WO2016101315A1

WO2016101315A1 - Method for repairing nickel-cobalt-manganese ternary battery material precursor

Info

Publication number: WO2016101315A1
Application number: PCT/CN2014/095727
Authority: WO
Inventors: 张云河; 郭苗苗; 乐绪清; 刘文泽
Original assignee: 深圳市格林美高新技术股份有限公司; 荆门市格林美新材料有限公司
Priority date: 2014-12-22
Filing date: 2014-12-30
Publication date: 2016-06-30
Also published as: CN105789616B; CN105789616A

Abstract

Provided in an embodiment of the present invention are a method for repairing nickel-cobalt-manganese ternary battery material precursor, comprising: mixing one or more than one of manganese salt solution, cobalt salt solution and nickel salt solution with nickel-cobalt-manganese ternary battery material precursor waste to acquire a mixture; calcining the mixture to acquire the nickel-cobalt-manganese ternary battery material precursor. The method of the present invention mixes the manganese salt solution with the nickel-cobalt-manganese ternary battery material precursor waste, so as to enable the manganese salt to be absorbed by the nickel-cobalt-manganese ternary battery material precursor waste and calcines to decompose the manganese salt and make the manganese salt to be uniformly distributed into a hole of the ternary material in a form of an oxide, and acquire the nickel-cobalt-manganese ternary battery material precursor satisfying requirements.

Description

Method for repairing nickel cobalt manganese ternary battery material precursor

Technical field

The invention belongs to the technical field of nickel-cobalt-manganese battery materials, and in particular relates to a method for repairing a precursor of a nickel-cobalt-manganese ternary battery material.

Background technique

Lithium-ion batteries are widely used in many fields such as mobile phones, digital cameras, computers, and electric vehicles because of their high energy, long service life, and low pollution. Among them, the positive electrode material occupies the most important position in the structure of lithium ion battery, and its performance directly determines the performance of the final product lithium ion battery, and the performance and price of the positive electrode material will directly affect the performance and price of the lithium ion battery. . Lithium nickel cobalt manganese oxide is a high-capacity positive electrode material, which combines the advantages of lithium cobaltate, lithium nickelate and lithium manganate, and has a large reversible specific capacity, and is a very promising positive electrode material. This material not only has the advantage of high specific capacity, but also has relatively good safety, relatively low price, good compatibility with electrolyte, excellent cycle performance, and is most likely to be applied simultaneously in small communication and small power fields. Battery cathode materials, even the possibility of application in large power fields. The common nickel-cobalt-manganese precursor ratios are 424, 333, 523, and the like. In the process of preparing the precursor of nickel-cobalt-manganese cathode material, an unsuitable proportion will occur, and recycling and recycling of these discarded ternary precursor materials is also a key issue.

At present, relevant reports mainly focus on the recycling of nickel-cobalt-manganese ternary cathode materials. A Chinese patent application such as CN200810198972.0 discloses a method for preparing lithium nickel cobalt manganese oxide from a waste lithium ion battery. Its main features are: the battery cathode material is nickel-cobalt-manganate, lithium nickel cobalt oxide and other waste lithium-ion batteries as raw materials, after dismantling, sorting, pulverizing, sieving and other pre-treatment, then high temperature debonding After the process of setting, sodium hydroxide and aluminum removal, the deactivated positive electrode material containing nickel, cobalt and manganese is obtained; then, the sulfuric acid and hydrogen peroxide system are leached, P ₂ O _{4 is used for} extraction and impurity removal, and a pure nickel, cobalt and manganese solution is obtained. , 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 the ammonium carbonate is used to adjust the pH value to form a nickel-cobalt-manganese carbonate precursor. Then, an appropriate amount of lithium carbonate is added, and the active nickel-cobalt-manganese lithium battery material is synthesized by high-temperature sintering. Chinese Patent Publication CN103199320A reports a method for recycling nickel-cobalt-manganese ternary cathode material. The main features are: first, the binder is removed by heat treatment, and aluminum is removed by acid leaching and pH adjustment in the presence of a reducing agent. According to the content of nickel, cobalt and manganese in the solution, an appropriate amount of nickel, cobalt and manganese sulfate is added to adjust the molar ratio of nickel, cobalt and manganese. The sodium hydroxide is used as a precipitant and the ammonia is used as a complexing agent to obtain nickel, cobalt and manganese by coprecipitation. The ternary material precursor is filtered to obtain a lithium salt solution, and the lithium salt solution is purified and precipitated to obtain lithium carbonate. Finally, the nickel-cobalt-manganese ternary material precursor is mixed with lithium carbonate in proportion, calcined at a high temperature, and cooled to obtain nickel-cobalt-manganese. Lithium acid.

