CN116240385A - Method for separating and purifying valuable metals of waste lithium batteries - Google Patents
Method for separating and purifying valuable metals of waste lithium batteries Download PDFInfo
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- C22B7/006—Wet processes
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Abstract
The invention belongs to the technical field of waste battery recovery, and discloses a method for separating and purifying valuable metals of waste lithium batteries, which comprises the following steps: carrying out microwave pyrolysis on the positive black powder; alkaline leaching is carried out on the anode material powder subjected to microwave pyrolysis by adopting alkaline solution, and an Al simple substance is removed, so that alkaline leaching solution is obtained; filtering alkali leaching liquid for one time by filter; carrying out acid leaching treatment on the filter cake under the microwave heating condition, wherein the acid leaching solution is a mixed solution of citric acid and hydrogen peroxide; cooling the solution, performing secondary filter pressing, adding ammonia water into the chlorine solution, precipitating metal ions in the filtrate, and performing tertiary filter pressing; will beThe filter cake is dissolved firstly and then NaHSO is adopted 3 The dimethylglyoxime ethanol solution and the ammonia water are precipitated step by step. The method of adjusting and controlling the pH value is adopted to separate valuable metal elements step by step, and Li, co, ni, mn elements are separated and extracted by a common salt and alkali precipitation method, so that the cost can be effectively reduced, the pollution generated by organic waste liquid can be reduced, and the metal purification rate can be improved.
Description
Technical Field
The invention belongs to the technical field of waste battery recycling, and particularly relates to a method for separating and purifying valuable metals of waste lithium batteries.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The main power source of the new energy automobile is a lithium ion power battery (hereinafter referred to as a lithium battery), and in recent years, as the occupation ratio of the new energy automobile in the whole automobile market is rapidly increased, the market scale of the lithium battery is continuously enlarged, and the demand is rapidly increased.
However, after 500-1000 charge-discharge cycles, the lithium battery deactivates the reactant and reduces the battery capacity, resulting in battery rejection, and if disposal methods such as landfill and incineration are adopted, environmental pollution and waste of a large amount of valuable metals are caused. The data show that the annual scrapping capacity of 2025-year power lithium batteries is estimated to reach 35 ten thousand tons, and the processing requirement is urgent. Therefore, in recent years, the recovery and regeneration of the waste lithium batteries become the industry with the most development prospect in the green industry.
At present, two types of recovery processes exist for waste lithium batteries: fire recovery and wet recovery. The fire recovery process generally adopts high-temperature roasting to refine valuable metals, and has the advantages of simple process, high energy consumption, low recovery rate, more waste gas and environmental pollution; the wet recovery is to separate and extract valuable metals in the battery anode material, then separate and extract the battery by using a mixer-settler or a centrifugal extractor to obtain valuable substances, and recycle the valuable substances. Compared with the fire recovery process, the traditional wet recovery process has the advantages of high purification degree and recovery rate of valuable metals, long period, low efficiency, more waste liquid generated after extraction by using an organic solvent, and environmental pollution.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a method for separating and purifying valuable metals of waste lithium batteries.
In order to achieve the above object, the present invention is realized by the following technical scheme:
a method for separating and purifying valuable metals of waste lithium batteries comprises the following steps:
crushing and screening the positive plate of the waste lithium battery, wherein the undersize material of the last-stage screen is positive black powder;
carrying out microwave pyrolysis on the positive electrode black powder at 300-600 ℃ for 30-60min;
alkaline leaching is carried out on the anode material powder subjected to microwave pyrolysis by adopting alkaline solution, and an Al simple substance is removed, so that alkaline leaching solution is obtained;
after primary filter pressing of alkaline leaching liquid, a filter cake a is reserved;
carrying out acid leaching treatment on the filter cake a under the microwave heating condition, wherein the microwave heating temperature is 55-65 ℃, the leaching time is 20-40min, the acid leaching solution is a mixed solution of citric acid and hydrogen peroxide, the molar ratio of the citric acid to the hydrogen peroxide is set to be 2-4:1, and the mass fraction of solute in the mixed solution is not lower than 10wt%;
cooling the acid leached solution, performing secondary filter pressing, and adding NH into the chlorine solution 3 ·H 2 O, precipitating metal ions in the filtrate, and then performing three times of filter pressing to obtain a filter cake c and filtrate;
dissolving filter cake c, and then adopting NaHSO 3 Dimethylglyoxime (C) 4 H 8 N 2 O 2 ) Ethanol solution and NH 3 ·H 2 O is precipitated step by step to obtain MnSO respectively 3 、Ni(C 4 H 7 N 2 O 2 ) 2 And Co (OH) 2 。
The purpose of carrying out microwave pyrolysis on the positive black powder at 300-600 ℃ is to remove impurities in the positive black powder, such as organic matter electrolyte, polymer diaphragm, conductive carbon and the like.
