CN103199320A - Method for recycling nickel-cobalt-manganese ternary anode material - Google Patents

Abstract

The invention relates to a method for recycling a nickel-cobalt-manganese ternary positive electrode material, and belongs to the technical field of waste battery recycling. The technical problem solved by the invention is to provide a method for recycling nickel-cobalt-manganese ternary positive electrode materials. It includes the step of removing the binder from the positive electrode sheet of the nickel-cobalt lithium manganese oxide ternary material through heat treatment, and the method for removing the binder in the positive electrode sheet of the nickel-cobalt lithium manganese oxide ternary material is: the positive electrode sheet of the nickel-cobalt lithium manganate ternary material is placed on the Heat treatment at 400~1000℃ for 0.5~5h.

Description

Method for recycling nickel-cobalt-manganese ternary cathode material

technical field

The invention relates to a method for recycling a nickel-cobalt-manganese ternary positive electrode material, and belongs to the technical field of waste battery recycling.

Background technique

Nickel-cobalt-manganese ternary cathode materials are developed from binary Ni-Mn-based materials. In 2001, OhZuku and Makimura synthesized the ternary composite material LiNi _1/3 Co ₁ with nNi:nCo:nMn=1:1:1 for the first time. _/3 Mn _1/3 O ₂ . At the same time, Canadian Dahn et al. studied the influence of composition changes on the crystal structure, capacity, rate discharge and thermal stability of cathode materials. Although LiNi _1/3 Co _1/3 Mn _1/3 O ₂ has not been studied for a long time, because it has a similar structure to LiCoO ₂ and has a good research foundation, it is considered to be the most likely to replace LiCoO ₂ once it is proposed. Received strong support from governments around the world.

Ternary cathode materials can be used in digital communication batteries, notebook batteries, electric tool batteries, power bicycle/car batteries, etc. In terms of communication batteries, in the last 3-5 years, the dominant position of lithium cobalt oxide will gradually weaken, and lithium cobalt oxide and nickel-cobalt-manganese ternary positive electrode materials may coexist. After 5 years, it may be nickel-cobalt-manganese ternary The era of material monopoly. In the field of power tools, nickel-cobalt-manganese ternary materials have high energy density, good high-current charge and discharge performance, excellent cycle performance and safety performance, and may become the main cathode material.

At present, there have been related reports on the recycling of nickel-cobalt-manganese ternary cathode materials. For example: CN200810198972 patent application discloses a method for preparing nickel-cobalt lithium manganese oxide from waste lithium-ion batteries. Its main features are: use waste lithium-ion batteries such as lithium nickel cobalt manganese oxide and lithium nickel cobalt oxide as the raw material for the positive electrode material of the battery, after dismantling, sorting, crushing, screening and other pretreatments, and then use high temperature debonding After processes such as binder and sodium hydroxide removal of aluminum, an inactivated positive electrode material containing nickel, cobalt, and manganese is obtained; then sulfuric acid and hydrogen peroxide system is used for leaching, and P2O4 extraction is used to remove impurities to obtain a pure nickel, cobalt, and manganese solution, which is mixed with Appropriate manganese sulfate, nickel sulfate or cobalt sulfate, so that the molar ratio of nickel, cobalt, and manganese in the solution is 1:1:1; then use ammonium carbonate to adjust the pH value to form a nickel-cobalt-manganese carbonate precursor, and then add An appropriate amount of lithium carbonate is sintered at high temperature to form an active nickel-cobalt-lithium manganese oxide battery material. Another example: CN200710308154 discloses a method for reclaiming precious metals from battery slag containing Co, Ni, Mn, which is to use 250g/ A hydrochloric acid solution with a concentration of 1 or more is used for stirring and leaching, or a sulfuric acid solution with a concentration of 200 g/l or more is used for heating and stirring leaching, and an acidic extractant is used for solvent extraction of the leaching solution, and approximately 100% of Mn and Co are extracted to generate solutions of the respective metals from which the metals are recovered.

