CN116565367A - A method for extraction-free regeneration of battery materials - Google Patents

Abstract

The invention provides a method for no-extraction regeneration of battery materials, which comprises the following steps: removing impurities from the battery black powder leaching solution by water to obtain a water impurity-removed solution; removing calcium ions and magnesium ions in the hydrolyzed and impurity-removed liquid by adopting fluoride to obtain calcium and magnesium-removed liquid; defluorination is carried out on the calcium-magnesium-removed solution to obtain a nickel-cobalt-manganese solution, and precursor synthesis is carried out on the nickel-cobalt-manganese solution to obtain a nickel-cobalt-manganese precursor material; the method can prevent nickel, cobalt and manganese from being separated, and directly remove impurities of calcium and magnesium, so that the process is extremely short, the traditional complex extraction steps are avoided, the consumption of corresponding acid, alkali, power and the like is saved, no waste water is generated, all input water completely enters the precursor synthesis process, and the recycled material meets the requirement of the precursor synthesis process on the impurity element content.

Description

A method for extraction-free regeneration of battery materials

technical field

The invention belongs to the technical field of battery recycling, and relates to a method for extraction-free regeneration of battery materials.

Background technique

With the rapid development of new energy sources of lithium batteries, the stock of lithium batteries has reached millions of tons, and with the passage of time, it has begun to enter the decommissioning stage. Decommissioned waste lithium batteries contain a large amount of metals such as lithium, nickel, cobalt, manganese, copper, and aluminum, and are rich in valuable metal minerals.

At present, the industry's conventional approach is to use lithium batteries as one of the sources of mineral resources and incorporate them into the traditional nickel-cobalt hydrometallurgical process. The main method is to pickle the black powder in the battery, let the valuable metals enter the solution in the form of ions, remove the impurity elements such as iron and aluminum by hydrolysis, and then remove the iron, aluminum, zinc, copper and so on through P204 , manganese, calcium and other elements are extracted, but the value of metals in the solution of this section of back extraction is very limited. In the prior art, manganese and the like are usually recovered directly in the form of precipitation, and cobalt is extracted from the solution after extraction and removal of impurities with P507 to obtain The cobalt sulfate solution is refined, and the raffinate is extracted with P507/C272 to extract magnesium; finally, nickel is extracted with P507 to obtain refined nickel sulfate.

For example, CN 109449523A discloses a method for comprehensive recovery of waste lithium ion batteries, including: first leaching the battery cell powder to obtain the first leaching liquid and the first leaching slag; selectively reducing and leaching the first leaching slag with hydrogen peroxide and sulfuric acid to obtain The second leaching solution and the second leaching residue: adjust the pH of the second leaching solution to 4.2-4.5, extract the second leaching solution with P204 to obtain the P204 raffinate and the P204-loaded organic phase, back-extract the P204-loaded organic phase with sulfuric acid, evaporate and crystallize to obtain manganese sulfate; adjust the pH value of the P204 raffinate to 4.5-5, extract the P204 raffinate with C272 to obtain the C272 extract and the C272-loaded organic phase; use sulfuric acid to extract the C727-loaded organic phase to obtain a cobalt sulfate solution , evaporation and crystallization to obtain battery-grade cobalt sulfate; adjust the pH of the C272 raffinate to 5-5.5, extract the C272 extract with P507 to obtain a P507-loaded organic phase, and P507-loaded organic phase is back-extracted with sulfuric acid to obtain a nickel sulfate solution. Evaporate and crystallize to obtain nickel sulfate.

But there are following problems in above-mentioned recovery method: (1) process flow is long, and control point is many; (2) consume a large amount of acid and alkali during extraction; (4) A large amount of raffinate is finally produced, the main components are COD, heavy metals and high-concentration salts, and the cost of environmental protection treatment is high; (5) a large amount of flammable organic matter is used in the process, which has very high requirements for fire protection and safety.

Based on the above research, it is necessary to provide a method for extraction-free regeneration of battery materials. The method does not require traditional large-scale extraction, saves the corresponding consumption of acid, alkali, and power, and does not generate waste water. The recovered materials meet the requirements of precursors. The requirements for the content of impurity elements in the body synthesis process.

