CN111733326A - A method for efficiently recycling waste lithium-ion battery ternary positive electrode material - Google Patents

Abstract

The invention relates to a method for efficiently recycling ternary positive electrode materials of waste lithium ion batteries. In the method, the positive electrode powder of the cathode of the waste lithium ion battery and the biomass powder are uniformly mixed, dried and pressed to form a lumpy mixed material, and the microwave roasted product is obtained by two-stage heating and roasting under nitrogen atmosphere and microwave conditions; Carbonation leaching, solid-liquid separation to obtain filtrate and filter residue; adding sufficient precipitant to the filtrate for precipitation treatment to obtain lithium phosphate precipitation; sulfuric acid leaching the filter residue, precipitation to remove the metal impurity ions in the leaching solution to obtain a purified leachate, and adding metal salts to the purified leachate , and then co-precipitated to obtain a nickel-cobalt-manganese ternary precursor. The invention realizes the efficient separation of lithium in the recovery process of lithium ion batteries, reduces the roasting temperature of the separation of lithium by in-situ reduction method, prepares ternary precursors by using low-lithium filter residues, and solves the problem that lithium ions are easily mixed into the precipitation during the co-precipitation process. .

Description

A method for efficiently recycling waste lithium-ion battery ternary positive electrode material

technical field

The invention relates to a method for efficiently recycling ternary positive electrode materials of waste and used lithium ion batteries, and belongs to the technical field of waste and used lithium ion battery recycling.

Background technique

Lithium-ion batteries have been mass-produced and applied due to their excellent electrochemical properties, and the subsequent scrapped lithium-ion batteries have become new "urban mines". Therefore, in the near future, there will be a large number of obsolete lithium-ion batteries that need to be recycled. Cathode materials have high recycling value as the most expensive part of lithium-ion battery production. On the contrary, waste lithium-ion batteries contain heavy metal oxides and toxic electrolytes, which will cause great harm to the human body and the natural environment if not handled properly.

The general steps for recycling spent lithium-ion batteries are disassembly, screening, crushing and extraction. The crushed cathode powder is then processed by wet method or fire method to obtain the desired product. Lithium, as a promising rare metal, is expected to be in short supply for some time to come. The advantage of wet processing is that the recovery rate is high, but the processing procedure is complex and the processing cost is high, and the wet recovery process usually extracts lithium at the end, which greatly increases the difficulty of recovering lithium. Fire method refers to adding positive electrode powder into slag-forming agent and then smelting and forming slag at high temperature above 1300℃ to separate valuable metals. Although fire method has large processing capacity and simple process, the recovery rate of lithium is very low.

At present, there are some methods trying to improve the separation efficiency of lithium by combining the wet method with the high-temperature roasting process, but there are the following shortcomings in these methods: (1) in the prior art, the electrode material after the roasting is impregnated with a sulfuric acid solution to obtain an acid leachate, The Li in the leaching solution is extracted and separated with PC-88A, carbonate is added to the water phase after extraction, and the Li ₂ CO ₃ product is obtained by filtration and separation. This method has a complicated technological process and a long period. (2) the prior art is roasted in a muffle furnace after the positive electrode material is mixed with graphite, by leaching the roasted product with water at normal temperature to separate lithium and other metals, the roasting temperature of this method is high, the energy consumption is large, and the pollution is relatively large, And the utilization of transition metals is not considered.

In addition, the current direct regeneration process basically adopts the method of co-precipitation to prepare the precursor of the cathode material, and lithium ions are easily mixed into the precipitation during the co-precipitation process. In the prior art, a ternary precursor is prepared by directly performing acid leaching-co-precipitation on the positive electrode material of waste lithium-ion batteries. The precursor prepared by this method is mixed with some lithium impurities, and the precursor is calcined at high temperature to prepare the positive electrode material. The process is difficult to control the morphology of the material. Therefore, it is urgent to study how to efficiently extract lithium from cathode powders of spent lithium-ion batteries.