The above method realizes the recycling of nickel-cobalt-manganese ternary positive electrode materials, but the separation effect is not good by crushing and sieving to separate nickel-cobalt-manganese lithium manganate and aluminum foil; the nickel-cobalt-manganese carbonate precursor is obtained by carbonate precipitation method , It is easy to cause segregation of components during the preparation process, and the uniformity of the distribution of each element of the oxide cannot be guaranteed, which affects the electrochemical performance of the positive electrode material; the use of organic solvents is easy to cause secondary pollution.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for recycling nickel-cobalt-manganese ternary positive electrode materials.

The method for recycling the nickel-cobalt-manganese ternary positive electrode material of the present invention includes the step of removing the binder from the positive electrode sheet of the nickel-cobalt-manganese oxide ternary material by heat treatment, and the method for removing the binder in the positive electrode sheet of the nickel-cobalt-manganese oxide ternary material positive electrode sheet The method is: heat-treat the positive electrode sheet of nickel-cobalt-lithium-manganese-oxide ternary material at 400-1000°C for 0.5-5 hours.

Wherein, as a preferred technical solution, the method for recycling the nickel-cobalt-manganese ternary positive electrode material of the present invention comprises the following steps:

a. Discharge the residual power of the used lithium battery, then disassemble the battery, and take out the positive electrode sheet of nickel-cobalt-lithium-manganese-oxide ternary material;

b. Vacuum roast the nickel-cobalt-lithium-manganese-oxide ternary material positive plate at 400-1000°C for 0.5-5 hours, then add acid for leaching, add a reducing agent during the leaching process to reduce a small amount of nickel, cobalt, and manganese oxidized during the roasting process, and obtain The mixed solution of nickel salt, cobalt salt, manganese salt, aluminum salt and lithium salt; Wherein, the consumption of reducing agent is to make the small amount of nickel of oxidation, cobalt, manganese reduction get final product, and the reducing agent that adopts is preferably sodium thiosulfate, At least one kind of hydrogen peroxide;

c. Adjust the pH value of the mixed solution to 3-9, preferably adjust the pH value of the mixed solution to 3-7, so that the aluminum in the solution is precipitated, and then filtered to remove the aluminum; among them, sodium hydroxide, potassium hydroxide, lithium hydroxide and other commonly used The lye adjusts the pH value of the mixed solution;

d, according to the nickel-cobalt-manganese content in the solution obtained in step c, add an appropriate amount of nickel-cobalt-manganese sulfate to adjust the nickel, cobalt, and manganese mol ratio in the solution to be 0.8～1.2:0.8～1.2:0.8～1.2;

e. Add sodium hydroxide as a precipitant, add nickel, cobalt, and manganese equivalent molar amounts of ammonia as a complexing agent, adjust the pH of the solution to 10-12, precipitate to obtain a nickel-cobalt-manganese ternary material precursor, filter to obtain lithium salt solution, the lithium salt solution obtains lithium carbonate through purification and precipitation;

f. Mix the nickel-cobalt-manganese ternary material precursor and lithium carbonate at a weight ratio of 2.4-2.6:1, then calcinate at 750-950° C. for 12-24 hours, and cool to obtain nickel-cobalt-manganese lithium manganate.

The above method adopts acid + reducing agent system leaching, and sodium hydroxide is used as precipitant to synthesize nickel cobalt lithium manganese oxide ternary positive electrode material precursor, so as to avoid the generation of Mn ³⁺ (MnOOH) or Mn ⁴⁺ (MnO ₂ ), which will affect the performance of recovered products , the segregation of components will not be caused during the preparation process, which ensures the uniformity of the distribution of each element of the oxide, thereby ensuring the stable electrochemical performance of the positive electrode material.

Further, in the method for recycling the nickel-cobalt-manganese ternary positive electrode material of the present invention, in step b, if the acid concentration is too high, nickel, cobalt, and manganese are easily oxidized; if the acid concentration is too low, the nickel, cobalt, and manganese The leaching rate is relatively low. Taking the above into consideration, it is preferable to use sulfuric acid, hydrochloric acid or nitric acid with a concentration of 10-15wt% for leaching.

