CN107666022A - Lithium, the recovery method of nickel cobalt manganese in a kind of discarded tertiary cathode material - Google Patents

Abstract

The invention discloses a method for recovering lithium, nickel, cobalt and manganese from waste ternary battery positive electrode materials. The waste ternary positive electrode materials are used as raw materials, and a carbon reducing agent is added. Carry out roasting and reduction under low temperature, the roasted product is added into water for water-soluble reaction, after the reaction is completed, filter to obtain lithium carbonate filtrate and filter residue 1, filter residue 1 to obtain nickel-cobalt-manganese filtrate and filter residue 2 after sulfuric acid leaching, add sulfate to adjust nickel-cobalt-manganese filtrate The ratio of nickel, cobalt, and manganese in the medium is subjected to precipitation reaction with sodium hydroxide solution and ammonia solution under a protective atmosphere. The reaction temperature is controlled at 50~70°C, and the reaction pH value is 10~11. After the precipitation reaction, the ternary precursor is obtained The slurry is filtered, washed and dried to obtain a ternary precursor. Compared with the prior art, the present invention has simple lithium carbonate separation conditions, low cost in the leaching process of nickel, cobalt and manganese and regeneration of ternary material precursor, and high recovery rate.

Description

A recovery method for lithium, nickel, cobalt and manganese in waste ternary positive electrode materials

technical field

The invention belongs to the field of solid waste recovery, and relates to a method for recovering lithium, nickel, cobalt and manganese in the positive electrode material of a waste ternary lithium ion battery.

Background technique

Lithium-ion batteries are favored by the market and consumers for their high energy density, long cycle life, and environmental friendliness. At present, the cheap and safe ternary material LiNi _x Co _{y Mnz} O ₂ is a commercial cathode material widely used in the market, mainly used in portable electronic devices such as laptops and cameras and electric vehicles. Since its promotion, its number has grown explosively. In 2016, the production of new energy vehicles in China exceeded 507,000, and the service life of power batteries is generally 3 years. Therefore, a large number of lithium-ion batteries will be scrapped this year and next. It is expected that by 2020, The amount of scrapped lithium-ion batteries reached 32.2Gwh, a total of about 500,000 tons of battery materials.

Lithium-ion batteries with ternary materials as the positive electrode account for about 40-50% of the lithium-ion batteries scrapped every year in my country. The positive electrode materials of these waste ternary batteries contain a large amount of valuable metal elements such as lithium, nickel, cobalt, and manganese, which are generally higher than The cumulative reserves of metal content in natural minerals will reach 5.0, 3.0, 20, and 15,000 tons respectively. For the purpose of environmental protection and sustainable economic development, it is of great significance to recycle waste ternary cathode materials.

People have carried out a lot of research on the recycling of waste lithium-ion ternary battery materials. At present, the hydrometallurgical process is the main method, and acid leaching is usually used to extract lithium, nickel, cobalt and manganese;

Chinese Patent Publication No. CN102956935A discloses a method for treating waste power battery ternary positive electrode materials, including the following steps: alkaline leaching, acid leaching to extract nickel lithium and manganese cobalt, separation of nickel lithium and manganese cobalt, recovery of nickel, recovery of lithium, recovery of cobalt , recovery of manganese;

Chinese Patent Publication No. CN106505272A discloses a treatment method for lithium battery anode material waste, including the following steps: A roasting, B acid leaching, C removing iron and aluminum, D removing copper and zinc, E fluoride lithium precipitation, F removing calcium and magnesium, G multi-stage extraction, H oil removal, etc.;

The above-mentioned patent improves the leaching efficiency by adding hydrogen peroxide as a reducing agent, and then separates lithium-nickel-cobalt-manganese through chemical precipitation and solvent extraction; the process is complex, the cost of the reducing agent is high, and the subsequent separation and purification procedures are numerous and complicated. At the same time, the solution after separation and purification contains The concentration of valence metals is low, and a large amount of waste water will be generated.

High-efficiency and energy-saving recycling of waste ternary cathode materials can protect the environment, realize the recycling of secondary resources, and at the same time promote sustainable economic development. In today's society with increasing awareness of environmental protection and increasingly tight resources, efficient and environmentally friendly recycling of lithium, nickel, cobalt, and manganese is of great importance. significance.