SUMMARY OF THE INVENTION

Aiming at the problems existing in the existing lithium ion battery recovery and regeneration technologies, the present invention provides a method for efficiently recovering the ternary positive electrode material of the waste lithium ion battery. Press molding to obtain a lumpy mixed material, carry out two-stage heating and roasting under nitrogen atmosphere and microwave conditions to obtain a microwave roasting product; carry out carbonation leaching of the microwave roasting product, and separate solid-liquid to obtain filtrate and filter residue; add enough precipitant to the filtrate to carry out Precipitation treatment to obtain lithium phosphate precipitate; sulfuric acid leaching the filter residue, precipitation to remove metal impurity ions in the leaching solution to obtain purified leaching solution, adding metal salts to the purified leaching solution, and co-precipitation to obtain a nickel-cobalt-manganese ternary precursor. The invention realizes the efficient separation of lithium in the recovery process of lithium ion batteries, reduces the roasting temperature of the separation of lithium by the in-situ reduction method, uses low-lithium filter residues to prepare ternary precursors, and solves the problem that lithium ions are easily mixed into the precipitation during the co-precipitation process. At the same time, it also solves the problem that it is difficult to control the material morphology in the process of calcining the precursor prepared with high lithium solution at high temperature to prepare the cathode material.

A method for efficiently recycling waste lithium-ion battery ternary positive electrode materials, the specific steps are as follows:

(1) respectively crushing and sieving the cathode and biomass of the waste lithium-ion battery to obtain cathode powder and biomass powder;

(2) Mixing the positive electrode powder and the biomass powder uniformly, drying and pressing to obtain a lumpy mixture;

(3) Under nitrogen atmosphere and microwave conditions, the block-like mixture is heated up to a temperature of 300-600°C at a constant speed and kept for 14-30min, and the second-stage temperature is raised to a temperature of 500-900°C and kept at a constant speed for 5-60min. Cool to room temperature with a furnace under nitrogen atmosphere to obtain a microwave calcined product;

(4) placing the microwave roasting product in an aqueous solution, and feeding carbon dioxide gas into the aqueous solution, carrying out carbonation leaching under agitation, and separating solid-liquid to obtain filtrate and filter residue;

(5) adding a sufficient amount of precipitating agent to the filtrate and adjusting the pH of the system to be 3 to 4 to carry out precipitation treatment to obtain lithium phosphate precipitation;

(6) adopt sulfuric acid to leach filter residue, adopt sodium hydroxide to adjust the pH value of leachate to be 3～7 to obtain purified leachate by precipitation to remove metal miscellaneous ions, and metal miscellaneous ions are one or more of aluminum ion, copper ion, iron ion;

(7) dissolving soluble metal sulfate in the purified leaching solution to adjust the atomic ratio of nickel, cobalt and manganese to obtain a mixed solution; add ammonia water to the mixed solution, and adjust the pH value to be 6 to 12 to carry out co-precipitation of nickel, cobalt and manganese ions to obtain nickel and cobalt Manganese ternary precursor.

In the step (1), the waste lithium ion battery is a waste lithium cobalt oxide battery, a waste lithium manganate battery or a waste nickel cobalt manganese ternary lithium ion battery.

The soluble metal sulfate is one or more of cobalt sulfate, nickel sulfate, and manganese sulfate; the atomic ratio of nickel, cobalt, and manganese in the mixed solution is (1-8):1:(1-1.5).

Preferably, the concentration of the ammonia water is 0.5-1.5 mol/L, and the co-precipitation time of nickel-cobalt-manganese ions is 20-40 h.

The sieve aperture of the cathode waste screening in the step (1) is 0.074-0.14 mm; the sieve aperture of the biomass screening is 0.074-0.104 mm.

The low calorific value of the biomass is not less than 3800 kcal, and the biomass is one or more of walnut shells, peanut shells, melon seed shells, coconut shells, and macadamia nut shells.

The mass of biomass powder in the bulk mixture material accounts for 17-28%;

Preferably, the block-shaped mixed material is a cylinder, the radius of the bottom surface of the cylinder is 1.5-2 cm, and the height is 2-3.5 cm.

In the step (3), the microwave power is 1000-2000W during the heating process, the microwave is automatically adjusted to maintain a constant temperature during the heating process, and the rotating speed of the block-shaped mixed material is 5-6 r/min;

In the step (4), the temperature of carbonation leaching is 5～15℃, the volume flow of carbon dioxide is 40～60mL/min, and the stirring rate is 500～800r/min; the method of solid-liquid separation is to stand for stratification;

In the step (5), the precipitation agent is trisodium phosphate dodecahydrate (Na ₃ PO ₄ ·12H ₂ O), and the precipitation treatment time is 30-120 min;

The concentration of sulfuric acid in the step (6) is 3-6 mol/L.