Further, in order to improve the electrochemical performance of the positive electrode material, in the method for recycling the above-mentioned nickel-cobalt-manganese ternary positive electrode material, in step d, it is preferable to adjust the molar ratio of nickel, cobalt, and manganese in the solution to 1:1:1.

Among them, in the method for recycling the above-mentioned nickel-cobalt-manganese ternary positive electrode material, in order to make the obtained ternary material have the best electrical properties, in step e, when precipitating the nickel-cobalt-manganese ternary material precursor, it is preferable to control the reaction temperature to be 40 ~90°C.

The present invention has the following beneficial effects: the method of the present invention realizes the recycling of nickel-cobalt-manganese lithium oxide, eliminates the defects existing in existing recycling methods, and in the long run is not only beneficial to the sustainable development of the industry, but also indirectly reduces nickel-cobalt-manganese The cost of metamaterials is conducive to the promotion and popularization of materials.

Detailed ways

The method for recycling the nickel-cobalt-manganese ternary positive electrode material of the present invention includes the step of removing the binder from the positive electrode sheet of the nickel-cobalt-manganese oxide ternary material by heat treatment, and the method for removing the binder in the positive electrode sheet of the nickel-cobalt-manganese oxide ternary material positive electrode sheet The method is: heat-treat the positive electrode sheet of nickel-cobalt-lithium-manganese-oxide ternary material at 400-1000°C for 0.5-5 hours.

Wherein, as a preferred technical solution, the method for recycling the nickel-cobalt-manganese ternary positive electrode material of the present invention comprises the following steps:

a. Discharge the residual power of the used lithium battery, then disassemble the battery, and take out the positive electrode sheet of nickel-cobalt-lithium-manganese-oxide ternary material;

b. Vacuum roast the nickel-cobalt-lithium-manganese-oxide ternary material positive plate at 400-1000°C for 0.5-5 hours, then add acid for leaching, add a reducing agent during the leaching process to reduce a small amount of nickel, cobalt, and manganese oxidized during the roasting process, and obtain The mixed solution of nickel salt, cobalt salt, manganese salt, aluminum salt and lithium salt; Wherein, the consumption of reducing agent is to make the small amount of nickel of oxidation, cobalt, manganese reduction get final product, and the reducing agent that adopts is preferably sodium thiosulfate, At least one kind of hydrogen peroxide;

c. Adjust the pH value of the mixed solution to 3-9, preferably adjust the pH value of the mixed solution to 3-7, so that the aluminum in the solution is precipitated, and then filtered to remove the aluminum; among them, sodium hydroxide, potassium hydroxide, lithium hydroxide and other commonly used The lye adjusts the pH value of the mixed solution;

d, according to the nickel-cobalt-manganese content in the solution obtained in step c, add an appropriate amount of nickel-cobalt-manganese sulfate to adjust the nickel, cobalt, and manganese mol ratio in the solution to be 0.8～1.2:0.8～1.2:0.8～1.2;

e. Add sodium hydroxide as a precipitant, add nickel, cobalt, and manganese equivalent molar amounts of ammonia as a complexing agent, adjust the pH of the solution to 10-12, precipitate to obtain a nickel-cobalt-manganese ternary material precursor, filter to obtain lithium salt solution, the lithium salt solution obtains lithium carbonate through purification and precipitation;

f. Mix the nickel-cobalt-manganese ternary material precursor and lithium carbonate at a weight ratio of 2.4-2.6:1, then calcinate at 750-950° C. for 12-24 hours, and cool to obtain nickel-cobalt-manganese lithium manganate.

The above method adopts acid + reducing agent system leaching, and sodium hydroxide is used as precipitant to synthesize nickel cobalt lithium manganese oxide ternary positive electrode material precursor, so as to avoid the generation of Mn ³⁺ (MnOOH) or Mn ⁴⁺ (MnO ₂ ), which will affect the performance of recovered products , the segregation of components will not be caused during the preparation process, which ensures the uniformity of the distribution of each element of the oxide, thereby ensuring the stable electrochemical performance of the positive electrode material.