Contents of the invention

The purpose of the present invention is to provide a method for extraction-free regeneration of battery materials. The method can directly remove impurities calcium and magnesium without separating nickel, cobalt, and manganese, so that the process is extremely short, avoiding traditional complicated extraction steps, and saving corresponding The consumption of acid, alkali and power, etc., no waste water is generated, all the input water enters the precursor synthesis process, and the recovered materials meet the requirements of the precursor synthesis process for the content of impurity elements.

To achieve this purpose of the invention, the present invention adopts the following technical solutions:

The invention provides a method for extraction-free regeneration of battery materials, the method comprising the following steps:

(1) The battery black powder leachate is hydrolyzed to remove impurities, and the liquid after hydrolysis is obtained;

(2) Using fluoride to remove calcium ions and magnesium ions in the liquid after hydrolysis and impurity removal described in step (1), to obtain the liquid after removing calcium and magnesium;

(3) Defluorine is removed from the solution after calcium and magnesium removal in step (2) to obtain a nickel-cobalt-manganese solution, and the nickel-cobalt-manganese solution is subjected to precursor synthesis to obtain a nickel-cobalt-manganese precursor material.

The present invention adopts the method of extraction-free, firstly carry out hydrolysis to remove impurities, remove aluminum and iron, then use fluoride to remove calcium and magnesium, and finally remove fluoride ions to obtain a solution containing nickel, cobalt and manganese, while the extraction sequence of traditional P507 is manganese, Calcium, cobalt, magnesium, and nickel cannot be extracted from nickel, cobalt, and manganese solutions at one time, and can only be extracted step by step in order, involving multi-step extraction. The invention can not separate nickel, cobalt, and manganese, avoiding a large number of extraction processes , to directly prepare a solution of nickel-cobalt-manganese, so that it can be directly used as a raw material for precursor synthesis, which not only shortens the overall process, but also does not introduce new impurity ions, and the obtained nickel-cobalt-manganese solution meets the requirements of ternary precursor synthesis. Require.

Preferably, the pH of the hydrolysis in step (1) is 3.5-4.5, such as 3.5, 4.0 or 4.5, but not limited to the listed values, other unlisted values within the range of values are also applicable.

Preferably, the temperature for hydrolysis and impurity removal in step (1) is 80-95°C, such as 80°C, 90°C or 95°C, and the time is 60-120min, such as 60min, 80min, 100min or 120min, but not Limited to the numerical values listed, other unlisted numerical values within the numerical range are also applicable.

Preferably, the pH regulator used in step (1) for hydrolysis and decompression includes sodium carbonate solution and/or calcium carbonate, preferably calcium carbonate.

In order to enable the obtained nickel-cobalt-manganese to be directly used as a synthetic precursor, calcium carbonate is preferably used as a pH regulator, which can avoid water swelling, reduce the amount of water, and produce no waste water, allowing all input water to enter the precursor synthesis process.

Preferably, in the liquid after hydrolysis and impurity removal described in step (1), the contents of iron ions and aluminum ions are respectively below 3 mg/L, such as 3 mg/L, 2 mg/L, 1 mg/L or 0.5 mg/L, But not limited to the listed values, other unlisted values within the range of values are also applicable.

Preferably, solid-liquid separation is carried out after the hydrolysis and impurity removal in step (1), to obtain the hydrolysis and impurity removal liquid and iron and aluminum slag.

Preferably, the solid-liquid separation method includes pressure filtration.

Preferably, the battery black powder leachate described in step (1) is prepared by the following method:

The waste batteries are disassembled and sorted to obtain black powder, and the black powder is subjected to acid leaching to obtain a battery black powder leaching solution.

Preferably, the fluoride in step (2) includes any one or a combination of at least two of ammonium fluoride, sodium fluoride or manganese fluoride, preferably ammonium fluoride.

The fluoride used in the present invention to remove calcium and magnesium is preferably ammonium fluoride. Since the obtained nickel-cobalt-manganese solution is directly applied to the synthesis of the precursor, ammonia itself needs to be added as a buffer, so it is beneficial to the subsequent ternary co-precipitation, so , without introducing new ions into the system, it can not only remove calcium and magnesium through fluoride precipitation, but also promote the synthesis of battery materials.

Preferably, the amount of fluoride used in step (2) is 110-300% of the theoretical amount, such as 110%, 150%, 200%, 250% or 300%, but not limited to the listed values, the range of values Other unlisted values also apply.