The beneficial effects of the present invention are:

(1) The present invention uses biomass as a reducing agent, and based on the dielectric properties of the waste lithium ion battery cathode powder, the metal ions in the waste lithium ion battery cathode powder are reduced by microwave roasting and reduction, and the biomass reducing agent is combined with microwaves. The roasting reduction method has the characteristics of high selectivity, fast heating rate, small heat loss and excellent reduction effect;

(2) The present invention realizes the efficient separation of lithium in the recovery process of lithium ion batteries, reduces the roasting temperature for separation of lithium by in-situ reduction method, and uses low-lithium filter residues to prepare ternary precursors, which solves the problem that lithium ions are easily mixed into the co-precipitation process. It also solves the problem of precipitation, and also solves the problem that it is difficult to control the morphology of the material during the process of calcining the precursor prepared with the high lithium solution at high temperature to prepare the cathode material;

(3) the method of the present invention is simple to operate, has a short flow process, and has low requirements on equipment, which not only solves the problems of complicated wet process flow and long cycle, but also makes up for the problems of high energy consumption and low recovery rate in the pyrotechnic process;

(4) The lithium salt precipitation product and the precursor product recovered by the present invention can be used to prepare the positive electrode material, which realizes the closed-loop design of the process and is beneficial to industrialization.

Description of drawings

Fig. 1 is the process flow diagram of the present invention;

Fig. 2 is the process flow diagram of microwave segmented roasting of the present invention.

Detailed ways

The present invention will be further described in detail below with reference to the specific embodiments, but the protection scope of the present invention is not limited to the content.

Embodiment 1: A kind of method (see Fig. 1) of the ternary positive electrode material of waste and old lithium ion battery efficiently reclaims, and concrete steps are as follows:

(1) The cathode and biomass (walnut shell) of the waste lithium ion battery (waste lithium cobalt oxide battery) are crushed and sieved respectively to obtain positive electrode powder and biomass powder; wherein the sieve aperture of the sieved cathode waste is 0.074mm ; The sieve aperture of biomass screening is 0.086mm;

(2) Mixing the positive electrode powder and biomass powder (walnut shell powder) uniformly, drying and pressing to obtain a block-shaped mixture; wherein the mass of the biomass powder in the block-shaped mixture accounts for 17%, and the block-shaped mixture is a cylinder , the radius of the bottom surface of the cylinder is 1.5cm, and the height is 3cm;

(3) Place the lumpy mixture in a glass tube with a rubber stopper, then place the glass tube in a box-type microwave oven, and ensure good airtightness of the microwave oven; before starting the microwave generator, use a volume of 80 mL/min The flow rate of nitrogen was introduced for 3min to remove the air in the glass tube, and then nitrogen was continuously introduced into the glass tube at a volume flow of 40mL/min to maintain the block mixture in the glass tube in a nitrogen protective atmosphere to avoid contact with oxygen, and adjust the glass tube. The rotation speed is 5r/min, the microwave power is 1000W during the heating process, and the microwave is automatically adjusted to maintain a constant temperature during the heat preservation process; under the conditions of nitrogen atmosphere and microwave, the temperature is increased at a uniform speed to 350 °C and kept for 20min to realize the conversion of biomass into biomass charcoal , the second stage is heated to a temperature of 600 °C at a constant speed and kept for 30 minutes to achieve the reduction of metal ions by biomass carbon, and maintained in a nitrogen atmosphere and cooled to room temperature with the furnace to obtain a microwave roasting reduction product (see Figure 2); the microwave roasting reduction product contains Elemental cobalt, lithium carbonate, bio-carbon and ash;

(4) The microwave roasting reduction product is placed in the aqueous solution in the leaching kettle, and carbon dioxide gas is continuously introduced into the aqueous solution, carbonation leaching is carried out under stirring conditions for 3.5 h, and the stratification is allowed to stand for solid-liquid separation to obtain a filtrate. and filter residue; wherein the temperature of carbonation leaching is 5℃, the volume flow of carbon dioxide is 40mL/min, and the stirring rate is 500r/min;

(5) add enough precipitation agent (trisodium phosphate dodecahydrate Na ₃ PO ₄ ·12H ₂ O) to the filtrate and adjust the pH value of the system to be 3 to carry out precipitation treatment for 60min to obtain lithium phosphate (Li ₃ PO ₄ ) precipitation; The recovery rate of lithium (Li ₃ PO ₄ ) is 93.5%;

(6) leaching the filter residue with sulfuric acid with a concentration of 3 mol/L, using sodium hydroxide to adjust the pH value of the leaching solution to 5.5 to precipitate and remove metal miscellaneous ions to obtain a purified leachate, and the metal miscellaneous ions are a kind of aluminum ion, copper ion, iron ion or more; the purified leachate can be directly treated with sewage and discharged.