Further, in the method for recycling the nickel-cobalt-manganese ternary positive electrode material of the present invention, in step b, if the acid concentration is too high, nickel, cobalt, and manganese are easily oxidized; if the acid concentration is too low, the nickel, cobalt, and manganese The leaching rate is relatively low. Taking the above into consideration, it is preferable to use sulfuric acid, hydrochloric acid or nitric acid with a concentration of 10-15wt% for leaching.

Further, in order to improve the electrochemical performance of the positive electrode material, in the method for recycling the above-mentioned nickel-cobalt-manganese ternary positive electrode material, in step d, it is preferable to adjust the molar ratio of nickel, cobalt, and manganese in the solution to 1:1:1.

Among them, in the method for recycling the above-mentioned nickel-cobalt-manganese ternary positive electrode material, in order to make the obtained ternary material have the best electrical properties, in step e, when precipitating the nickel-cobalt-manganese ternary material precursor, it is preferable to control the reaction temperature to be 40 ~90°C.

The specific implementation of the present invention will be further described below in conjunction with the examples, and the present invention is not limited to the scope of the examples.

Embodiment 1 adopts the method of the present invention to recycle nickel-cobalt-manganese ternary positive electrode material

Discharge the residual power of the waste nickel-cobalt-lithium-manganese-oxide battery, disassemble the battery, take out the positive electrode sheet, and recycle the battery case according to aluminum shell, steel shell, plastic, etc.; calcinate the nickel-cobalt lithium-manganese oxide positive electrode sheet at 1000°C for 0.5h.

Take 100 kg of the calcined nickel-cobalt lithium manganese oxide positive plate, stir and leaching with 10wt% sulfuric acid, add 1 kg of sodium thiosulfate during the leaching process, and filter to obtain a mixture of nickel sulfate, cobalt sulfate, manganese sulfate, aluminum sulfate and lithium sulfate. solution. The pH value of the mixed solution was adjusted to 4.5 to form aluminum hydroxide precipitate, and the aluminum hydroxide was removed by filtration to obtain a mixed solution of nickel sulfate, cobalt sulfate, manganese sulfate, and lithium sulfate. Add nickel-cobalt-manganese sulfate to the solution to adjust the molar ratio of nickel-cobalt-manganese to 1:1:1, then add sodium hydroxide as a precipitant, add an appropriate amount of ammonia as a complexing agent, control the reaction temperature to 40°C, pH value 12, and precipitate The nickel-cobalt-manganese ternary material precursor is obtained, and separated by filtration to obtain a lithium sulfate solution.

The nickel-cobalt-manganese ternary material precursor was mixed with 34.7kg lithium carbonate ball mill, and the mixture was placed in a calciner, calcined at 750°C, kept at a constant temperature for 12 hours, and naturally cooled in the furnace to obtain a nickel-cobalt lithium manganate ternary positive electrode material. The lithium sulfate solution was concentrated and then added with sodium carbonate to precipitate to obtain lithium carbonate. The electrochemical properties of nickel-cobalt lithium manganese oxide ternary positive electrode material recovered are shown in Table 1:

Table 1

Embodiment 2 adopts the method of the present invention to recycle nickel-cobalt-manganese ternary positive electrode material

Discharge the residual power of the waste nickel-cobalt-lithium manganese oxide battery, disassemble the battery, take out the positive plate, and recycle the battery case according to aluminum shell, steel shell, plastic, etc.; bake the nickel-cobalt lithium manganese oxide positive plate at 700°C for 3 hours.