The purpose of alkaline leaching is to remove residual Al in the positive black powder, and the following reaction occurs:
the component of the filter cake a is LiCoO 2 、LiNiO 2 、LiMnO 2 、C。
The purpose of acid leaching under the microwave heating condition is to enable active substances in the anode powder to react with acid, enable valuable metals to be dissolved in a solution in an ionic form, strengthen the acid leaching by microwaves, improve the reaction rate, reduce the leaching liquid consumption, reduce the cost and shorten the wet recovery period, and the following reactions occur:
specifically, citric acid is a tricarboxylic acid, and has strong acidity and weak volatility, and is more commonly used acid leaching solution H 2 SO 4 Has weaker oxidizing property and can effectively reduce Mn 2+ Oxidation affects Mn recovery, and hydrogen peroxide is used as a reducing agent.
The filtrate of the secondary filter pressing contains Li + 、Co 2+ 、Ni 2+ 、Mn 2+ The composition of the filter cake b was residual C.
Step precipitation to respectively produce MnSO 3 、Ni(C 4 H 7 N 2 O 2 ) 2 And Co (OH) 2 The following reactions specifically occur:
the precipitant used is NaHSO 3 Dimethylglyoxime (C) 4 H 8 N 2 O 2 ) Ethanol solution and NH 3 ·H 2 And separating the valuable metal elements Mn, ni and Co sequentially through fractional precipitation and centrifugation.
In some embodiments, the alkaline solution is sodium hydroxide, potassium hydroxide, or the like.
In some embodiments, NH is added to the chlorine solution after the secondary filter press 3 ·H 2 And O, when metal ions in the filtrate are precipitated, controlling the pH value of the solution to be more than 10.
According to the precipitation dissolution equilibrium constant K sp (Ni(OH) 2 )=5.48×10 -16 、K sp (Co(OH) 2 )=5.92×10 -15 、K sp (Mn(OH) 2 )=4×10 -14 It follows that Ni when ph=8.8, 9.4 and 9.8 2+ 、Co 2+ 、Mn 2+ The precipitation is complete, so that the pH of step (7) is controlled to > 10, and Li + At this time, the lithium ion is released into the solution, and Li can be further extracted.
In some embodiments, the concentration of dimethylglyoxime in the dimethylglyoxime ethanol solution is not less than 20g/L.
Dimethylglyoxime (C) 4 H 8 N 2 O 2 ) Is insoluble in water, so that the above step (10) uses dimethylglyoxime (C) 4 H 8 N 2 O 2 ) Ethanol solution, adding NH into the solution system 3 ·H 2 Purpose of O on the one hand, NH 3 ·H 2 O is alkaline, the pH value of a solution system can be adjusted, no impurity is introduced, and the solution system is a good precipitator; on the other hand, introduce NH 4 + Is Ni 2+ And dimethylglyoxime (C) 4 H 8 N 2 O 2 ) The reaction provides an ammoniacal medium to accelerate the generation of precipitated nickel dimethylglyoxime Ni (C) 4 H 7 N 2 O 2 ) 2 。
In some embodiments, when the positive electrode plate of the waste lithium battery is obtained, the waste lithium battery is subjected to discharge treatment, and after the waste lithium battery is completely dried, the battery core part is manually disassembled, and the positive electrode plate is obtained.
Preferably, the discharging treatment process means that the waste lithium batteries are placed in saline water for soaking for more than 24 hours so as to be completely discharged.
In some embodiments, when the positive plate is crushed and screened, a multi-stage crushing mode is adopted, a linear screen is arranged after each stage of crushing, and the screening specification of the linear screen at the last stage is 100 meshes. The undersize powder is black powder of the anode material of the lithium battery.