The fluoride of the present invention reacts with calcium and magnesium ions to form magnesium fluoride and calcium fluoride precipitation, the actual amount of fluoride is higher than the theoretical amount, if the amount is too low compared to the theoretical amount, the effect of calcium and magnesium ion precipitation cannot be guaranteed , if the amount of fluoride is too much compared to the theoretical amount, too much fluoride impurity will be introduced, which is not conducive to the subsequent fluorine removal. Guarantee the effect of the defluoridation step.

Preferably, step (2) carries out calcium and magnesium end-point pH to be 5-6, for example can be 5, 5.2, 5.4, 5.6, 5.8 or 6, but not limited to listed numerical value, other unlisted numerical value within numerical range The same applies.

The pH at the end point of calcium and magnesium removal in the present invention will affect the impurity removal effect, if the pH at the end point is too low, too much precipitant will be consumed, and if the pH at the end point is too high, the precipitation loss of nickel and cobalt will easily be caused.

Preferably, the temperature for step (2) to remove calcium and magnesium is 85-100°C, such as 85°C, 90°C, 95°C or 100°C, and the time is 60-120min, such as 60min, 80min, 100min or 120min , but not limited to the listed values, other unlisted values within the range of values are also applicable.

Preferably, in step (2), the contents of calcium ions and magnesium ions in the liquid after decalcification and magnesium ions are respectively below 5 mg/L, such as 5 mg/L, 4 mg/L, 3 mg/L, 2 mg/L or 1 mg /L, but not limited to the listed values, other unlisted values within the range of values are also applicable.

Preferably, ion exchange resin is used to carry out the defluorination described in step (3).

Preferably, the ion exchange resin includes an anion extractant, preferably N235 extractant.

In the present invention, the anion extractant is adsorbed on the resin carrier as an ion exchange resin, selectively adsorbs fluoride ions, and retains nickel, cobalt, and manganese ions in the solution, so as to realize the removal of fluoride ions in the liquid after calcium and magnesium removal, and obtain a solution that satisfies the preparation of precursors. The nickel-cobalt-manganese solution does not require a large amount of separate extraction of nickel ions, cobalt ions and manganese ions.

Preferably, the amount of the ion exchange resin is 1.2-2 times the theoretical amount, for example, 1.2 times, 1.5 times or 2 times, but not limited to the listed values, and other unlisted values within the range of values are also applicable.

The amount of ion exchange resin used in the present invention matches the overall process flow of the present invention. Since the ion exchange resin is placed in the ion exchange column to form a fixed bed, if the amount used is too much, the investment will increase; Fluorine effect.

Preferably, the aspect ratio of the ion exchange column used for the defluorination in step (3) is (2.5-4):1, such as 2.5:1, 3:1, 3.5:1 or 4:1, but not Limited to the numerical values listed, other unlisted numerical values within the numerical range are also applicable.

Preferably, the liquid inlet method for removing fluorine in step (3) is bottom-in and top-out.

Preferably, in the nickel-cobalt-manganese solution described in step (3), the content of fluoride ions is below 3 mg/L, such as 3 mg/L, 2.5 mg/L, 2 mg/L, 1.5 mg/L or 1 mg/L, But not limited to the listed values, other unlisted values within the range of values are also applicable.

Preferably, before the nickel-cobalt-manganese solution in step (3) is used for precursor synthesis, the content of nickel ions, cobalt ions and manganese ions is first adjusted, and then the adjusted nickel-cobalt-manganese solution is directly used as a raw material for precursor synthesis.

As a preferred technical solution of the present invention, the method comprises the steps of:

(1) Dismantling and sorting waste batteries to obtain black powder, acid leaching the black powder to obtain battery black powder leaching solution, adding a pH regulator to the battery black powder leaching solution at a temperature of 80-95°C to make the system pH 3.5 After -4.5, carry out hydrolysis to remove impurity for 60-120min, obtain the liquid after hydrolysis, in the liquid after hydrolysis, the content of iron ion and aluminum ion is respectively below 3mg/L;

(2) At a temperature of 85-100°C, add fluoride to the liquid after hydrolysis and impurity removal described in step (1) to react for 60-120 minutes, remove calcium ions and magnesium ions, and obtain a liquid after decalcification and magnesium removal. In the magnesium after solution, the content of calcium ions and magnesium ions are respectively below 5mg/L;