Take 100 kg of the calcined nickel-cobalt lithium manganese oxide positive electrode sheet, use 15wt% sulfuric acid to stir and leach, add 0.8 kg of sodium thiosulfate during the leaching process, and obtain nickel sulfate, cobalt sulfate, manganese sulfate, aluminum sulfate and lithium sulfate by filtering after leaching mixture. The pH value of the mixed solution was adjusted to 5 to form aluminum hydroxide precipitate, and the aluminum hydroxide was removed by filtration to obtain a mixed solution of nickel sulfate, cobalt sulfate, manganese sulfate, and lithium sulfate. Add nickel-cobalt-manganese sulfate to the solution to adjust the molar ratio of nickel-cobalt-manganese to 0.9:1:0.9, then add sodium hydroxide as a precipitating agent, add an appropriate amount of ammonia as a complexing agent, control the reaction temperature at 60°C, pH value 10, and precipitate The nickel-cobalt-manganese ternary material precursor is obtained, and separated by filtration to obtain a lithium sulfate solution.

The nickel-cobalt-manganese ternary material precursor was mixed with 34kg lithium carbonate ball mill, the mixture was placed in a calciner, calcined at 950°C, kept at a constant temperature for 24 hours, and cooled naturally in the furnace to obtain a nickel-cobalt lithium manganate ternary positive electrode material. The lithium sulfate solution was concentrated and then added with sodium carbonate to precipitate to obtain lithium carbonate. The electrochemical properties of nickel-cobalt lithium manganese oxide ternary positive electrode material recovered are as shown in table 2:

Table 2

Embodiment 3 adopts the method of the present invention to recycle nickel-cobalt-manganese ternary positive electrode material

Discharge the residual power of the waste nickel-cobalt-lithium-manganese-oxide battery, disassemble the battery, take out the positive electrode sheet, and recycle the battery case according to aluminum shell, steel shell, plastic, etc.; roast the nickel-cobalt lithium-manganese oxide positive electrode sheet at 400°C for 5 hours.

Take 100kg of the calcined nickel-cobalt lithium manganese oxide positive electrode sheet, and use 12wt% sulfuric acid to stir and leach, add 1.2kg of sodium thiosulfate during the leaching process, and filter to obtain nickel sulfate, cobalt sulfate, manganese sulfate, aluminum sulfate and lithium sulfate after leaching. mixture. The pH value of the mixed solution was adjusted to 6 to form aluminum hydroxide precipitate, and the aluminum hydroxide was removed by filtration to obtain a mixed solution of nickel sulfate, cobalt sulfate, manganese sulfate, and lithium sulfate. Add nickel-cobalt-manganese sulfate to the solution to adjust the molar ratio of nickel-cobalt-manganese to 1:0.9:1, then add sodium hydroxide as a precipitant, add an appropriate amount of ammonia as a complexing agent, control the reaction temperature to 45°C, pH value 11, and precipitate The nickel-cobalt-manganese ternary material precursor is obtained, and separated by filtration to obtain a lithium sulfate solution.

The nickel-cobalt-manganese ternary material precursor was mixed with 35kg of lithium carbonate ball mill, the mixture was placed in a calciner, calcined at 850°C, kept at a constant temperature for 15 hours, and naturally cooled in the furnace to obtain a nickel-cobalt lithium manganate ternary positive electrode material. The lithium sulfate solution was concentrated and then added with sodium carbonate to precipitate to obtain lithium carbonate. The electrochemical properties of nickel-cobalt lithium manganese oxide ternary positive electrode material recovered are as shown in table 3:

table 3

Embodiment 4 adopts the method of the present invention to recycle nickel-cobalt-manganese ternary positive electrode material

Discharge the residual power of the waste nickel-cobalt-lithium manganese oxide battery, disassemble the battery, take out the positive plate, and recycle the battery case according to aluminum shell, steel shell, plastic, etc.; bake the nickel-cobalt lithium manganese oxide positive plate at 600°C for 4 hours.