The above method realizes the recycling of the ternary cathode material, but does not involve the recycling of the nickel-cobalt-manganese ternary precursor waste, and the method for recovering the nickel-cobalt-manganese ternary waste by extraction and the like is complicated and the recovery cost is relatively high. High, and involves organic solvents, which are likely to cause secondary pollution of materials.

technical problem

The purpose of the embodiments of the present invention is to overcome the above-mentioned deficiencies of the prior art, and to provide a method for repairing a precursor of a nickel-cobalt-manganese ternary battery material, and a spherical nickel-cobalt-manganese precursor material having a regular shape and uniform distribution can be obtained.

Technical solution

In order to achieve the above object, the technical solution of the embodiment of the present invention is as follows:

A method for repairing a precursor of a nickel-cobalt-manganese ternary battery material, comprising:

Mixing one or more of a manganese salt solution, a cobalt salt solution and a nickel salt solution with a nickel-cobalt-manganese ternary battery material precursor waste to obtain a mixture;

The mixture is calcined to obtain a nickel cobalt manganese ternary battery material precursor.

Beneficial effect

The method of the embodiment of the present invention mixes one of the manganese salt solution, the cobalt salt solution and the nickel salt solution with the nickel cobalt manganese ternary battery material precursor waste to make one of the manganese salt, the cobalt salt and the nickel salt. One or more kinds of adsorbed on the nickel-cobalt-manganese ternary battery material precursor waste, and then decomposed one or more of the manganese salt, the cobalt salt and the nickel salt by calcination and uniformly distributed in the form of oxide in the ternary material In the hole, a nickel-cobalt-manganese ternary battery material precursor is obtained.

DRAWINGS

The present invention will be further described below in conjunction with the accompanying drawings and embodiments, in which:

1 is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 1 of the present invention;

2 is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 2 of the present invention;

3 is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 3 of the present invention;

4 is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 4 of the present invention;

5 is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 5 of the present invention;

6 is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 6 of the present invention;

7 is a diagram showing the element distribution of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 6 of the present invention; wherein A represents purple, B represents blue, and C represents yellow.

Embodiments of the invention

The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Embodiments of the present invention provide a method for repairing a precursor of a nickel-cobalt-manganese ternary battery material, comprising the following steps:

Step S01: mixing one or more of a manganese salt solution, a cobalt salt solution and a nickel salt solution with a nickel-cobalt-manganese ternary battery material precursor waste to obtain a mixture;

Step S02: calcining the mixture to obtain a nickel cobalt manganese ternary battery material precursor.

The method of the embodiment of the present invention mixes the metal salt solution of the manganese salt, the cobalt salt and the nickel salt with the nickel cobalt manganese ternary battery material precursor waste, so that the metal salt is adsorbed on the nickel cobalt manganese ternary battery material precursor waste. . The precursor waste of nickel-cobalt-manganese ternary battery material has a pore structure, and the manganese salt, the cobalt salt and the nickel salt are all fine-grained materials, and the nickel-cobalt-manganese ternary battery material precursor waste material and the metal salt solution are mixed and stirred. Under capillary action, the liquid of these metal salts is adsorbed and penetrated into the pores of the nickel-cobalt-manganese ternary battery material precursor waste by physical adsorption along the pores of the nickel-cobalt-manganese ternary battery material precursor waste, and is uniformly distributed. The metal salt is adsorbed not only inside the pores but also on the surface of the nickel-cobalt-manganese ternary battery material precursor waste. Then, these metal salts are decomposed by calcination and uniformly distributed in the pores of the ternary material and the surface of the nickel-cobalt-manganese ternary battery precursor waste in the form of oxides, thereby obtaining a nickel-cobalt-manganese ternary battery material precursor which meets the requirements. .

