radical copolymerization, and the specific mechanism is as follows: Initiation stage: Potassium persulfate (K2S2O8) decomposes at 60-80℃ to produce sulfate free radicals (SO4· ... - This triggers the polymerization of monomeric double bonds: K2S2O8 = 2 SO4· - +2K + Chain growth stage: Methacryloxyethyltrimethylammonium chloride (DMC) provides quaternary ammonium groups to form water-soluble segments; Hydroxyethyl acrylate (HEA) introduces hydroxyl groups, providing sites for the coordination of metal ions; Bisphenol A propoxydiacrylate glycerol ester (BPADA), as a branched monomer, forms a three-dimensional network structure through a double bond addition reaction.

[0021] Chain termination stage: Polymerization is terminated by free radical coupling or disproportionation reaction, forming branched polymers with a narrow molecular weight distribution (weight average molecular weight 50,000-80,000 Da).

[0022] Multi-coordination synergistic leaching mechanism The interaction mechanism between auxiliaries and metal ions can be divided into three synergistic processes: Electrostatic adsorption and structural destruction: The positive charge of the quaternary ammonium group and the negative charge on the surface of the cathode material (mainly from O) 2- This forms electrostatic attraction, weakening the binding energy of the metal-oxygen bond (MO); The three-dimensional network structure of branched polymers disrupts the layered lattice of NCM materials through physical entanglement, exposing more active sites.

[0023] Coordination bond formation and complexation enhancement: The O atom of the hydroxyl group and Co 2+ Ni 2+ A coordinate bond is formed (bond energy approximately 200-250 kJ / mol), with the O atom of the ester group reacting with Mn. 2+ Formation of coordinate bonds; EDTA acts as a strong complexing agent, forming stable six-membered ring chelates with metal ions (such as [Co(EDTA)]). - The stability constant logK = 16.3) promotes the dissociation of metal ions from the crystal lattice.

[0024] Microwave-assisted kinetic enhancement: In a microwave field, the high-frequency vibration of polar molecules (such as water, additives, and EDTA) generates an internal heat source, causing the temperature of the reaction system to rise uniformly and the molecular motion rate to increase by 2-3 times. Microwave-induced "non-thermal effects" lower the activation energy of the coordination reaction, making [M(L)(EDTA)]... n- The generation rate of complex ions is increased by more than 50%.

[0025] Selectivity mechanism of gradient pH precipitation The difference in solubility product (Ksp) of different metal hydroxides is the theoretical basis for gradient separation: Co(OH)2: Ksp = 1.6 × 10 -15 The optimal precipitation pH is 8.5-9.0; Ni(OH)2: Ksp = 5.4 × 10 -16 The optimal precipitation pH is 9.5-10.0. Mn(OH)2: Ksp = 2.1 × 10 -13 The optimal precipitation pH is 10.5-11.0.

[0026] The complex formed by the additive and EDTA further broadens the precipitation pH window and reduces co-precipitation by adjusting the free concentration of metal ions. For example, Co... 2+ The coordination with the additives reduces its free concentration by 1-2 orders of magnitude, thus preferentially precipitating at lower pH levels.

[0027] II. Technical Effects 1: Simultaneous and efficient leaching of multiple metals: The leaching rates of Co, Ni and Mn are all ≥95%, which is 10% higher than the traditional system, and the reaction time is shortened to less than 3 hours under microwave assistance. 2: The lithium carbonate obtained by gradient precipitation has a purity of 99.5%, and the purity of Co (OH)2, Ni (OH)2 and Mn (OH)2 is ≥98%. The impurity content (Fe≤10ppm, Al≤5ppm) meets the requirements of GB / T 26026-2010 "Battery Grade Lithium Carbonate" and "Hydroxides for Cathode Materials of Lithium-ion Batteries". Detailed Implementation

[0028] The present invention will be described in detail below with reference to specific embodiments. Example 1

[0029] 1. A method for preparing a lithium cobalt nickel manganese oxide battery containing a quaternary ammonium carboxyl hydroxyl additive, characterized by comprising the following steps: A. After crushing the positive electrode material containing aluminum foil, take 1g of lithium nickel cobalt manganese oxide positive electrode sheet and mix it with 8g of sulfuric acid solution. Add the mixture to a reaction vessel and react at 25°C for 1 hour. Then, add 0.09g of nitric acid-EDTA mixed solution containing appropriate additives and microwave-assisted reaction at 70°C for 3 hours in a microwave reaction vessel. After filtration, separate the metal ions by gradient pH precipitation.

[0030] After the reaction is completed, a clear leachate is obtained by plate and frame filtration (pressure 0.4 MPa) or centrifugation (speed 4000 rpm).