Take 100kg of the calcined nickel-cobalt-lithium-manganese-oxide positive plate, stir and leach with 12wt% hydrochloric acid, add 2.5kg of hydrogen peroxide during the leaching process, and obtain nickel chloride, cobalt chloride, manganese chloride, aluminum chloride and chlorine chloride by filtering after leaching. lithium mixed solution. The pH value of the mixed solution was adjusted to 6 to form aluminum hydroxide precipitate, and the aluminum hydroxide was removed by filtration to obtain a mixed solution of nickel chloride, cobalt chloride, manganese chloride, and lithium chloride. Add nickel-cobalt-manganese salt to the solution to adjust the molar ratio of nickel-cobalt-manganese to 1:0.9:1, then add sodium hydroxide as a precipitating agent, add an appropriate amount of ammonia as a complexing agent, control the reaction temperature at 45°C, pH value 11, and precipitate to obtain The nickel-cobalt-manganese ternary material precursor is separated by filtration to obtain a lithium chloride solution.

The nickel-cobalt-manganese ternary material precursor was mixed with 35kg of lithium carbonate ball mill, the mixture was placed in a calciner, calcined at 850°C, kept at a constant temperature for 15 hours, and naturally cooled in the furnace to obtain a nickel-cobalt lithium manganate ternary positive electrode material. The lithium sulfate solution was concentrated and then added with sodium carbonate to precipitate to obtain lithium carbonate. The electrochemical properties of nickel-cobalt lithium manganese oxide ternary positive electrode material recovered are as shown in table 3:

table 3

Embodiment 5 adopts the method of the present invention to recycle nickel-cobalt-manganese ternary positive electrode material

Discharge the residual power of the waste nickel-cobalt-lithium-manganese-oxide battery, disassemble the battery, take out the positive electrode piece, and recycle the battery case according to aluminum shell, steel shell, plastic, etc.; bake the nickel-cobalt lithium-manganese oxide positive plate at 900°C for 1 hour.

Take 100 kg of the calcined nickel-cobalt-lithium-manganese-oxide positive plate, stir and leach with 12wt% nitric acid, add 2.5 kg of hydrogen peroxide during the leaching process, and filter to obtain a mixed solution of nickel nitrate, cobalt nitrate, manganese nitrate, aluminum nitrate and lithium nitrate. The pH value of the mixed solution was adjusted to 6 to form aluminum hydroxide precipitate, and the aluminum hydroxide was removed by filtration to obtain a mixed solution of nickel nitrate, cobalt nitrate, manganese nitrate and lithium nitrate. Add nickel-cobalt-manganese salt to the solution to adjust the molar ratio of nickel-cobalt-manganese to 1:0.9:1, then add sodium hydroxide as a precipitating agent, add an appropriate amount of ammonia as a complexing agent, control the reaction temperature at 45°C, pH value 11, and precipitate to obtain The nickel-cobalt-manganese ternary material precursor is separated by filtration to obtain a lithium nitrate solution.

The nickel-cobalt-manganese ternary material precursor was mixed with 35kg of lithium carbonate ball mill, the mixture was placed in a calciner, calcined at 850°C, kept at a constant temperature for 15 hours, and naturally cooled in the furnace to obtain a nickel-cobalt lithium manganate ternary positive electrode material. The lithium sulfate solution was concentrated and then added with sodium carbonate to precipitate to obtain lithium carbonate. The electrochemical properties of nickel-cobalt lithium manganese oxide ternary positive electrode material recovered are as shown in table 3:

table 3

Embodiment 6 adopts the method of the present invention to recycle nickel-cobalt-manganese ternary positive electrode material

Discharge the residual power of the waste nickel-cobalt-lithium-manganese-oxide battery, disassemble the battery, take out the positive electrode sheet, and recycle the battery case according to aluminum shell, steel shell, plastic, etc.; bake the nickel-cobalt lithium-manganese oxide positive electrode sheet at 800°C for 1.5 hours.

Take 100 kg of the calcined nickel-cobalt-lithium manganese oxide positive electrode sheet, stir and leaching with 12wt% sulfuric acid, add 2.5 kg of hydrogen peroxide during the leaching process, and filter to obtain a mixed solution of nickel sulfate, cobalt sulfate, manganese sulfate, aluminum sulfate and lithium sulfate after leaching. The pH value of the mixed solution was adjusted to 6 to form aluminum hydroxide precipitate, and the aluminum hydroxide was removed by filtration to obtain a mixed solution of nickel sulfate, cobalt sulfate, manganese sulfate, and lithium sulfate. Add nickel-cobalt-manganese sulfate to the solution to adjust the molar ratio of nickel-cobalt-manganese to 1:0.9:1, then add sodium hydroxide as a precipitant, add an appropriate amount of ammonia as a complexing agent, control the reaction temperature to 45°C, pH value 11, and precipitate The nickel-cobalt-manganese ternary material precursor is obtained, and separated by filtration to obtain a lithium sulfate solution.