In some embodiments, the step of fractional precipitation is: mixing the filter cake c with NaHSO 3 The solution is mixed and dissolved, and then NaHSO is continuously added into the solution 3 Regulating pH value of the solution to be 2-3, stirring and precipitating for 20-30min, separating solid from liquid to obtain clear solution a and precipitate a, and collecting precipitate a to obtain MnSO 3 ；
Adding ethanol solution of dimethylglyoxime and NH into the clear solution a 3 ·H 2 Regulating pH of the solution to 4.5-5, stirring and precipitating for 20-30min, separating solid from liquid to obtain clear solution b and precipitate b, and collecting precipitate b to obtain Ni (C) 4 H 7 N 2 O 2 ) 2 ；
Adding NH to the supernatant b 3 ·H 2 O, when pH is more than 10, stirring for 5-15min, collecting precipitate to obtain Co (OH) 2 。
Preferably, naHSO 3 The concentration of the solution is not lower than 50g/L.
In some embodiments, the method further comprises the step of treating the waste gas, and collecting and treating a small amount of waste gas generated by the reaction in the microwave pyrolysis process. So as to reach the atmospheric emission standard, and the whole system is green and pollution-free.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
(1) The purpose of acid leaching under the microwave heating condition is to enable active substances in the anode powder to react with acid, enable valuable metals to be dissolved in a solution in an ionic form, strengthen the acid leaching by microwaves, improve the reaction rate, reduce the leaching liquid consumption, reduce the cost and shorten the wet recovery period.
(2) The acid leaching adopts citric acid, the citric acid is tricarboxylic acid, the acidity is stronger, the volatility is weaker, and the acid leaching solution H is more commonly used 2 SO 4 Has weaker oxidizing property and can effectively reduce Mn 2+ Oxidation affects Mn recovery, and hydrogen peroxide is used as a reducing agent.
(3) The precipitant used is NaHSO 3 Dimethylglyoxime (C) 4 H 8 N 2 O 2 ) Ethanol solution and NH 3 ·H 2 O, the method of adjusting and controlling the pH value is adopted to separate valuable metal elements step by step, and the common salt and alkali precipitation method is used for separating and extracting Li, co, ni, mn elements to replace the organic solvent extraction method, so that the cost can be effectively reduced, the pollution caused by organic waste liquid is reduced, and the metal purification rate is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
Fig. 1 is a schematic diagram of a separation and purification system for valuable metals of a waste lithium battery according to an embodiment of the invention.
Fig. 2 is a schematic flow chart of a method for separating and purifying valuable metals of waste lithium batteries in an embodiment of the invention.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention is further illustrated below with reference to examples.
Example 1
A method for separating and purifying valuable metals of waste lithium batteries adopts the waste lithium batteries as commercial products.
In the embodiment of the invention, the pH value in the solution system is controlled and regulated by adopting a pH automatic regulating dosing device, and the medicament is added into the solution according to a set value.
In the embodiment of the invention, the deionized water is adopted, and the pH value is more than or equal to 6 and less than or equal to 7.
A method for separating and purifying valuable metals of waste lithium batteries comprises the following steps:
(1) Discharging and disassembling: and (3) performing discharge treatment on the waste ternary lithium battery, namely soaking the waste ternary lithium battery in a storage battery for storing salt water for 24 hours to discharge completely, and then drying the waste ternary lithium battery in drying equipment, wherein the drying temperature is set to 80 ℃, and the heat preservation time is set to 12 hours. Manually disassembling after drying, and removing the reserved battery core parts such as the lithium battery big package shell, the upper cover and the like;
(2) Crushing and screening: and (3) putting the battery core obtained in the step (1) into a multi-stage pulverizer for pulverization treatment, wherein the pulverizer can carry out multi-stage pulverization treatment, a linear screen device is arranged in the pulverizer, the primary screening is carried out after each stage of pulverization, the final stage screening specification of the linear screen is 100 meshes, and the final undersize powder is lithium battery anode material black powder.