Contents of the invention

In view of the above problems, the purpose of the present invention is to provide an efficient separation and recovery of lithium, nickel, cobalt and manganese in waste ternary positive electrode materials.

The purpose of the invention of the present invention is to be realized through the following technical solutions:

A recovery method for lithium, nickel, cobalt and manganese in waste ternary positive electrode materials, using waste ternary positive electrode materials as raw materials, adding a carbon reducing agent, after mixing ingredients, performing roasting and reduction under a protective atmosphere at 500-700°C, roasting The product is added to distilled water for water-soluble reaction. After the reaction is completed, filter to obtain lithium carbonate filtrate and filter residue 1. After the filter residue is leached with sulfuric acid, filter to obtain nickel-cobalt-manganese filtrate and filter residue 2. Add sulfate to adjust nickel and cobalt in the nickel-cobalt-manganese filtrate. , manganese ratio, and then carry out precipitation reaction with sodium hydroxide solution and ammonia solution under protective atmosphere, control the reaction temperature at 50~70℃, and the reaction pH value is 10~11, and obtain the slurry of ternary precursor after precipitation reaction , filtered, washed, and dried to obtain a ternary precursor;

Wherein, sodium hydroxide solution can be replaced by sodium carbonate solution.

Preferably, the protective atmosphere involved in the present invention is nitrogen, argon or other inert gases.

Preferably, the mixing process of the raw materials and the reducing agent in the present invention uses a ball mill for mixing, and more preferably the ball milling time is 0.5~2h, and the rotation speed is 100~300rpm.

Preferably, the added amount of the carbon reducing agent is 5-30% of the mass of the waste ternary cathode material; further preferably, the carbon reducing agent is coke, and the carbon content of the coke is greater than or equal to 85%.

Preferably, the liquid-solid ratio of the calcined product obtained in the water dissolution reaction to the distilled water is 10-100ml/g.

Preferably, the liquid-solid ratio of the filter residue obtained in the sulfuric acid leaching process to the sulfuric acid solution is 5-15ml/g.

Preferably, the ratio of nickel, cobalt, and manganese in the filtrate containing nickel, cobalt, and manganese is 1 ~ 8: 1 ~ 2: 1 ~ 4 by adding sulfate; more preferably 1: 1: 1, 4: 2: 4, 5: One of 2:3, 6:2:2, 8:1:1.

The invention provides an optimized recovery method for lithium, nickel, cobalt and manganese in waste ternary positive electrode materials, comprising the following steps:

S1. Mixing: use waste ternary cathode materials as raw materials, add carbon reducing agent, and mix ingredients;

S2. Reduction roasting: the mixture after mixing the ingredients of S1 is roasted and reduced in a protective atmosphere at 500~700°C;

S3. Water-soluble: the roasted product obtained in step S2 is added to distilled water for water-soluble reaction, and after the reaction is completed, filter to obtain lithium carbonate filtrate and filter residue one;

S4. Sulfuric acid leaching: adding the filter residue obtained in step S3 to the configured sulfuric acid solution for leaching, and filtering after leaching to obtain the nickel-cobalt-manganese filtrate and filter residue II;

S5. Preparing the precursor: adding nickel sulfate, cobalt sulfate, and manganese sulfate to the nickel-cobalt-manganese solution obtained in step S4 to adjust the ratio of nickel, cobalt, and manganese; Under the atmosphere, it is fed into the reactor in parallel flow, the reaction temperature is controlled at 50-70°C, and the reaction pH is 10-11. After the reaction is completed, the slurry containing the ternary precursor is filtered, washed, and dried to obtain the ternary precursor.

In the technical solution of the present invention, coke is used as a reducing agent to reduce and roast waste ternary positive electrode materials, and carbon reducing agent and active material _LiNix Co _{y Mnz} O ₂ are used for reduction and roasting to obtain roasted products Li ₂ CO ₃ , MnO, Ni , NiO, Co, and then the roasted product is added to distilled water for water-soluble reaction, and the lithium carbonate solution and the filter residue containing MnO, Ni, NiO, Co are separated. After the ion ratio, sodium hydroxide and ammonia solution are added to carry out precipitation reaction to obtain ternary precursor slurry.

Preferably, the calcining reduction time in step S1 is 0.5~3h.

Preferably, the dissolution temperature in step S2 is room temperature, and the dissolution time is 2 to 5 hours.