Specifically, the nickel-cobalt-manganese ternary battery material precursor waste is a washed waste material, that is, the nickel-cobalt-manganese ternary battery material precursor waste component is a pure nickel-cobalt-manganese ternary composite compound, and does not include other Impurities. The composition of the nickel-cobalt-manganese ternary battery material precursor waste may be nickel-cobalt-manganese ternary composite hydroxide, nickel-cobalt-manganese ternary composite oxide, nickel-cobalt-manganese ternary composite salt or the like.

Specifically, in order to sufficiently wet the manganese salt, the nickel salt and/or the cobalt salt and the nickel cobalt manganese ternary battery material precursor waste, the nickel cobalt manganese ternary battery material precursor waste may be pulverized and ground before mixing, nickel The particle size of the precursor waste of the cobalt-manganese ternary battery material is 3 to 18 μm.

Specifically, in the process of step S01, the concentration of the nickel-cobalt-manganese ternary battery material precursor waste in the manganese salt solution, the cobalt salt solution, and/or the nickel salt solution is 2 to 10 g/mL. This concentration ensures sufficient wetting of the metal salt solution with the nickel-cobalt-manganese ternary battery material precursor. If the concentration is too small, the adsorption between the metal salt and the nickel-cobalt-manganese ternary battery material precursor is deteriorated. If the concentration is too large, the solution is relatively viscous, which is detrimental to sufficient wetting between the metal salt and the nickel-cobalt-manganese ternary battery material precursor waste. Stirring may also be accompanied by the process of step S01. The stirring time is 5 to 30 minutes, and the stirring speed is 100-200 r/min. The mixing and agitating process can be carried out in a waxing mixer. The stirring time is favorable for uniform mixing of the materials, and the adsorption is sufficient, and the stirring time is generally as long as possible, but from the economic point of view, the stirring time is generally not longer than 30 minutes; if the time is shorter than 5 minutes, the adsorption effect is affected. The adsorption is insufficient. Stirring speed is 100-200 At r/min, the agitation speed does not affect the agitation adsorption effect while maintaining the life of the mixer.

Specifically, the ratio of nickel in the cobalt and/or nickel salt solution in the manganese salt solution to the nickel, cobalt, and manganese in the precursor waste of the nickel-cobalt-manganese ternary battery material makes the nickel in the system The molar ratio of cobalt to manganese is 4:2:4, 3:3:3 or 5:2:3. This molar ratio is the molar ratio of nickel, cobalt, and manganese of a common nickel-cobalt-manganese ternary battery material.

Preferably, the manganese salt solution is mixed with the nickel cobalt manganese ternary battery material precursor waste in step S01 to obtain a mixture. Since the decomposition temperature of the manganese salt is low, it is advantageous to carry out step S02 at a low temperature. When the manganese salt is preferably used in step S01, the molar ratio of nickel, cobalt and manganese in the precursor waste of the suitable nickel-cobalt-manganese ternary battery material is preferably 4:2:2, 3:3:1 or 5:2:2.

When the manganese salt is preferably used in the step S01, when the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary battery precursor waste material is 4:2:2, the manganese and nickel-cobalt-manganese ternary in the manganese salt solution The molar ratio of nickel, cobalt and manganese in the battery material precursor waste is 2:4:2:2. The ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 4:2:4, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor. Or, when the molar ratio of nickel, cobalt, and manganese in the precursor waste of the nickel-cobalt-manganese ternary battery material is 3:3:1, the nickel in the manganese and nickel-cobalt-manganese ternary battery material precursor waste in the manganese salt solution The molar ratio of cobalt to manganese is 2:3:3:1. The ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 3:3:3, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor. Or, when the molar ratio of nickel, cobalt, and manganese in the precursor waste of the nickel-cobalt-manganese ternary battery material is 5:2:2, the nickel in the manganese and nickel-cobalt-manganese ternary battery material precursor waste in the manganese salt solution The molar ratios of cobalt and manganese are 1:5:2:2, respectively. The ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 5:2:3, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor. According to the above ratio, the manganese salt solution in the step S01 can be obtained by dissolving a certain mass of the manganese salt in water so that the volume of the manganese salt solution is 100 to 500 mL. The solution of the above volume is mainly considered to be sufficiently wetted during the mixing process of the metal salt solution and the nickel-cobalt-manganese ternary battery material precursor waste. The volume of the metal salt solution is too small to ensure the precursor of the nickel-cobalt-manganese ternary battery material. The body waste is completely wetted, resulting in uneven doping; while the metal salt solution is too bulky, part of the metal salt still exists in the form of an aqueous solution during the mixing process, and is separately precipitated in the form of metal oxide during the calcination process, thereby It also causes uneven doping. The manganese salt preferably decomposes a manganese salt having a low temperature, so that the subsequent calcination step can be carried out at a low temperature, such as manganese acetate Mn(Ac) ₂ and manganese carbonate MnCO ₃ . The manganese salt is more preferably Mn(Ac) ₂ , and Mn(Ac) ₂ has the advantages of low decomposition temperature, high solubility in water, and low cost, and manganese acetate is also selected because it does not introduce new impurities after pyrolysis. If MnCl _{2 is} calcined at a high temperature, Cl will remain in the precursor, resulting in a high impurity content. The high solubility of the manganese salt in water ensures the full utilization of the manganese salt and is more effectively wetted with the nickel-cobalt-manganese ternary battery material precursor waste.