[0031] Lithium precipitation: Add Na₂CO₃ solution to the leachate to adjust the pH to 10.5, so that Li… + The precipitate was formed as Li2CO3, filtered, and dried at 60°C for 3 hours to obtain battery-grade lithium carbonate (purity ≥99.5%).

[0032] The cobalt-nickel-manganese gradient precipitation method is as follows: Add NH3·H2O to the lithium-removed solution to adjust the pH to 8.5-9.0. Co 2+ It precipitates as Co(OH)2 with a purity ≥98%; After filtration, continue adjusting the pH to 9.5-10.0, Ni 2+ It precipitates as Ni(OH)2 with a purity ≥98%; Finally, adjust the pH to 10.5-11.0, Mn 2+ It precipitates as Mn(OH)2 with a purity ≥98%.

[0033] The preparation method of the auxiliary agent: In the presence of potassium persulfate initiator, 10 g of methacryloyloxyethyltrimethylammonium chloride, 11 g of hydroxyethyl acrylate, and 6 g of bisphenol A propoxydiacrylate glycerol ester were dissolved in deionized water and reacted at 60 °C for 2 hours. After the reaction was completed, the product was spray-dried to obtain the branched polymer auxiliary. B. The leaching rates of nickel, cobalt, and manganese are calculated to be 92%, 90%, and 91%, respectively. Example 2

[0034] 1. A method for preparing a lithium cobalt nickel manganese oxide battery containing a quaternary ammonium carboxyl hydroxyl additive, characterized by comprising the following steps: A. After crushing the positive electrode material containing aluminum foil, take 5g of lithium nickel cobalt manganese oxide positive electrode sheet and mix it with 40g of sulfuric acid solution. Add the mixture to a reaction vessel and react at 50℃ for 3 hours. Then, add 2.25g of nitric acid-EDTA mixed solution containing appropriate additives and microwave-assisted reaction at 80℃ for 3.5 hours in a microwave reaction vessel. After filtration, separate the metal ions by gradient pH precipitation.

[0035] In step A, after the reaction is completed, a clear leachate is obtained by plate and frame filtration (pressure 0.5 MPa) or centrifugation (speed 5000 rpm).

[0036] Lithium precipitation: Add Na₂CO₃ solution to the leachate to adjust the pH to 10.8, so that Li… + The precipitate was formed as Li2CO3, filtered, and dried at 80°C for 4 hours to obtain battery-grade lithium carbonate.

[0037] The cobalt-nickel-manganese gradient precipitation method is as follows: Add NH3·H2O to the lithium-removed solution to adjust the pH to 8.8, Co 2+ It precipitates as Co(OH)2.

[0038] After filtration, further adjust the pH to 9.8, Ni 2+ It precipitates as Ni(OH)2.

[0039] Finally, adjust the pH to 10.8, Mn 2+ It precipitates as Mn(OH)2.

[0040] The preparation method of the auxiliary agent: In the presence of potassium persulfate initiator, 13 g of methacryloyloxyethyltrimethylammonium chloride, 13 g of hydroxyethyl acrylate, and 8 g of bisphenol A propoxydiacrylate glycerol ester were dissolved in deionized water and reacted at 70°C for 3 hours. After the reaction was completed, the product was spray-dried to obtain the branched polymer auxiliary. B. The leaching rates of nickel, cobalt, and manganese are calculated to be 95%, 94%, and 96%, respectively. Example 3

[0041] 1. A method for preparing a lithium cobalt nickel manganese oxide battery containing a quaternary ammonium carboxyl hydroxyl additive, characterized by comprising the following steps: A. After crushing the positive electrode material containing aluminum foil, take 8g of lithium nickel cobalt manganese oxide positive electrode sheet and mix it with 80g of sulfuric acid solution. Add the mixture to a reaction vessel and react at 80℃ for 5 hours. Then, add 8g of nitric acid-EDTA mixed solution containing appropriate additives and microwave-assisted reaction at 90℃ for 4 hours in a microwave reaction vessel. After filtration, separate the metal ions by gradient pH precipitation.

[0042] In step A, after the reaction is completed, a clear leachate is obtained by plate and frame filtration (pressure 0.4-0.6 MPa) or centrifugation (speed 4000-6000 rpm).

[0043] Lithium precipitation: Add Na₂CO₃ solution to the leachate to adjust the pH to 11.0, so that Li… + The precipitate was formed as Li2CO3, filtered, and dried at 90°C for 6 hours to obtain battery-grade lithium carbonate (purity ≥99.5%).

[0044] The cobalt-nickel-manganese gradient precipitation method is as follows: Add NH3·H2O to the lithium-removed solution to adjust the pH to 9.0. Co 2+ It precipitates as Co(OH)2 with a purity ≥98%; After filtration, continue adjusting the pH to 10.0, Ni 2+ It precipitates as Ni(OH)2 with a purity ≥98%; Finally, adjust the pH to 11.0, Mn 2+ It precipitates as Mn(OH)2 with a purity ≥98%.