Preferably, stirring is carried out during the water-soluble reaction in step S2, and the stirring speed is 100-500 rpm.

Preferably, the concentration of the sulfuric acid solution in step S3 is 0.1-4mol/L, and the leaching time is 1-8h.

Stirring is preferably carried out during the sulfuric acid leaching process in step S3, and the stirring intensity is 100-500 rpm.

Preferably, in step S4, the concentration of the nickel-cobalt-manganese solution is 0.5-5 mol/L, the concentration of the sodium hydroxide solution is 0.5-4 mol/L, the concentration of ammonia water is 0.5-8 mol/L, and the reaction time is 10-20 h , by controlling the flow rate of sodium hydroxide solution to control the reaction pH value of 10 ~ 11.

Preferably, step S4 is drying at 80-120°C.

Compared with prior art, the beneficial effect of the present invention:

(1) In the technical solution of the present invention, the discarded ternary positive electrode material is used as the object, and the lithium is separated by reduction and roasting, and then washed with water, and then the obtained filter residue is leached with sulfuric acid to obtain a nickel-cobalt-manganese filtrate, and the nickel-cobalt-manganese solution is adjusted according to different needs The ratio of nickel, cobalt, and manganese in the mixture, and then carry out precipitation reaction to obtain different ternary precursors. The method of the present invention can realize the efficient and harmless utilization of waste ternary cathode materials, with short process, low energy consumption, clean process, and easy to carry out Industrial production.

(2) The present invention uses cheap coke as a reducing agent to carry out reduction roasting with waste ternary positive electrode materials, and does not need to use more expensive hydrogen peroxide as a reducing agent in the leaching process, and uses water dissolution and acid leaching for the reduction products step by step, which can be Efficiently separate lithium and nickel-cobalt-manganese elements, eliminating the need to separate lithium and nickel-cobalt-manganese elements.

(3) After the mixing and reduction roasting of the present invention, in the water dissolution process, when the liquid-solid ratio is 100ml/g, the dissolution temperature is 30°C, the dissolution time is 4h, and the stirring intensity is 100rpm, lithium and lithium can be dissolved efficiently. The dissolution rate can reach 93.68%. During the sulfuric acid leaching process, when the liquid-solid ratio is 10ml/g, the leaching temperature is 90°C, the leaching time is 3h, and the stirring intensity is 100rpm, the leaching efficiencies of nickel, cobalt, and manganese can reach 99.56%, 99.14%, and 95.9% respectively. .

(4) The ternary precursor prepared by the present invention has good sphericity, uniform particle size, and smooth surface, reaching the level of commercially available common precursors.

Description of drawings

Fig. 1 is the implementation process flow chart of the present invention.

Figure 2 is a SEM image of the ternary precursor prepared in Example 1.

Figure 3 is a SEM image of the ternary precursor prepared in Example 2.

Figure 4 is a SEM image of the ternary precursor prepared in Example 3.

5 is an SEM image of the ternary precursor prepared in Example 4.

6 is an SEM image of the ternary precursor prepared in Example 5.

detailed description

The present invention will be further described below in conjunction with specific examples. The following examples are for illustrative purposes only, and should not be construed as limiting the present invention. Unless otherwise specified, the raw materials and equipment used in the following examples are those conventionally used in the art.

Example 1

Process flow chart of the present invention is as shown in accompanying drawing 1.

In this embodiment, a method for recovering lithium, nickel, cobalt, and manganese from waste ternary positive electrode materials comprises the following steps:

S1. Ball milling and mixing: mill the waste ternary cathode material and coke accounting for 10% of the mass of the waste ternary cathode material in a planetary ball mill at a speed of 200 rpm for 1 hour;

S2. Reduction roasting: the mixture of the waste ternary cathode material and coke after ball milling is roasted in 99.99% argon atmosphere, the roasting temperature is 600°C, and the roasting time is 2h;

S3. Water dissolution: add the cooled roasted product into water to dissolve, the dissolution temperature is 30°C, the dissolution time is 4h, the liquid-solid ratio is 100ml/g, and the stirring intensity is 100rpm. After the reaction is completed, the slurry is filtered to obtain the filtrate and Filter residue, sampling analysis detects that the dissolution rate of lithium in the filtrate reaches 93.68%;

S4. Sulfuric acid leaching: add the filter residue obtained by filtering after water leaching into the prepared sulfuric acid solution, the sulfuric acid concentration is 4mol/L, the liquid-solid ratio is 10ml/g, the leaching temperature is 90°C, and the leaching time is 4 h. Stir The intensity is 100rpm. After the reaction is completed, the slurry is filtered to obtain a solution containing nickel, cobalt and manganese and filter residue. Sampling analysis detects that the leaching rates of nickel, cobalt and manganese in the filtrate reach 99.56%, 99.14%, and 95.9%, respectively.