Preferably, the nickel salt solution is mixed with the nickel-cobalt-manganese ternary battery material precursor waste in step S01 to obtain a mixture. When the nickel salt is preferably used in the step S01, the molar ratio of nickel, cobalt and manganese in the precursor waste of the suitable nickel-cobalt-manganese ternary battery material is preferably 2:2:4, 1:3:3 or 2:2:3. .

When the nickel salt is preferably used in step S01, when the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary battery precursor waste material is 2:2:4, the nickel and nickel-cobalt-manganese ternary battery in the nickel salt solution The molar ratio of nickel, cobalt and manganese in the material precursor waste is 2:2:2:4. The ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 4:2:4, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor. Alternatively, when the molar ratio of nickel, cobalt, and manganese in the nickel-cobalt-manganese ternary battery material precursor waste is 1:3:3, nickel in the nickel and nickel-cobalt-manganese ternary battery material precursor waste in the nickel salt solution The molar ratio of cobalt to manganese is 2:1:3:3. The ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 3:3:3, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor. Or, when the molar ratio of nickel, cobalt, and manganese in the precursor waste of the nickel-cobalt-manganese ternary battery material is 2:2:3, the nickel in the nickel and nickel-cobalt-manganese ternary battery material precursor waste in the nickel salt solution The molar ratios of cobalt and manganese are 3:2:2:3, respectively. The ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 5:2:3, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor. According to the above ratio, the nickel salt solution in the step S01 can be obtained by dissolving a certain amount of the nickel salt in water so that the volume of the nickel salt solution is 100 to 500 mL. The nickel salt preferably decomposes a nickel salt having a low temperature, so that the subsequent calcination step can be carried out at a low temperature, such as nickel acetate Ni(Ac) ₂ and nickel carbonate NiCO ₃ . The nickel salt is more preferably Ni(Ac) ₂ .

Preferably, the cobalt salt solution is mixed with the nickel-cobalt-manganese ternary battery material precursor waste in step S01 to obtain a mixture. When the cobalt salt is preferably used in step S01, the molar ratio of nickel, cobalt and manganese in the precursor waste of the suitable nickel-cobalt-manganese ternary battery material is preferably 4:1:4, 3:1:3 or 5:1:3. .

When the cobalt salt is preferably used in step S01, when the molar ratio of nickel, cobalt and manganese in the precursor waste of the nickel-cobalt-manganese ternary battery material is 4:1:4, the cobalt and nickel-cobalt-manganese ternary battery in the cobalt salt solution The molar ratio of nickel, cobalt and manganese in the material precursor waste is 1:4:1:4. The ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 4:2:4, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor. Alternatively, when the molar ratio of nickel, cobalt, and manganese in the precursor waste of the nickel-cobalt-manganese ternary battery material is 3:1:3, the nickel in the cobalt and nickel-cobalt-manganese ternary battery material precursor waste in the cobalt salt solution The molar ratio of cobalt to manganese is 2:3:1:3. The ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 3:3:3, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor. Or, when the molar ratio of nickel, cobalt, and manganese in the precursor waste of the nickel-cobalt-manganese ternary battery material is 5:1:3, the nickel in the cobalt and nickel-cobalt-manganese ternary battery material precursor waste in the cobalt salt solution The molar ratios of cobalt and manganese are 1:5:1:3, respectively. The ratio of the nickel, cobalt and manganese in the precursor of the nickel-cobalt-manganese ternary battery material finally obtained is 5:2:3, which satisfies the composition of the conventional nickel-cobalt-manganese ternary battery material precursor. According to the above ratio, the cobalt salt solution in the step S01 can be obtained by dissolving a certain amount of the cobalt salt in water so that the volume of the cobalt salt solution is 100 to 500 mL. The cobalt salt preferably decomposes a cobalt salt having a low temperature, so that the subsequent calcination step can be carried out at a low temperature, such as cobalt acetate Co(Ac) ₂ and cobalt carbonate CoCO ₃ . The cobalt salt is more preferably Co(Ac) ₂ .