[0045] The method for preparing the auxiliary agent: In the presence of potassium persulfate initiator, 15 g of methacryloyloxyethyltrimethylammonium chloride, 14 g of hydroxyethyl acrylate, and 10 g of bisphenol A propoxydiacrylate glycerol ester were dissolved in deionized water and reacted at 80°C for 5 hours. After the reaction was completed, the product was spray-dried to obtain the branched polymer auxiliary. B. The leaching rates of nickel, cobalt, and manganese are calculated to be 99%, 98%, and 98%, respectively.

[0046] Comparative Example 1 A method for preparing a lithium cobalt nickel manganese oxide battery containing a quaternary ammonium carboxyl hydroxyl additive, characterized by comprising the following steps: A. After crushing the positive electrode material containing aluminum foil, take 1g of lithium nickel cobalt manganese oxide positive electrode sheet and mix it with 8g of sulfuric acid solution. Add the mixture to the reaction vessel and react at 25°C for 1 hour. Then separate the aluminum foil and the positive electrode powder and collect the positive electrode material.

[0047] In step A, after the reaction is completed, a clear leachate is obtained by plate and frame filtration (pressure 0.4 MPa) or centrifugation (speed 4000 rpm).

[0048] Lithium precipitation: Add Na₂CO₃ solution to the leachate to adjust the pH to 10.5, so that Li… +The precipitate was formed as Li2CO3, filtered, and dried at 60°C for 3 hours to obtain battery-grade lithium carbonate.

[0049] The cobalt-nickel-manganese gradient precipitation method is as follows: Add NH3·H2O to the lithium-removed solution to adjust the pH to 8.5. Co 2+ It precipitates as Co(OH)2.

[0050] After filtration, further adjust the pH to 9.5, Ni 2+ It precipitates as Ni(OH)2.

[0051] Finally, adjust the pH to 10.5, Mn 2+ It precipitates as Mn(OH)2.

[0052] B. The leaching rates of nickel, cobalt, and manganese are calculated to be 87%, 86%, and 87%, respectively.

[0053] Comparative Example 2 A method for preparing a lithium cobalt nickel manganese oxide battery containing a quaternary ammonium carboxyl hydroxyl additive, characterized by comprising the following steps: A. After crushing the positive electrode material containing aluminum foil, take 5g of lithium nickel cobalt manganese oxide positive electrode sheet and mix it with 40g of sulfuric acid solution. Add the mixture to the reaction vessel and react at 50℃ for 3 hours. Then separate the aluminum foil from the positive electrode powder and collect the aluminum foil.

[0054] After the reaction is completed, a clear leachate is obtained by plate and frame filtration (pressure 0.5 MPa) or centrifugation (speed 5000 rpm).

[0055] Lithium precipitation: Add Na₂CO₃ solution to the leachate to adjust the pH to 10.8, so that Li… + The precipitate was formed as Li2CO3, filtered, and dried at 80°C for 4 hours to obtain battery-grade lithium carbonate.

[0056] The cobalt-nickel-manganese gradient precipitation method is as follows: Add NH3·H2O to the lithium-removed solution to adjust the pH to 8.8, Co 2+ It precipitates as Co(OH)2.

[0057] After filtration, further adjust the pH to 9.8, Ni 2+ It precipitates as Ni(OH)2.

[0058] Finally, adjust the pH to 10.8, Mn 2+ It precipitates as Mn(OH)2.

[0059] B. The leaching rates of nickel, cobalt, and manganese are calculated to be 89%, 89%, and 89%, respectively.

[0060] Compared to traditional methods for recycling spent lithium-cobalt-nickel-manganese oxide batteries, the recycling method of this invention has a higher metal leaching rate and product purity, with cobalt, nickel, and manganese leaching rates all ≥95%. This method utilizes a branched polymer auxiliary containing quaternary ammonium groups, hydroxyl groups, and ester groups, generated by the copolymerization of quaternary ammonium salt monomers and bisphenol A derivatives initiated by potassium persulfate. Its multiple coordination sites can form stable complexes with metal ions. Combined with the microwave-assisted "non-thermal effect," this lowers the reaction activation energy and accelerates metal dissolution. Simultaneously, a gradient pH precipitation method is used to achieve precise separation by utilizing the difference in solubility products of different metal hydroxides, shortening the reaction time to 3-4 hours, reducing strong acid usage by 50%, lowering energy consumption and pollution, and meeting the needs of green recycling and battery-grade material regeneration.