S5. Preparation of precursor: add nickel sulfate, cobalt sulfate, and manganese sulfate according to the ratio of nickel, cobalt, and manganese metal ions in the leaching solution to adjust the ratio of nickel, cobalt, and manganese metal ions to 1:1:1, and the concentration of the nickel-cobalt-manganese solution is 2 mol/L, the concentration of sodium hydroxide solution is 2mol/L, and the concentration of ammonia water is 0.5mol/L. The three solutions are added to the reactor in parallel with the peristaltic pump under the protection of nitrogen. The reaction temperature is controlled at 60°C. The reaction time was 20 h, and the pH value of the reaction was controlled by controlling the flow rate of the sodium hydroxide solution to be 10-11. After the reaction, the ternary precursor slurry was filtered, washed, and dried at 100 °C to obtain the 111-type ternary precursor.

Figure 2 is the SEM image of the 111-type ternary precursor prepared in this example. SEM detection and analysis shows that the ternary precursor particles prepared by the present invention are evenly distributed, have good sphericity, smooth surface, and evenly dispersed particles.

Example 2

Experimental raw material, step are with embodiment 1.

In this embodiment, a method for recovering lithium, nickel, cobalt, and manganese from waste ternary positive electrode materials comprises the following steps:

S1. Ball milling and mixing: mill the waste ternary cathode material and coke accounting for 5% of the mass of the waste ternary cathode material in a planetary ball mill at a speed of 100rpm for 2h;

S2. Reduction roasting: the mixture of the ball milled waste ternary cathode material and coke is roasted in 99.99% argon atmosphere, the roasting temperature is 500°C, and the roasting time is 0.5h;

S3. Water dissolution: add the cooled roasted product into water to dissolve, the dissolution temperature is 25°C, the dissolution time is 2h, the liquid-solid ratio is 50ml/g, and the stirring intensity is 200rpm. After the reaction is completed, the slurry is filtered to obtain the filtrate and Filter residue, sampling analysis detects that the dissolution rate of lithium in the filtrate reaches 91.98%;

S4. Sulfuric acid leaching: Add the filter residue obtained by filtering after water leaching into the prepared sulfuric acid solution, the sulfuric acid concentration is 3mol/L, the liquid-solid ratio is 5ml/g, the leaching temperature is 70°C, and the leaching time is 2 h. Stir The intensity is 200rpm. After the reaction is completed, the slurry is filtered to obtain a solution containing nickel, cobalt and manganese and filter residue. Sampling analysis detects that the leaching rates of nickel, cobalt and manganese in the filtrate reach 92.36%, 94.74%, and 90.16%, respectively.

S5. Preparation of precursor: add nickel sulfate, cobalt sulfate, and manganese sulfate according to the ratio of nickel, cobalt, and manganese metal ions in the leaching solution to adjust the ratio of nickel, cobalt, and manganese metal ions to 4:2:4, and the concentration of the nickel-cobalt-manganese solution is 4 mol/L, the concentration of sodium hydroxide solution is 4mol/L, and the concentration of ammonia water is 3mol/L. The three solutions are added to the reactor in parallel with the peristaltic pump under the protection of nitrogen. The reaction temperature is controlled at 50 ° C. The reaction time The reaction time was 15 h, and the pH value of the reaction was controlled by controlling the flow rate of sodium hydroxide solution to 10-11. After the reaction, the ternary precursor slurry was filtered, washed, and dried at 80 °C to obtain the 424-type ternary precursor.

Figure 3 is the SEM image of the 424-type ternary precursor prepared in this example. SEM detection and analysis shows that the ternary precursor particles prepared by the present invention are evenly distributed, have good sphericity, smooth surface, and evenly dispersed particles.

Example 3

Experimental raw material, step are with embodiment 1.