Of course, according to the content of nickel, cobalt and manganese in the precursor waste of nickel-cobalt-manganese ternary battery material, a suitable nickel salt, cobalt salt and manganese salt with a low decomposition temperature may be selected as a metal salt solution. use.

Specifically, in the process of step S02, the calcination temperature is 350 ° C to 500 ° C, and the calcination time is 2 to 6 hours. The calcination temperature is selected in consideration of the fact that the metal salt can be completely decomposed while reducing the calcination temperature as much as possible and reducing the cost. If the calcination temperature is lower than 350 ° C, the temperature is too low to reach the decomposition temperature of the metal salt. The calcination time is selected based on whether the metal salt can be completely decomposed during the calcination process. If the calcination time is more than 6 hours, the calcination time is too long, and the cost is increased; if the calcination time is less than 2 hours, the calcination time is too short, which may cause incomplete decomposition of the metal salt.

The technical solution of the present invention will be further described below by way of specific embodiments.

Example 1

300 mL of a solution containing 469.90 g of manganese acetate and 1 kg of nickel-cobalt-manganese ternary battery material precursor waste were stirred and mixed in a waxing mixer to obtain a mixture. Wherein, the composition of the nickel-cobalt-manganese ternary battery material precursor waste material is Ni _1/2 Co _1/4 Mn _1/4 (OH) ₂ . The stirring speed was 100 r/min, and the stirring time was 5 min. The mixture was then calcined in a muffle furnace at 400 ° C for 6 hours to obtain a nickel cobalt manganese ternary battery material precursor. The molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 4:2:4. As shown in FIG. 1 , it is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 1 of the present invention. It can be seen from the figure that the precursor of the nickel-cobalt-manganese ternary battery material obtained in Example 1 is spherical, and the sphericity is good, the particles are relatively uniform, and no precipitation and agglomeration of the manganese salt occurs. The spherical particles have a relatively small sliding friction factor, have superior expandability and ductility, and exhibit good miscibility and good processing properties in the process of preparing a lithium ion battery by mixing with a lithium salt. Therefore, the nickel-cobalt-manganese ternary battery material precursor of Example 1 is spherical in shape to facilitate the preparation of a lithium-ion battery.

Example 2

500 mL of a solution containing 534.85 g of manganese acetate and 1 kg of nickel-cobalt-manganese ternary battery material precursor waste were stirred and mixed in a waxing mixer to obtain a mixture. Wherein, the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni _3/7 Co _3/7 Mn _1/7 (OH) ₂ . The stirring speed was 100 r/min, and the stirring time was 30 min. The mixture was then calcined in a muffle furnace at 450 ° C for 2 hours to obtain a nickel cobalt manganese ternary battery material precursor. The molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 3:3:3. As shown in FIG. 2, it is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 2 of the present invention. As can be seen from the figure, the precursor of the nickel-cobalt-manganese ternary battery material obtained in Example 2 was spherical, and the sphericity was good, and the phenomenon of precipitation and agglomeration of the manganese salt did not occur, but the distribution of the particle size was relatively uneven.

Example 3

100 mL of a solution containing 208.65 g of manganese acetate and 1 kg of nickel-cobalt-manganese ternary battery material precursor waste were stirred and mixed in a waxing mixer to obtain a mixture. Wherein, the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni _5/9 Co _2/9 Mn _2/9 (OH) ₂ . The stirring speed was 200 r/min and the stirring time was 12 min. The mixture was then calcined in a muffle furnace at 430 ° C for 3 hours to obtain a nickel cobalt manganese ternary battery material precursor. The molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 5:2:3. As shown in FIG. 3, it is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 3 of the present invention. It can be seen from the figure that the precursor of the nickel-cobalt-manganese ternary battery material obtained in Example 3 is spherical, and the sphericity is good, the particles are relatively uniform, and no precipitation and agglomeration of the manganese salt occurs.