The nickel-cobalt-manganese ternary material precursor was mixed with 35kg of lithium carbonate ball mill, the mixture was placed in a calciner, calcined at 850°C, kept at a constant temperature for 15 hours, and naturally cooled in the furnace to obtain a nickel-cobalt lithium manganate ternary positive electrode material. The lithium sulfate solution was concentrated and then added with sodium carbonate to precipitate to obtain lithium carbonate. The electrochemical properties of nickel-cobalt lithium manganese oxide ternary positive electrode material recovered are as shown in table 3:

table 3

Claims (6)

1. the method recycled of nickel-cobalt-manganese ternary positive electrode, comprise from the heat treatment of nickle cobalt lithium manganate ternary material positive plate and remove the binding agent step, it is characterized in that: remove that the binding agent method is in the nickle cobalt lithium manganate ternary material positive plate: with nickle cobalt lithium manganate ternary material positive plate in 400～1000 ℃ of heat treatment 0.5～5h.

2. the method for nickel-cobalt-manganese ternary positive electrode recycling according to claim 1 is characterized in that comprising the steps:

A, the waste lithium cell remaining capacity has been put, disassembled battery then, taken out nickle cobalt lithium manganate ternary material positive plate;

B, with nickle cobalt lithium manganate ternary material positive plate in 400～1000 ℃ of vacuum baking 0.5～5h, adding acidleach then goes out, leaching process adds minor amount of nickel, cobalt, the manganese that reducing agent is used for the reducing roasting process oxidation, obtains the mixed solution of nickel salt, cobalt salt, manganese salt, aluminium salt and lithium salts;

PH value to 3～9 of c, adjusting mixed solution make aluminum precipitation in the solution, filter then and remove aluminium;

D, according to nickel cobalt manganese content in the mixed solution, the nickel, cobalt, the manganese mol ratio that add in an amount of nickel cobalt-manganese salt regulator solution are 0.8～1.2:0.8～1.2:0.8～1.2;

E, add NaOH as precipitation reagent, add nickel, cobalt, manganese with the ammoniacal liquor of equimolar amounts as compounding ingredient, regulator solution pH value is 10～12, precipitation obtains nickel-cobalt-manganese ternary material presoma, filter, obtain lithium salt solution, lithium salt solution obtains lithium carbonate through purifying precipitation;

F, with nickel-cobalt-manganese ternary material presoma and lithium carbonate by weight 2.4～2.6:1 mixing, in 750～950 ℃ of calcining 12～24h, cooling obtains nickle cobalt lithium manganate then.

3. the method for nickel-cobalt-manganese ternary positive electrode recycling according to claim 2 is characterized in that in the b step, and adopting concentration is sulfuric acid, hydrochloric acid or the nitric acid leaching of 10～15wt%; Described reducing agent is at least a in sodium thiosulfate, the hydrogen peroxide.

4. according to the method for claim 2 or 3 described nickel-cobalt-manganese ternary positive electrodes recyclings, it is characterized in that: in the c step, regulate pH value to 3～7 of mixed solution.

5. according to the method for each described nickel-cobalt-manganese ternary positive electrode recycling of claim 2～4, it is characterized in that: in the d step, the nickel in the regulator solution, cobalt, manganese mol ratio are 1:1:1.

6. according to the method for each described nickel-cobalt-manganese ternary positive electrode recycling of claim 2～5, it is characterized in that: in the e step, when coprecipitated nickel hydroxide cobalt-manganese ternary material presoma, also controlling reaction temperature is 40～90 ℃.