(7) soluble metal sulfate (soluble metal sulfate is one or more of cobalt sulfate, nickel sulfate, manganese sulfate) is dissolved in the purification leaching solution to adjust the atomic ratio of nickel-cobalt-manganese to obtain a mixed solution, wherein the mixed solution The atomic ratio of nickel, cobalt, and manganese is 1:1:1; ammonia water with a concentration of 1.0 mol/L is added to the mixed solution, and the pH value is adjusted to 11 to carry out co-precipitation of nickel, cobalt and manganese ions for 30 hours to obtain nickel cobalt manganese Ni ₁ /3Co ₁ /3Mn ₁ /3(OH) ₂ ternary precursor;

In this embodiment, the nickel-cobalt-manganese Ni ₁ /3Co ₁ /3Mn ₁ /3(OH) ₂ ternary precursor and the lithium salt precipitation can be directly used to synthesize the positive electrode material of the ternary lithium ion battery, thereby realizing the closed-loop design of the process flow.

Embodiment 2: a kind of method (see Fig. 1) of the ternary positive electrode material of waste and old lithium ion battery efficiently reclaims, and concrete steps are as follows:

(1) Crushing and sieving the cathode and biomass (peanut shells) of the waste lithium ion battery (waste lithium manganate battery) respectively to obtain positive electrode powder and biomass powder; wherein the sieve aperture of the cathode waste screening is 0.086mm ; The sieve aperture of biomass screening is 0.086mm;

(2) Mixing the positive electrode powder and biomass powder (peanut shell powder) uniformly, drying and pressing to obtain a block-shaped mixture; wherein the mass of the biomass powder in the block-shaped mixture accounts for 25%, and the block-shaped mixture is a cylinder , the radius of the bottom surface of the cylinder is 2.0cm and the height is 3.5cm;

(3) Place the lumpy mixture in a glass tube with a rubber stopper, then place the glass tube in a box-type microwave oven, and ensure good airtightness of the microwave oven; before starting the microwave generator, use a volume of 80 mL/min The flow rate of nitrogen was introduced for 3min to remove the air in the glass tube, and then nitrogen was continuously introduced into the glass tube at a volume flow of 40mL/min to maintain the block mixture in the glass tube in a nitrogen protective atmosphere to avoid contact with oxygen, and adjust the glass tube. The rotating speed is 6r/min, the microwave power is 1500W during the heating process, and the microwave is automatically adjusted to maintain a constant temperature during the heat preservation process; under nitrogen atmosphere and microwave conditions, a period of uniform heating to a temperature of 450 °C and holding for 24min is performed to realize the conversion of biomass into biomass charcoal , the second stage is heated to a temperature of 750 °C at a constant speed and kept for 20 min to realize the reduction of metal ions by biomass carbon, and maintained in a nitrogen atmosphere and cooled to room temperature with the furnace to obtain a microwave roasting reduction product (see Figure 2); the microwave roasting reduction product contains Lithium carbonate, manganese oxide, biochar and ash;

(4) The microwave roasting reduction product is placed in the aqueous solution in the leaching kettle, and carbon dioxide gas is continuously introduced into the aqueous solution, and carbonation leaching is carried out for 1 h under stirring conditions, and the stratification is allowed to stand to achieve solid-liquid separation to obtain filtrate and Filter residue; wherein the temperature of carbonation leaching is 7°C, the volume flow of carbon dioxide is 60mL/min, and the stirring rate is 700r/min;

(5) Add enough precipitation agent (trisodium phosphate dodecahydrate Na ₃ PO ₄ ·12H ₂ O) to the filtrate and adjust the pH value of the system to 3.5 to carry out precipitation treatment for 120min to obtain lithium phosphate (Li ₃ PO ₄ ) precipitation; The recovery rate of lithium (Li ₃ PO ₄ ) is 94.2%;

(6) adopt the sulfuric acid that the concentration is 5mol/L to leach the filter residue, adopt sodium hydroxide to adjust the pH value of the leachate to be 5.5 to obtain the purified leachate by precipitation and removal of metal miscellaneous ions, and the metal miscellaneous ions are a kind of aluminum ion, copper ion, iron ion or more;