Example 4

350 mL of a solution containing 388.05 g of manganese carbonate and 1 kg of nickel-cobalt-manganese ternary battery material precursor waste were stirred and mixed in a waxing mixer to obtain a mixture. Wherein, the composition of the nickel-cobalt-manganese ternary battery material precursor waste material is NiCo _1/2 Mn _1/2 O ₂ . The stirring speed was 120 r/min, and the stirring time was 20 min. The mixture was then calcined in a muffle furnace at 420 ° C for 5 hours to obtain a nickel cobalt manganese ternary battery material precursor. The molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 4:2:4. As shown in FIG. 4, it is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 4 of the present invention. It can be seen from the figure that the precursor of the nickel-cobalt-manganese ternary battery material obtained in Example 4 is spherical, and the sphericity is good, the particles are relatively uniform, and no precipitation and agglomeration of the manganese salt occurs.

Example 5

420 mL of a solution containing 441.35 g of manganese carbonate and 1 kg of nickel-cobalt-manganese ternary battery material precursor waste were stirred and mixed in a waxing mixer to obtain a mixture. Wherein, the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni _6/7 Co _6/7 Mn _2/7 O ₂ . The stirring speed was 150 r/min, and the stirring time was 8 min. The mixture was then calcined in a muffle furnace at 440 ° C for 3 hours to obtain a nickel cobalt manganese ternary battery material precursor. The molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 3:3:3. As shown in FIG. 5, it is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 5 of the present invention. It can be seen from the figure that the precursor of the nickel-cobalt-manganese ternary battery material obtained in Example 5 is spherical, and the sphericity is good, the particles are relatively uniform, and no precipitation and agglomeration of the manganese salt occurs.

Example 6

150 mL of a solution containing 172.30 g of manganese carbonate and 1 kg of nickel-cobalt-manganese ternary battery material precursor waste were stirred and mixed in a waxing mixer to obtain a mixture. Wherein, the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni _10/9 Co _4/9 Mn _4/9 O ₂ . The stirring speed was 180 r/min and the stirring time was 25 min. The mixture was then calcined in a muffle furnace at 410 ° C for 5 hours to obtain a nickel cobalt manganese ternary battery material precursor. The molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 5:2:3. As shown in FIG. 6, it is a scanning electron micrograph of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 6 of the present invention. As can be seen from the figure, the precursor of the nickel-cobalt-manganese ternary battery material obtained in Example 6 was spherical, and the sphericity was good, and the phenomenon of precipitation and agglomeration of the manganese salt did not occur, but the distribution of the particle size was relatively uneven. FIG. 7 is an elemental distribution diagram of a precursor of a nickel-cobalt-manganese ternary battery material prepared in Example 6 of the present invention, wherein A represents purple, B represents blue, and C represents yellow. It can be seen from the figure that in the nickel-cobalt-manganese ternary precursor obtained by the method of the present invention, the manganese element is uniformly distributed in the pores and on the surface.

Example 7

400 mL of a solution containing 483.91 g of nickel acetate and 1 kg of nickel-cobalt-manganese ternary battery material precursor waste were stirred and mixed in a waxing mixer to obtain a mixture. Wherein, the composition of the nickel-cobalt-manganese ternary battery material precursor waste material is Ni _1/4 Co _1/4 Mn _1/2 (OH) ₂ . The stirring speed was 130 r/min and the stirring time was 15 min. The mixture was then calcined in a muffle furnace at 350 ° C for 6 hours to obtain a nickel cobalt manganese ternary battery material precursor. The molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 4:2:4. In the nickel-cobalt-manganese ternary precursor of Example 7, the nickel element was uniformly distributed in the pores and on the surface, and nickel salt precipitation and agglomeration did not occur.

Example 8

480 mL of a solution containing 543.92 g of nickel acetate and 1 kg of nickel-cobalt-manganese ternary battery material precursor waste were stirred and mixed in a waxing mixer to obtain a mixture. Wherein, the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni _1/7 Co _3/7 Mn _3/7 (OH) ₂ . The stirring speed was 120 r/min and the stirring time was 7 min. The mixture was then calcined in a muffle furnace at 500 ° C for 2 hours to obtain a nickel cobalt manganese ternary battery material precursor. The molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 4:2:4. In the nickel-cobalt-manganese ternary precursor of Example 8, the nickel element was uniformly distributed in the pores and on the surface, and no nickel salt precipitation and agglomeration occurred.