In this embodiment, a method for recovering lithium, nickel, cobalt, and manganese from waste ternary positive electrode materials comprises the following steps:

S1. Ball mill mixing: mill the waste ternary cathode material and coke accounting for 20% of the mass of the waste ternary cathode material in a planetary ball mill at a speed of 300rpm for 0.5h;

S2. Reduction roasting: the mixture of the ball milled waste ternary cathode material and coke is roasted in 99.99% argon atmosphere, the roasting temperature is 700°C, and the roasting time is 3h;

S3. Water dissolution: add the cooled roasted product into water to dissolve, the dissolution temperature is 28°C, the dissolution time is 5h, the liquid-solid ratio is 60ml/g, and the stirring intensity is 500rpm. After the reaction is completed, the slurry is filtered to obtain the filtrate and Filter residue, sampling analysis detects that the dissolution rate of lithium in the filtrate reaches 92.68%;

S4. Sulfuric acid leaching: Add the filter residue obtained by filtering after water leaching into the prepared sulfuric acid solution, the concentration of sulfuric acid is 2mol/L, the liquid-solid ratio is 15ml/g, the leaching temperature is 70°C, and the leaching time is 8 h. Stir The intensity is 500rpm. After the reaction is completed, the slurry is filtered to obtain a solution containing nickel, cobalt and manganese and filter residue. Sampling analysis detects that the leaching rates of nickel, cobalt and manganese in the filtrate reach 98.76%, 98.64%, and 94.9%, respectively.

S5. Preparation of precursor: add nickel sulfate, cobalt sulfate, and manganese sulfate according to the ratio of nickel, cobalt, and manganese metal ions in the leaching solution to adjust the ratio of nickel, cobalt, and manganese metal ions to 5:2:3, and the concentration of the nickel-cobalt-manganese solution is 2 mol/L, the concentration of sodium hydroxide solution is 2mol/L, and the concentration of ammonia water is 0.5mol/L. The three solutions are added to the reactor in parallel with the peristaltic pump under the protection of nitrogen. The reaction temperature is controlled at 70°C. The time is 16 hours, and the pH value of the reaction is controlled by controlling the flow rate of the sodium hydroxide solution to be 10-11. After the reaction is completed, the ternary precursor slurry is filtered, washed, and dried at 100°C to obtain the 523-type ternary precursor.

Figure 4 is the SEM image of the 523-type ternary precursor prepared in this example. SEM detection and analysis shows that the ternary precursor particles prepared by the present invention are evenly distributed, have good sphericity, smooth surface, and evenly dispersed particles.

Example 4

Experimental raw material, step are with embodiment 1.

In this embodiment, a method for recovering lithium, nickel, cobalt, and manganese from waste ternary positive electrode materials comprises the following steps:

S1. Ball mill mixing: mill the waste ternary cathode material and coke accounting for 20% of the mass of the waste ternary cathode material in a planetary ball mill at a speed of 300rpm for 0.5h;

S2. Reduction roasting: the mixture of the ball milled waste ternary cathode material and coke is roasted in 99.99% argon atmosphere, the roasting temperature is 600°C, and the roasting time is 3h;

S3. Water dissolution: add the cooled roasted product into water to dissolve, the dissolution temperature is 28°C, the dissolution time is 5h, the liquid-solid ratio is 10ml/g, and the stirring intensity is 500rpm. After the reaction is completed, the slurry is filtered to obtain the filtrate and Filter residue, sampling analysis detects that the dissolution rate of lithium in the filtrate reaches 91.68%;

S4. Sulfuric acid leaching: add the filter residue obtained by filtering after water leaching into the prepared sulfuric acid solution, the sulfuric acid concentration is 3mol/L, the liquid-solid ratio is 15ml/g, the leaching temperature is 50°C, and the leaching time is 8 h. Stir The intensity is 500rpm. After the reaction is completed, the slurry is filtered to obtain a solution containing nickel, cobalt and manganese and filter residue. Sampling analysis detects that the leaching rates of nickel, cobalt and manganese in the filtrate reach 99.26%, 98.94%, and 94.63%, respectively.