Wherein, the amount of fluoride is 110-300% of the theoretical amount, and the pH at the end of the reaction is 5-6;

(3) adopt ion exchange resin to remove the fluoride ion of step (2) described after removing calcium and magnesium, the consumption of described ion exchange resin is 1.2-2 times of theoretical amount, obtain nickel cobalt manganese solution, described nickel cobalt manganese In the solution, the content of fluoride ion is below 3mg/L;

The nickel-cobalt-manganese solution first adjusts the content of nickel ions, cobalt ions and manganese ions, and then directly uses the adjusted nickel-cobalt-manganese solution as a raw material for precursor synthesis to obtain a nickel-cobalt-manganese precursor material.

Compared with the prior art, the present invention has the following beneficial effects:

In the present invention, firstly, the aluminum and iron are removed to obtain the hydrolysis-removal impurity liquid, and then the fluoride is used to remove the calcium and magnesium to obtain the liquid after the calcium and magnesium removal, and the liquid after the calcium and magnesium removal is defluorinated, and the nickel, cobalt, and manganese are not separated, that is, The nickel-cobalt-manganese solution that can be directly used for the synthesis of precursor materials can be obtained. The content of iron and aluminum can be reduced to below 3mg/L, the content of calcium and magnesium can be reduced to below 5mg/L, and the content of fluorine can be reduced to below 3mg/L. The requirement of the synthesis process on the content of impurity elements eliminates a large number of extraction processes, the overall process flow is extremely short, saves the corresponding consumption of acid, alkali, power, etc., and no waste water is generated, and all the input water enters the precursor synthesis process.

Description of drawings

Fig. 1 is a flowchart of the method described in Embodiment 1 of the present invention.

Detailed ways

The technical solutions of the present invention will be further described below through specific embodiments. It should be clear to those skilled in the art that the examples are only for helping to understand the present invention, and should not be regarded as specific limitations on the present invention.

Example 1

This embodiment provides a method for extraction-free regeneration of battery materials. The flow chart of the method is shown in Figure 1, including the following steps:

(1) Dismantling and sorting waste batteries to obtain black powder, acid leaching the black powder to obtain battery black powder leaching solution, placing the battery black powder leaching solution in a reaction kettle, adding pH adjustment at a temperature of 90°C and stirring After the pH of the system was adjusted to 4, the hydrolysis and impurity removal was carried out for 100 minutes. After the reaction was completed, the liquid-solid separation was carried out through a plate and frame filter press to obtain the hydrolysis and impurity removal liquid and the iron and aluminum slag;

The pH regulator is calcium carbonate;

(2) At a temperature of 90°C, add fluoride to the liquid after hydrolysis and impurity removal described in step (1) to react for 80 minutes. Filter for liquid-solid separation to obtain liquid after calcium and magnesium removal;

Wherein, the fluoride is ammonium fluoride, and the consumption of the fluoride is 200% of the theoretical consumption;

(3) adopt ion exchange resin to remove the fluoride ion of step (2) described after removing calcium and magnesium, the consumption of described ion exchange resin is 1.5 times of theoretical amount, and the aspect ratio of ion exchange column is 3:1, obtains nickel cobalt manganese solution;

Described ion exchange resin comprises N235 extraction agent;

The nickel-cobalt-manganese solution first adjusts the content of nickel ions, cobalt ions and manganese ions, and then directly uses the adjusted nickel-cobalt-manganese solution as a raw material for precursor synthesis to obtain a nickel-cobalt-manganese precursor material.