(3) Microwave pyrolysis: and (3) feeding the lithium battery anode material black powder obtained by screening treatment in the step (2) into a microwave pyrolysis device through a feeding machine for heating and decomposing, wherein the temperature of the microwave pyrolysis device is set to 400 ℃, and the heat preservation time is controlled to be 40 minutes, so as to remove impurities such as organic matters electrolyte, polymer diaphragms, conductive carbon and the like in the lithium battery anode material black powder. The upper part of the microwave pyrolysis equipment is provided with an exhaust outlet, the exhaust outlet is connected with a tail gas collecting and treating device, and the exhaust gas generated in the pyrolysis process can be treated to reach the atmospheric emission standard and then be discharged. And cooling the anode material powder obtained by pyrolysis, and then, collecting the anode material powder in a discharge bin.
(4) Alkaline leaching: the NaOH solution with a certain concentration is stored in the liquid storage tank. The bottom of the discharging bin is provided with a gravity sensor, the positive electrode material powder collected after microwave pyrolysis and cooling in the step (3) is weighed, then the powder enters leaching equipment through a conveyor, naOH solution is added into the leaching equipment according to the solid-liquid mass ratio of 1:1, alkaline leaching treatment is carried out on the positive electrode material, a stirrer is arranged on the upper portion of the leaching equipment, the rotating speed of the stirrer is set to be 80r/min, the stirring time is controlled to be 30min, and the purpose is to remove residual Al in the positive electrode material.
(5) Primary filter pressing: pumping the alkaline leaching solution obtained in the step (4) into a filter press through a solution pump to carry out filter pressing treatment, and collecting a filter cake in the filter press after the filter pressing is finished, wherein the filter cake is named as a filter cake a.
(6) Microwave acid leaching: the leaching solution used in this process is citric acid (C) 6 H 8 O 7 ) Solution and hydrogen peroxide (H) 2 O 2 ) The solutions are respectively stored in liquid storage tanks for standby.
And (5) weighing the filter cake a obtained in the step (5), and then, feeding the filter cake a into a leaching tank through a conveyor. And adding a mixed solution of citric acid and hydrogen peroxide (the mixed solution is prepared by mixing the two solutions according to the molar ratio of 2:1) into a leaching tank through a liquid adding device, wherein the mass fraction of the mixed solution is 20 percent, the top and the side surfaces of the leaching tank are provided with microwave generating devices, and microwave acid leaching treatment is carried out by utilizing the characteristics of strong catalysis and rapid heating of microwaves, wherein the microwave heating temperature is set to 60 ℃, and the leaching time is controlled to be 30 minutes.
(7) Secondary filter pressing: and (3) naturally cooling the leaching solution obtained after the microwave acid leaching in the step (6) to room temperature, then performing filter pressing on the leaching solution in a filter press, and collecting filtrate in a liquid collector.
(8) Adding alkali for precipitation: and (3) pumping filtrate in the liquid trap in the step (7) into a reaction tank through a solution pump, wherein a stirrer is arranged at the upper part of the reaction tank, and simultaneously, the pH value of a solution system is monitored in real time by using a pH automatic regulating dosing device, so that the solution is acidic.
Specifically, the above-mentioned pH automatic regulating dosing device is provided with a medicament storage bin in which NH with a concentration of 10 vol.% is stored 3 ·H 2 O (not exceeding 1/3 of the capacity of the medicament storage bin), at the moment, the dosing rate is controlled to be 1L/h, and NH is automatically added into the reaction tank 3 ·H 2 O, simultaneously starting the stirrer, controlling the rotating speed of the stirrer to be 80r/min, gradually developing alkalinity of the solution, starting to continuously generate precipitate, and reducing NH at the moment 3 ·H 2 The dosing rate of O is 0.5L/h, the pH value is regulated to be less than 10 and less than 12, the equipment is set into a mode of automatically regulating the dosing rate according to the pH value, and the stirring time is controlled to be 40min;
(9) And (3) carrying out pressure filtration for three times: and (3) pumping the liquid in the reaction tank in the step (8) into a filter press for secondary filter pressing, and collecting a filter cake in the filter press after the completion of the filter pressing, and the filter cake is named as a filter cake c. Meanwhile, the filtrate is stored, the components are mainly LiOH, and Li can be further extracted.