(7) soluble metal sulfate (soluble metal sulfate is one or more of cobalt sulfate, nickel sulfate, manganese sulfate) is dissolved in the purification leaching solution to adjust the atomic ratio of nickel-cobalt-manganese to obtain a mixed solution, wherein the mixed solution The atomic ratio of nickel, cobalt and manganese in the medium is 5:2:3; ammonia water with a concentration of 1.0 mol/L is added to the mixed solution, and the pH value is adjusted to 11 to carry out co-precipitation of nickel, cobalt and manganese ions for 30h to obtain nickel cobalt manganese Ni ₁ /2Co ₁ /5Mn ₃ /10(OH) ₂ ternary precursor;

In this embodiment, the nickel-cobalt-manganese Ni ₁ /2Co ₁ /5Mn ₃ /10(OH) ₂ ternary precursor and lithium salt precipitation can be directly used to synthesize the positive electrode material of the ternary lithium ion battery, thereby realizing the closed-loop design of the process flow.

Embodiment 3: a kind of method (see Fig. 1) of the ternary positive electrode material of waste and old lithium ion battery efficiently reclaims, and concrete steps are as follows:

(1) The cathode and biomass (macadamia nut shell) of waste and old lithium-ion batteries (waste and old nickel-cobalt-manganese ternary lithium-ion batteries) are respectively crushed and sieved to obtain positive electrode powder and biomass powder; The sieve aperture is 0.104mm; the sieve aperture of biomass screening is 0.084mm;

(2) Mixing the positive electrode powder and biomass powder (macadamia nut shell powder) uniformly, drying and pressing to obtain a lumpy mixture; wherein the mass of the biomass powder in the lumpy mixture accounts for 22%, and the lumpy mixture is Cylinder, the radius of the bottom surface of the cylinder is 2.5cm, and the height is 3cm;

(3) Place the lumpy mixture in a glass tube with a rubber stopper, then place the glass tube in a box-type microwave oven, and ensure good airtightness of the microwave oven; before starting the microwave generator, use a volume of 80 mL/min The flow rate of nitrogen was introduced for 5min to remove the air in the glass tube, and then nitrogen was continuously introduced into the glass tube at a volume flow rate of 50mL/min to maintain the bulk mixture in the glass tube in a nitrogen protective atmosphere to avoid contact with oxygen, and adjust the glass tube. The rotating speed is 5r/min, the microwave power is 2000W during the heating process, and the microwave is automatically adjusted to maintain a constant temperature during the heat preservation process; under nitrogen atmosphere and microwave conditions, a period of uniform heating to a temperature of 450°C and holding for 20min is performed to realize the conversion of biomass into biomass charcoal , the second stage is heated to a temperature of 700 °C at a constant speed and kept for 60 minutes to achieve the reduction of metal ions by biomass carbon, and maintained in a nitrogen atmosphere and cooled to room temperature with the furnace to obtain a microwave roasting reduction product (see Figure 2); the microwave roasting reduction product contains Lithium carbonate, nickel-cobalt alloys, manganese oxide, biochar and ash;

(4) The microwave roasting reduction product is placed in the aqueous solution in the leaching kettle, and carbon dioxide gas is continuously introduced into the aqueous solution, and carbonation leaching is carried out under stirring conditions for 3h, and the stratification is allowed to stand to achieve solid-liquid separation to obtain filtrate and Filter residue; wherein the temperature of carbonation leaching is 8°C, the volume flow of carbon dioxide is 55mL/min, and the stirring rate is 650r/min;

(5) Add enough precipitation agent (trisodium phosphate dodecahydrate Na ₃ PO ₄ ·12H ₂ O) to the filtrate and adjust the pH value of the system to be 3 to carry out precipitation treatment for 100 min to obtain lithium phosphate (Li ₃ PO ₄ ) precipitation; The recovery rate of lithium (Li ₃ PO ₄ ) is 94.9%;

(6) using the sulfuric acid with a concentration of 3.5mol/L to leaching the filter residue, using sodium hydroxide to adjust the pH value of the leaching solution to 4.8 to precipitate and remove metal ions to obtain a purified leaching solution, and the metal ions are one of aluminum ions, copper ions, and iron ions. one or more;