Example 2

This embodiment provides a method for extraction-free regeneration of battery materials, the method comprising the following steps:

(1) Dismantling and sorting waste batteries to obtain black powder, acid leaching the black powder to obtain battery black powder leaching solution, placing the battery black powder leaching solution in a reaction kettle, adding pH adjustment at 95°C and stirring After the pH of the system was adjusted to 3.5, hydrolysis and impurity removal was carried out for 60 minutes. After the reaction was completed, the liquid-solid separation was carried out through a plate and frame filter press to obtain the hydrolysis and impurity removal liquid and iron and aluminum slag;

The pH regulator is a saturated sodium carbonate solution;

(2) At a temperature of 100°C, add fluoride to the liquid after hydrolysis and impurity removal described in step (1) to react for 60 minutes, and the pH at the end of the reaction is 5 to obtain the liquid after calcium and magnesium removal. Filter for liquid-solid separation to obtain liquid after calcium and magnesium removal;

Wherein, the fluoride is ammonium fluoride, and the consumption of the fluoride is 300% of the theoretical consumption;

(3) Using ion exchange resin to remove the fluoride ions of the liquid after removing calcium and magnesium in step (2), the consumption of the ion exchange resin is 2 times of the theoretical amount, and the aspect ratio of the ion exchange column is 4:1 to obtain nickel cobalt manganese solution;

Described ion exchange resin comprises N235 extraction agent;

The nickel-cobalt-manganese solution first adjusts the content of nickel ions, cobalt ions and manganese ions, and then directly uses the adjusted nickel-cobalt-manganese solution as a raw material for precursor synthesis to obtain a nickel-cobalt-manganese precursor material.

Example 3

This embodiment provides a method for extraction-free regeneration of battery materials, the method comprising the following steps:

(1) Dismantling and sorting waste batteries to obtain black powder, acid leaching the black powder to obtain battery black powder leaching solution, placing the battery black powder leaching solution in a reaction kettle, adding pH adjustment at 80°C and stirring After the pH of the system was adjusted to 4.5, the hydrolysis and impurity removal was carried out for 120 minutes. After the reaction was completed, the liquid-solid separation was carried out through a plate and frame filter press to obtain the hydrolysis and impurity removal liquid and the iron and aluminum slag;

The pH regulator is calcium carbonate;

(2) At a temperature of 85°C, add fluoride to the liquid after hydrolysis and impurity removal described in step (1) to react for 120 minutes, and the pH at the end point of the reaction is 6 to obtain the liquid after removing calcium and magnesium, and press the plate and frame after the reaction is completed. Filter for liquid-solid separation to obtain liquid after calcium and magnesium removal;

Wherein, the fluoride is ammonium fluoride, and the consumption of the fluoride is 110% of the theoretical consumption;

(3) Using ion exchange resin to remove the fluoride ions of the liquid after removing calcium and magnesium described in step (2), the consumption of the ion exchange resin is 1.2 times of the theoretical amount, and the aspect ratio of the ion exchange column is 2.5:1 to obtain nickel cobalt manganese solution;

Described ion exchange resin comprises N235 extraction agent;

The nickel-cobalt-manganese solution first adjusts the content of nickel ions, cobalt ions and manganese ions, and then directly uses the adjusted nickel-cobalt-manganese solution as a raw material for precursor synthesis to obtain a nickel-cobalt-manganese precursor material.

Example 4

This embodiment provides a method for extraction-free regeneration of battery materials. The method is the same as that of Embodiment 1 except that the pH regulator in step (1) is a saturated sodium carbonate solution.

Example 5

This embodiment provides a method for extraction-free regeneration of battery materials. The method is the same as that of Embodiment 1 except that the fluoride in step (2) is sodium fluoride.

Example 6

This embodiment provides a method for extraction-free regeneration of battery materials. The method is the same as in Embodiment 1 except that the amount of fluoride in step (2) is 100% of the theoretical amount.

Example 7

This embodiment provides a method for extraction-free regeneration of battery materials. The method is the same as that in Embodiment 1 except that the amount of fluoride used in step (2) is 400% of the theoretical amount.

Example 8

This example provides a method for extraction-free regeneration of battery materials, which is the same as Example 1 except that step (2) adaptively adjusts the amount of fluoride added so that the pH at the end of the reaction is 4.

Example 9

This example provides a method for extraction-free regeneration of battery materials, which is the same as in Example 1 except that step (2) adaptively adjusts the amount of fluoride added so that the pH at the end of the reaction is 7.

Example 10

This embodiment provides a method for extraction-free regeneration of battery materials. The method is the same as in Embodiment 1 except that the ion exchange resin in step (3) is CH-87 ion exchange resin.

Comparative example 1

This embodiment provides a method for extraction-free regeneration of battery materials, which is the same as that of Embodiment 1 except that step (3) is not performed.