Example 9

500 mL of a solution containing 827.48 g of nickel acetate and 1 kg of nickel-cobalt-manganese ternary battery material precursor waste were stirred and mixed in a waxing mixer to obtain a mixture. Wherein, the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni _2/7 Co _2/7 Mn _3/7 (OH) ₂ . The stirring speed was 160 r/min and the stirring time was 24 min. The mixture was then calcined in a muffle furnace at 380 ° C for 5.5 hours to obtain a nickel cobalt manganese ternary battery material precursor. The molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 4:2:4. In the nickel-cobalt-manganese ternary precursor of Example 9, the nickel element was uniformly distributed in the pores and on the surface, and nickel salt precipitation and agglomeration did not occur.

Example 10

250 mL of a solution containing 215.13 g of cobalt acetate and 1 kg of nickel-cobalt-manganese ternary battery material precursor waste were stirred and mixed in a waxing mixer to obtain a mixture. Wherein, the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni _4/9 Co _1/9 Mn _4/9 (OH) ₂ . The stirring speed was 100 r/min and the stirring time was 25 min. The mixture was then calcined in a muffle furnace at 450 ° C for 4.5 hours to obtain a nickel cobalt manganese ternary battery material precursor. The molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 4:2:4. In the nickel-cobalt-manganese ternary precursor of Example 10, cobalt elements were uniformly distributed in the pores and on the surface, and no precipitation and agglomeration of cobalt salts occurred.

Example 11

400 mL of a solution containing 552.85 g of cobalt acetate and 1 kg of nickel-cobalt-manganese ternary battery material precursor waste were stirred and mixed in a waxing mixer to obtain a mixture. Wherein, the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni _3/7 Co _1/7 Mn _3/ 7(OH) ₂ . The stirring speed was 170 r/min, and the stirring time was 8 min. The mixture was then calcined in a muffle furnace at 400 ° C for 3.5 hours to obtain a nickel cobalt manganese ternary battery material precursor. The molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 4:2:4. In the nickel-cobalt-manganese ternary precursor of Example 11, the cobalt element was uniformly distributed in the pores and on the surface, and no precipitation and agglomeration of the cobalt salt occurred.

Example 12

200 mL of a solution containing 214.38 g of cobalt acetate and 1 kg of nickel-cobalt-manganese ternary battery material precursor waste were stirred and mixed in a waxing mixer to obtain a mixture. Wherein, the composition of the nickel-cobalt-manganese ternary battery material precursor waste is Ni _5/9 Co _1/9 Mn _3/9 (OH) ₂ . The stirring speed was 110 r/min, and the stirring time was 20 min. The mixture was then calcined in a muffle furnace at 420 ° C for 5 hours to obtain a nickel cobalt manganese ternary battery material precursor. The molar ratio of nickel, cobalt and manganese in the precursor of the obtained nickel-cobalt-manganese ternary battery material was 4:2:4. In the nickel-cobalt-manganese ternary precursor of Example 12, cobalt elements were uniformly distributed in the pores and on the surface, and no precipitation and agglomeration of cobalt salts occurred.

In summary, the method of the present invention is simple in process and easy to operate. The nickel-cobalt-manganese ternary battery material precursor waste is used to make full use of resources, and the recycling cost is low, which is suitable for commercial production. In addition, the entire preparation process does not involve organic solvents and is less polluting to the environment. The product obtained by the method has a regular shape and a uniform distribution.

The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. Within the scope.

Claims

A method for repairing a precursor of a nickel-cobalt-manganese ternary battery material, comprising:

Mixing one or more of a manganese salt solution, a cobalt salt solution and a nickel salt solution with a nickel-cobalt-manganese ternary battery material precursor waste to obtain a mixture;