S5. Preparation of precursor: add nickel sulfate, cobalt sulfate, and manganese sulfate according to the ratio of nickel, cobalt, and manganese metal ions in the leaching solution to adjust the ratio of nickel, cobalt, and manganese metal ions to 6:2:2, and the concentration of the nickel-cobalt-manganese solution is 1 mol/L, the concentration of sodium hydroxide solution is 2 mol/L, and the concentration of ammonia water is 1 mol/L. The three solutions are added to the reactor in parallel with the peristaltic pump under the protection of nitrogen. The reaction temperature is controlled at 70 °C, and the reaction time is For 12 hours, the pH value of the reaction was controlled by controlling the flow rate of the sodium hydroxide solution to be 10-11. After the reaction, the ternary precursor slurry was filtered, washed, and dried at 120°C to obtain the 622-type ternary precursor.

Fig. 5 is an SEM image of the 622-type ternary precursor prepared in this example. SEM detection and analysis shows that the ternary precursor particles prepared by the present invention are evenly distributed, have good sphericity, smooth surface, and evenly dispersed particles.

Example 5

Experimental raw material, step are with embodiment 1.

In this embodiment, a method for recovering lithium, nickel, cobalt, and manganese from waste ternary positive electrode materials comprises the following steps:

S1. Ball milling and mixing: mill the waste ternary cathode material and coke accounting for 15% of the mass of the waste ternary cathode material in a planetary ball mill at a speed of 400rpm for 2h;

S2. Reduction roasting: the mixture of the ball milled waste ternary cathode material and coke is roasted in 99.99% argon atmosphere, the roasting temperature is 650°C, and the roasting time is 2h;

S3. Water dissolution: add the cooled roasted product into water to dissolve, the dissolution temperature is 30°C, the dissolution time is 4h, the liquid-solid ratio is 50ml/g, and the stirring intensity is 200rpm. After the reaction is completed, the slurry is filtered to obtain the filtrate and Filter residue, sampling analysis detects that the dissolution rate of lithium in the filtrate reaches 90.68%;

S4. Sulfuric acid leaching: add the filter residue obtained by filtering after water leaching into the prepared sulfuric acid solution, the sulfuric acid concentration is 2.5mol/L, the liquid-solid ratio is 5ml/g, the leaching temperature is 65°C, and the leaching time is 7 h. The stirring intensity was 400rpm. After the reaction was completed, the slurry was filtered to obtain a solution containing nickel, cobalt and manganese and filter residue. Sampling analysis detected that the leaching rates of nickel, cobalt and manganese in the filtrate reached 98.86%, 98.54%, and 94.93%, respectively.

S5. Preparation of precursor: add nickel sulfate, cobalt sulfate, and manganese sulfate according to the ratio of nickel, cobalt, and manganese metal ions in the leaching solution to adjust the ratio of nickel, cobalt, and manganese metal ions to 8:1:1, and the concentration of the nickel-cobalt-manganese solution is 2mol/L, the concentration of sodium hydroxide solution is 2mol/L, and the concentration of ammonia water is 2mol/L. The three solutions are added to the reactor in parallel with the peristaltic pump under the protection of nitrogen. The reaction temperature is controlled at 70 °C, and the reaction time is After 18 hours, the pH value of the reaction was controlled to be 10-11 by controlling the flow rate of the sodium hydroxide solution. After the reaction was completed, the ternary precursor slurry was filtered, washed, and dried at 100°C to obtain the 811-type ternary precursor.

Fig. 6 is an SEM image of the 811-type ternary precursor prepared in this example. SEM detection and analysis shows that the ternary precursor particles prepared by the present invention are evenly distributed, have good sphericity, smooth surface, and evenly dispersed particles.

Claims (10)

1. lithium, the recovery method of nickel cobalt manganese in a kind of discarded tertiary cathode material, it is characterised in that to discard tertiary cathode material For raw material, add carbonaceous reducing agent, after blended dispensing under protective atmosphere, roasting reduction, product of roasting are carried out at 500 ~ 700 DEG C It is added in distilled water and carries out water-soluble reaction, is filtrated to get lithium carbonate filtrate and filter residue one after completion of the reaction, filter residue is once sulfuric acid Nickel and cobalt containing manganese filtrate and filter residue two are filtrated to get after leaching, addition sulfate adjusts nickel, cobalt, the ratio of manganese in nickel and cobalt containing manganese filtrate Example, then carries out precipitation reaction under protective atmosphere with sodium hydroxide solution and ammonia spirit, and controlling reaction temperature is 50 ~ 70 DEG C, pH value in reaction is 10 ~ 11, and the slurry of ternary precursor is obtained after precipitation reaction, filters, wash, being dried to obtain ternary forerunner Body.