Comparative example 2

This comparative example provides a kind of method of battery material regeneration, and described method comprises the steps:

(1) Dismantling and sorting waste batteries to obtain black powder, acid leaching the black powder to obtain battery black powder leaching solution, placing the battery black powder leaching solution in a reaction kettle, adding pH adjustment at a temperature of 90°C and stirring After the pH of the system was adjusted to 4, the hydrolysis and impurity removal was carried out for 100 minutes. After the reaction was completed, the liquid-solid separation was carried out through a plate and frame filter press to obtain the hydrolysis and impurity removal liquid and the iron and aluminum slag;

The pH regulator is calcium carbonate;

(2) Extract iron, aluminum, zinc, copper, manganese, calcium and other elements with P204 extractant, recover manganese in the form of precipitation in the back-extracted solution; extract cobalt with P507 to obtain refined Cobalt sulfate solution; extract magnesium with C272 from the raffinate; finally extract nickel with P507 to obtain refined nickel sulfate.

In the above examples 1-10 and comparative example 1, the content of iron ion and aluminum ion in the liquid after hydrolysis and impurity removal, the content of calcium ion and magnesium ion in the liquid after removing calcium and magnesium, and the content of fluoride ion in the nickel-cobalt-manganese solution content and the total content of nickel ions, cobalt ions and manganese ions are shown in the table below:

Table 1

It can be seen from Table 1:

(1) The method for extraction-free regeneration of battery materials provided by the present invention can obtain a solution with less impurity content and simultaneously include nickel ions, cobalt ions and manganese ions, so that it can directly carry out the preparation of precursor materials; by Example 1 Compared with Comparative Example 1, it can be seen that the nickel-cobalt-manganese solution will contain a large amount of impurity fluorine ions without the fluorine removal step, and the high fluorine content will affect the preparation of the precursor and seriously corrode the metal equipment. It is made of stainless steel, high fluorine content will cause severe corrosion to the equipment, and the precursor synthesis kettle cannot work for a long time; from Example 1 and Comparative Example 2, it can be seen that the traditional method is used for recovery in Comparative Example 2, the process is long, and the extraction will consume A large amount of acid and alkali, a large amount of solution and extraction agent are used, and a large amount of raffinate is finally produced. The cost of environmental protection treatment is high and the safety requirements are high.

(2) From Example 1 and Example 4, it can be seen that directly adopting calcium carbonate as the pH regulator does not need to add extra water, because the finally obtained nickel-cobalt-manganese solution is directly prepared for the precursor, thus avoiding the amount of water added Too much is unfavorable for the direct preparation of follow-up precursor; As can be known from embodiment 1 and embodiment 5, adopting ammonium fluoride as fluoride to remove calcium magnesium can match with the direct preparation process of follow-up precursor; By embodiment 1 and implementation Examples 6-9 show that when step (2) removes calcium and magnesium, the amount of fluoride and the pH at the end point will affect the impurity removal effect; it can be seen from Example 1 and Example 10 that the present invention adopts the ion exchange resin that includes the extractant , which is beneficial to increase the content of nickel-cobalt-manganese in the nickel-cobalt-manganese solution, and can effectively remove fluoride ions at the same time.

In summary, the present invention provides a method for extraction-free regeneration of battery materials. The method can directly remove impurities calcium and magnesium without separating nickel, cobalt, and manganese, making the process extremely short and avoiding traditional complicated extraction steps. The corresponding acid, alkali and power consumption are saved, no waste water is generated, all the input water enters the precursor synthesis process, and the recovered materials meet the requirements of the precursor synthesis process for the content of impurity elements.

The above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any person skilled in the art is within the technical scope disclosed in the present invention. Easily conceivable changes or substitutions all fall within the scope of protection and disclosure of the present invention.