The mixture is calcined to obtain a nickel cobalt manganese ternary battery material precursor.
The method for repairing a precursor of a nickel-cobalt-manganese ternary battery material according to claim 1, wherein: manganese in said manganese salt solution, cobalt in said cobalt salt solution, and/or said nickel salt solution The ratio of nickel to nickel, cobalt and manganese in the precursor waste of the nickel-cobalt-manganese ternary battery material is such that the molar ratio of nickel, cobalt and manganese in the system is 4:2:4, 3:3:3 or 5 :2:3.
The method for repairing a nickel-cobalt-manganese ternary battery material precursor according to claim 1 or 2, wherein the manganese salt solution is mixed with the nickel-cobalt-manganese ternary battery material precursor waste to obtain the mixture. The molar ratio of nickel, cobalt and manganese in the precursor waste of the nickel-cobalt-manganese ternary battery material is 4:2:2, 3:3:1 or 5:2:2.
A method of repairing a nickel cobalt manganese ternary battery material precursor according to claim 3, wherein:

When the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary battery material precursor waste is 4:2:2, the manganese in the manganese salt solution and the nickel-cobalt-manganese ternary battery material precursor The molar ratio of nickel, cobalt and manganese in the waste is 2:4:2:2; or,

When the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary battery material precursor waste is 3:3:1, the manganese in the manganese salt solution and the nickel-cobalt-manganese ternary battery material precursor The molar ratio of nickel, cobalt and manganese in the waste is 2:3:3:1; or,

When the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary battery material precursor waste is 5:2:2, the manganese in the manganese salt solution and the nickel-cobalt-manganese ternary battery material precursor The molar ratio of nickel, cobalt and manganese in the waste is 1:5:2:2.
The method for repairing a nickel-cobalt-manganese ternary battery material precursor according to claim 1 or 2, wherein the nickel salt solution is mixed with the nickel-cobalt-manganese ternary battery material precursor waste to obtain the mixture. The molar ratio of nickel, cobalt and manganese in the precursor waste of the nickel-cobalt-manganese ternary battery material is 2:2:4, 1:3:3 or 2:2:3.
A method of repairing a nickel cobalt manganese ternary battery material precursor according to claim 5, wherein:

When the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary battery material precursor waste is 2:2:4, the nickel in the nickel salt solution and the nickel-cobalt-manganese ternary battery material precursor The molar ratio of nickel, cobalt and manganese in the waste is 2:2:2:4; or,

When the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary battery material precursor waste is 1:3:3, the nickel in the nickel salt solution and the nickel-cobalt-manganese ternary battery material precursor The molar ratio of nickel, cobalt and manganese in the waste is 2:1:3:3; or,

When the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary battery material precursor waste is 2:2:3, the nickel in the nickel salt solution and the nickel-cobalt-manganese ternary battery material precursor The molar ratio of nickel, cobalt and manganese in the waste is 3:2:2:3.
The method for repairing a nickel-cobalt-manganese ternary battery material precursor according to claim 1 or 2, wherein the cobalt salt solution is mixed with the nickel-cobalt-manganese ternary battery material precursor waste to obtain the mixture. The molar ratio of nickel, cobalt and manganese in the precursor waste of the nickel-cobalt-manganese ternary battery material is 4:1:4, 3:1:3 or 5:1:3.
A method of repairing a nickel cobalt manganese ternary battery material precursor according to claim 7, wherein:

When the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary battery material precursor waste is 4:1:4, the cobalt in the cobalt salt solution and the nickel-cobalt-manganese ternary battery material precursor The molar ratio of nickel, cobalt and manganese in the waste is 1:4:1:4; or,

When the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary battery material precursor waste is 3:1:3, the cobalt in the cobalt salt solution and the nickel-cobalt-manganese ternary battery material precursor The molar ratio of nickel, cobalt and manganese in the waste is 2:3:1:3; or,

When the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary battery material precursor waste is 5:1:3, the cobalt in the cobalt salt solution and the nickel-cobalt-manganese ternary battery material precursor The molar ratio of nickel, cobalt and manganese in the waste is 1:5:1:3.
The method for repairing a nickel-cobalt-manganese ternary battery material precursor according to claim 1 or 2, wherein the mixing to obtain a mixture is accompanied by stirring, and the stirring time is 5 to 30 minutes. The stirring speed is 100 to 200 r/min, and/or the baking temperature is 350 to 500 ° C, and the baking time is 2 to 6 hours.
The method for repairing a nickel-cobalt-manganese ternary battery material precursor according to claim 1 or 2, wherein the nickel-cobalt-manganese ternary battery material precursor waste is in the manganese salt solution and the cobalt salt solution. And/or the concentration in the nickel salt solution is 2 to 10 g/mL.