2. lithium, the recovery method of nickel cobalt manganese in tertiary cathode material are discarded according to claim 1, it is characterised in that institute State 5 ~ 30% that carbonaceous reducing agent addition is discarded tertiary cathode material quality；It is preferred that the carbonaceous reducing agent is coke, the coke Carbon content is more than or equal to 85%.

3. lithium, the recovery method of nickel cobalt manganese in tertiary cathode material are discarded according to claim 1, it is characterised in that institute It is 10 ~ 100ml/g to state the liquid-solid ratio of gained product of roasting and distilled water in water-soluble reaction.

4. lithium, the recovery method of nickel cobalt manganese in tertiary cathode material are discarded according to claim 1, it is characterised in that institute The liquid-solid ratio of gained filter residue one and sulfuric acid solution is 5 ~ 15ml/g during stating sulfuric acid leaching.

5. lithium, the recovery method of nickel cobalt manganese in tertiary cathode material are discarded according to claim 1, it is characterised in that add It is 1 ~ 8 to add nickel, cobalt, the ratio of manganese in sulfate regulation nickel and cobalt containing manganese filtrate：1~2：1~4；Preferably 1:1:1、4:2:4、5:2: 3、6:2:2、8:1:One kind in 1.

6. according to lithium in any one of the claim 1 ~ 5 discarded tertiary cathode material, the recovery method of nickel cobalt manganese, its feature exists In comprising the following steps：

S1. batch mixing：Using discarded tertiary cathode material as raw material, carbonaceous reducing agent is added, carries out mix；

S2. reduction roasting：Mixture after S1 mixes is subjected to roasting reduction at protective atmosphere, 500 ~ 700 DEG C；

S3. it is water-soluble：Product of roasting obtained by step S2 is added in distilled water and carries out water-soluble reaction, is filtrated to get after completion of the reaction Lithium carbonate filtrate and filter residue one；

S4. sulfuric acid leaching：The obtained filter residues of step S3 are added in the sulfuric acid solution configured and leached, are filtered after leaching Obtain nickel and cobalt containing manganese filtrate and filter residue two；

S5. presoma is prepared：In the nickel and cobalt containing manganese solution obtained to step S4 add nickel sulfate, cobaltous sulfate, manganese sulfate regulation nickel, The ratio of cobalt, manganese, by nickel cobalt manganese solution, sodium hydroxide solution and ammonia spirit, cocurrent is added in reactor under protective atmosphere, Controlling reaction temperature be 50 ~ 70 DEG C, pH value in reaction be 10 ~ 11, after completion of the reaction by the slurries filtration containing ternary precursor, wash Wash, be dried to obtain ternary precursor.

7. lithium, the recovery method of nickel cobalt manganese in tertiary cathode material are discarded according to claim 6, it is characterised in that institute State 0.5 ~ 3h of roasting reduction time in step S1.

8. lithium, the recovery method of nickel cobalt manganese in tertiary cathode material are discarded according to claim 6, it is characterised in that institute It is room temperature to state leaching temperature in step S2, and dissolution time is 2 ~ 5h, is preferably stirred in water-soluble course of reaction, speed of agitator For 100 ~ 500rpm.

9. lithium, the recovery method of nickel cobalt manganese in tertiary cathode material are discarded according to claim 6, it is characterised in that institute It is 0.1 ~ 4mol/L to state sulfuric acid solution concentration in step S3, and 50 ~ 90 DEG C of extraction temperature, extraction time is 1 ~ 8h, preferably in sulfuric acid Leaching process is stirred, the rpm of stirring intensity 100 ~ 500.

10. lithium, the recovery method of nickel cobalt manganese in tertiary cathode material are discarded according to claim 6, it is characterised in that step In rapid S4, the concentration of nickel cobalt manganese solution is 0.5 ~ 5 mol/L, and the concentration of sodium hydroxide solution is 0.5 ~ 4mol/L, ammonia concn For 0.5 ~ 8 mol/L, the reaction time is 10 ~ 20h, is 10 ~ 11 by controlling sodium hydroxide solution flow control pH value in reaction.