Claims (10)

1. A method for extraction-free regeneration of battery materials, characterized in that said method comprises the steps of: (1) The battery black powder leachate is hydrolyzed to remove impurities, and the liquid after hydrolysis is obtained; (2) Using fluoride to remove calcium ions and magnesium ions in the liquid after hydrolysis and impurity removal described in step (1), to obtain the liquid after removing calcium and magnesium; (3) Defluorine is removed from the solution after calcium and magnesium removal in step (2) to obtain a nickel-cobalt-manganese solution, and the nickel-cobalt-manganese solution is subjected to precursor synthesis to obtain a nickel-cobalt-manganese precursor material. 2. The method according to claim 1, characterized in that, the pH of the hydrolysis and impurity removal described in step (1) is 3.5-4.5; Preferably, the temperature for the hydrolysis and impurity removal in step (1) is 80-95° C., and the time is 60-120 min. 3. The method according to claim 1 or 2, characterized in that, the pH regulator used in the hydrolysis and impurity removal described in step (1) comprises sodium carbonate solution and/or calcium carbonate; Preferably, the contents of iron ions and aluminum ions in the solution after hydrolysis and impurity removal in step (1) are respectively below 3 mg/L. 4. according to the method described in any one of claim 1-3, it is characterized in that, step (1) carries out solid-liquid separation after the hydrolysis of impurity removal, obtains described hydrolysis after impurity removal and iron-removing aluminum slag; Preferably, the battery black powder leachate described in step (1) is prepared by the following method: The waste batteries are disassembled and sorted to obtain black powder, and the black powder is subjected to acid leaching to obtain a battery black powder leaching solution. 5. The method according to any one of claims 1-4, characterized in that the fluoride in step (2) comprises any one or at least two of ammonium fluoride, sodium fluoride or manganese fluoride combination, preferably ammonium fluoride; Preferably, the amount of fluoride used in step (2) is 110-300% of the theoretical amount. 6. according to the method described in any one of claim 1-5, it is characterized in that, step (2) carries out the terminal pH of decalcification magnesium is 5-6; Preferably, the temperature for step (2) to remove calcium and magnesium is 85-100°C, and the time is 60-120min; Preferably, the contents of calcium ions and magnesium ions in the liquid after calcium and magnesium removal described in step (2) are below 5 mg/L respectively. 7. according to the method described in any one of claim 1-6, it is characterized in that, adopt ion exchange resin to carry out the described defluorination of step (3); Preferably, the ion exchange resin includes an anion extractant, preferably an N235 extractant; Preferably, the amount of the ion exchange resin used is 1.2-2 times the theoretical amount. 8. The method according to any one of claims 1-7, characterized in that, the aspect ratio of the ion-exchange column used in the defluorination described in step (3) is (2.5-4): 1; Preferably, the liquid inlet method for removing fluorine in step (3) is bottom-in and top-out. 9. according to the method described in any one of claim 1-8, it is characterized in that, in the described nickel-cobalt-manganese solution of step (3), the content of fluoride ion is below 3mg/L; Preferably, before the nickel-cobalt-manganese solution in step (3) is used for precursor synthesis, the content of nickel ions, cobalt ions and manganese ions is first adjusted, and then the adjusted nickel-cobalt-manganese solution is directly used as a raw material for precursor synthesis. 10. The method according to any one of claims 1-9, characterized in that the method comprises the steps of: (1) Dismantling and sorting waste batteries to obtain black powder, acid leaching the black powder to obtain battery black powder leaching solution, adding a pH regulator to the battery black powder leaching solution at a temperature of 80-95°C to make the system pH 3.5 After -4.5, carry out hydrolysis to remove impurity for 60-120min, obtain the liquid after hydrolysis, in the liquid after hydrolysis, the contents of iron ion and aluminum ion are respectively below 3mg/L; (2) At a temperature of 85-100°C, add fluoride to the liquid after hydrolysis and impurity removal described in step (1) to react for 60-120min, remove calcium ions and magnesium ions, and obtain the liquid after decalcification and magnesium removal. In the magnesium after solution, the content of calcium ions and magnesium ions are respectively below 5mg/L; Wherein, the amount of fluoride is 110-300% of the theoretical amount, and the pH at the end of the reaction is 5-6; (3) adopt ion exchange resin to remove the fluoride ion of step (2) described after removing calcium and magnesium, the consumption of described ion exchange resin is 1.2-2 times of theoretical amount, obtain nickel cobalt manganese solution, described nickel cobalt manganese In the solution, the content of fluoride ion is below 3mg/L; The nickel-cobalt-manganese solution first adjusts the content of nickel ions, cobalt ions and manganese ions, and then directly uses the adjusted nickel-cobalt-manganese solution as a raw material for precursor synthesis to obtain a nickel-cobalt-manganese precursor material.