[0061] 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 method for preparing a lithium cobalt nickel manganese oxide battery containing a quaternary ammonium carboxyl hydroxyl additive, characterized in that... Includes the following steps: A. Raw material crushing and screening: The waste NCM battery positive electrode sheet is crushed to a particle size ≤1mm. The current collectors such as aluminum foil are separated by a vibrating screen to obtain positive electrode active material powder. A certain mass of aluminum-containing positive electrode powder is mixed with an appropriate amount of sulfuric acid solution and added to a reaction vessel. The mixture is reacted at different temperatures for a period of time, and a nitric acid-EDTA mixed solution containing an appropriate amount of additives is added. The mixture is transferred to a microwave reaction vessel and heated for microwave-assisted reaction. After the reaction is completed, a clear leachate is obtained by plate and frame filtration. Na2CO3 solution and NH3·H2O are added to the leachate, and the pH is adjusted to obtain Li, Ni, Co, and Mn precipitates. B. Calculate the leaching rates of nickel, cobalt, and manganese: The concentrations of various metal ions in the leachate were determined using inductively coupled plasma optical emission spectrometry (ICP-OES), and the leaching rate was calculated using the following formula: Leaching rate (%) = , Where C is the concentration of metal ions in the leachate (mg / L), V is the volume of the leachate (L), M is the molar mass of the metal (g / mol), m is the mass of the cathode powder (g), and w is the mass fraction of the metal in the cathode (%).

2. The preparation method of a lithium cobalt nickel manganese oxide battery containing a quaternary ammonium carboxyl hydroxyl additive according to claim 1, characterized in that: In step A, the mass ratio of the lithium nickel cobalt manganese oxide positive electrode to the sulfuric acid solution is 1-10:8-80.

3. The preparation method of a lithium cobalt nickel manganese oxide battery containing quaternary ammonium carboxyl hydroxyl additive according to claim 1, characterized in that: In step A, the reaction temperature is 25-80℃ and the reaction time is 1-5 hours.

4. The preparation method of a lithium cobalt nickel manganese oxide battery containing a quaternary ammonium carboxyl hydroxyl additive according to claim 1, characterized in that: In step A, the amount of the additive is 1%-10% of the total mass.

5. The preparation method of a lithium cobalt nickel manganese oxide battery containing a quaternary ammonium carboxyl hydroxyl additive according to claim 1, characterized in that: In step A, the method for preparing the auxiliary agent is as follows: In the presence of potassium persulfate initiator, 10-15 parts by weight of methacryloyloxyethyltrimethylammonium chloride, 11-14 parts by weight of hydroxyethyl acrylate and 6-10 parts by weight of bisphenol A propoxydiacrylate glycerol ester are dissolved in deionized water (solid content 20-30%), heated and reacted for a period of time, and spray-dried after the reaction is completed to obtain the branched polymer auxiliary.

6. The preparation method of a lithium cobalt nickel manganese oxide battery containing a quaternary ammonium carboxyl hydroxyl additive according to claim 5, characterized in that: In step A, the heating reaction temperature is 60-80℃.

7. The preparation method of a lithium cobalt nickel manganese oxide battery containing a quaternary ammonium carboxyl hydroxyl additive according to claim 5, characterized in that: In step A, the heating reaction time is 2-5 hours.

8. The preparation method of a lithium cobalt nickel manganese oxide battery containing a quaternary ammonium carboxyl hydroxyl additive according to claim 1, characterized in that: In step A, the dipotassium hydrogen phosphate-citric acid buffer solution of the auxiliary agent undergoes a microwave-assisted reaction at 70-90°C.

9. The method for preparing a lithium cobalt nickel manganese oxide battery containing a quaternary ammonium carboxyl hydroxyl additive according to claim 1, characterized in that: In step A, the microwave-assisted reaction time is 3-4 hours.

10. The preparation method of a lithium cobalt nickel manganese oxide battery containing quaternary ammonium carboxyl hydroxyl additive according to claim 1, characterized in that: in step A, after the reaction is completed, a clear leachate is obtained by plate and frame filtration (pressure 0.4-0.6MPa) or centrifugation (speed 4000-6000rpm); Lithium precipitation: Add Na₂CO₃ solution to the leachate to adjust the pH to 10.5-11.0, so that Li… + The precipitate is formed as Li2CO3, filtered, and dried at 60-90℃ for 3-6 hours to obtain battery-grade lithium carbonate. The cobalt-nickel-manganese gradient precipitation method is as follows: Add NH3·H2O to the lithium-removed solution to adjust the pH to 8.5-9.

0. Co 2+ The precipitate was formed as Co(OH)₂, and the purity was calculated; after filtration, the pH was further adjusted to 9.5-10.0, and Ni... 2+ The precipitate was formed as Ni(OH)₂, and the purity was calculated. Finally, the pH was adjusted to 10.5-11.0, and Mn... 2+ The purity was calculated by precipitating the substance as Mn(OH)2.

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