(7) soluble metal sulfate (soluble metal sulfate is one or more of cobalt sulfate, nickel sulfate, manganese sulfate) is dissolved in the purification leaching solution to adjust the atomic ratio of nickel-cobalt-manganese to obtain a mixed solution, wherein the mixed solution The atomic ratio of nickel, cobalt and manganese is 8:1:1; ammonia water with a concentration of 1.3 mol/L is added to the mixed solution, and the pH value is adjusted to 7.5 to carry out co-precipitation of nickel, cobalt and manganese ions for 25 hours to obtain nickel cobalt manganese Ni ₄ /5Co ₁ /10Mn _1/10 (OH) ₂ ternary precursor;

In this embodiment, the nickel-cobalt-manganese ternary precursor and the lithium salt precipitation can be directly used to synthesize the positive electrode material of the ternary lithium-ion battery, so as to realize the closed-loop design of the process flow.

The specific embodiments of the present invention have been described in detail above, but the present invention is not limited to the above-mentioned embodiments. Within the scope of knowledge possessed by those of ordinary skill in the art, various Variety.

Claims (8)

1. A method for efficiently recovering a ternary cathode material of a waste lithium ion battery is characterized by comprising the following specific steps:

(1) respectively crushing and screening the cathode and the biomass of the waste lithium ion battery to obtain anode powder and biomass powder;

(2) uniformly mixing the anode powder and the biomass powder, drying and pressing to form a blocky mixed material;

(3) carrying out first-stage constant-speed heating on the blocky mixed material under the nitrogen atmosphere and microwave conditions to the temperature of 300-600 ℃ and keeping the temperature for 14-30 min, carrying out second-stage constant-speed heating to the temperature of 500-900 ℃ and keeping the temperature for 5-60 min, and carrying out furnace cooling to the room temperature under the nitrogen atmosphere to obtain a microwave roasting product;

(4) placing the microwave roasting product in an aqueous solution, introducing carbon dioxide gas into the aqueous solution, carrying out carbonation leaching under the stirring condition, and carrying out solid-liquid separation to obtain filtrate and filter residue;

(5) adding sufficient precipitator into the filtrate, and adjusting the pH value of the system to 3-4 for precipitation treatment to obtain lithium phosphate precipitate;

(6) leaching filter residues by using sulfuric acid, and adjusting the pH value of the leachate to 3-7 by using sodium hydroxide to precipitate and remove metal impurity ions to obtain a purified leachate, wherein the metal impurity ions are one or more of aluminum ions, copper ions and iron ions;

(7) dissolving soluble metal sulfate in the purified leaching solution to adjust the atomic ratio of nickel, cobalt and manganese to obtain a mixed solution; adding ammonia water into the mixed solution, and adjusting the pH value to be 6-12 to perform nickel-cobalt-manganese ion coprecipitation to obtain a nickel-cobalt-manganese ternary precursor.

2. The method for efficiently recycling the ternary cathode material of the waste lithium ion battery according to claim 1, is characterized in that: the waste lithium ion battery in the step (1) is a waste lithium cobaltate battery, a waste lithium manganate battery or a waste nickel-cobalt-manganese ternary lithium ion battery.

3. The method for efficiently recycling the ternary cathode material of the waste lithium ion battery according to claim 1, is characterized in that: the mesh aperture of the screened cathode waste in the step (1) is 0.074-0.14 mm; the mesh aperture of the biomass screening is 0.074-0.104 mm.

4. The method for efficiently recycling the ternary cathode material of the waste lithium ion battery according to claim 1, is characterized in that: the biomass has low calorific value not less than 3800 kilocalorie, and is one or more of walnut shell, peanut shell, melon seed shell, coconut shell, and macadamia nut shell.

5. The method for efficiently recycling the ternary cathode material of the waste lithium ion battery according to claim 1, is characterized in that: the mass of the biomass powder in the massive mixed material accounts for 17-28%.

6. The method for efficiently recycling the ternary cathode material of the waste lithium ion battery according to claim 1, is characterized in that: the temperature of carbonation leaching in the step (4) is 5-15 ℃, the volume flow of carbon dioxide is 40-60 mL/min, and the stirring speed is 500-800 r/min.

7. The method for efficiently recycling the ternary cathode material of the waste lithium ion battery according to claim 1, is characterized in that: and (5) the precipitator is trisodium phosphate dodecahydrate.

8. The method for efficiently recycling the ternary cathode material of the waste lithium ion battery according to claim 1, is characterized in that: the concentration of the sulfuric acid in the step (6) is 3-6 mol/L.

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