(10) Precipitation separation: the precipitants used in this process are: naHSO with concentration of 50g/L 3 Solution, 20g/L of glyoxime (C) 4 H 8 N 2 O 2 ) Ethanol solution and 10 vol.% NH 3 ·H 2 O is respectively stored in three medicament storage bins of the pH automatic regulating and dosing device.
Delivering the filter cake c obtained in the step (9) to a grading precipitation device, wherein the grading precipitation device consists of a multi-stage precipitation reaction tank, a stirrer is arranged in the precipitation reaction tank, a centrifuge is arranged at the lower part of each stage of precipitation reaction tank, the two are connected by a liquid guide pipe, and the NaHSO is added into the first stage of precipitation reaction tank according to the mass ratio of 2:1 3 The solution is dissolved, the stirrer is in a closed state at the moment, and simultaneously, the solution is monitored in real time by using the pH automatic regulating and dosing deviceThe pH of the system, at which time the solution is acidic.
Starting the stirrer, controlling the stirring rotation speed of the stirrer to be 60r/min, and carrying out the following detailed fractional precipitation separation process:
(a) Maintaining NaHSO 3 The valve of the solution medicament storage bin is in an open state, the dosing speed is controlled to be 0.4L/h, a first-stage precipitation reaction tank starts to continuously generate precipitation, equipment is set to be in a mode of automatically adjusting the dosing speed according to the pH value, the pH value is controlled to be less than 2 and less than 3, the stirring time is controlled to be 30min, centrifugal separation is carried out, the precipitation is collected, and the precipitation components are mainly MnSO 3 ；
(b) Pumping the clear liquid obtained in the step (a) into a second-stage precipitation reaction tank through a solution pump, stirring, and simultaneously opening and loading dimethylglyoxime (C) 4 H 8 N 2 O 2 ) Ethanol solution and NH 3 ·H 2 O agent storage bin valve, controlling the dosing speed to be 0.3L/h, and closing the dimethylglyoxime (C) after 30min 4 H 8 N 2 O 2 ) Reagent storage bin valve of ethanol solution only continuously adds NH 3 ·H 2 O agent, the process continuously produces red precipitate, the pH is regulated and controlled to be less than 4.5 and less than 5, the stirring time is controlled to be 25min, then centrifugal separation is carried out, the precipitate is collected, and the precipitate component is mainly nickel-dimethylglyoxime Ni (C) 4 H 7 N 2 O 2 ) 2 。
(c) Pumping the clear liquid obtained in the step (b) into a third-stage precipitation reaction tank through a solution pump, stirring and maintaining NH 3 ·H 2 The valve of the O medicament storage bin is in an open state, and NH is continuously added 3 ·H 2 O, controlling the dosing rate to be 0.3L/h, continuously generating light red precipitate, continuously stirring for 10min after the pH value is more than 10, centrifuging, and collecting precipitate, wherein the precipitate component is mainly Co (OH) 2 。
Example 2
The differences from the above-described example 1 are: in the step (3), the temperature of the microwave pyrolysis equipment is set to 300 ℃, the heat preservation time is controlled to 30min, and other steps and parameters are unchanged.
Example 3
The differences from example 1 are: in the step (3), the temperature of the microwave pyrolysis equipment is set to 600 ℃, the heat preservation time is controlled to 60min, and other steps and parameters are unchanged.
Example 4
The difference from example 1 is that the mixed solution is prepared by the microwave acid leaching citric acid and hydrogen peroxide in the molar ratio of 3:1 in the step (6), the mass fraction of the mixed solution is 20wt%, and other steps and parameters are unchanged.
Example 5
The differences from example 1 are: and (3) preparing a mixed solution with the molar ratio of the citric acid and the hydrogen peroxide of 2:1 by microwave acid leaching in the step (6), wherein the mass fraction of the mixed solution is 30wt%, and other steps and parameters are unchanged.
Comparative example 1
The differences from example 1 are: the microwave pyrolysis in the step (3) is changed into traditional calcination pyrolysis, and other steps and parameters are unchanged.
Comparative example 2
The differences from example 1 are: the microwave acid leaching in the step (6) is changed into normal-temperature acid leaching, and other steps and parameters are unchanged.
The positive electrode materials of the waste lithium batteries used in the examples contain 13.65% of nickel Ni, 35.19% of cobalt Co, 10.75% of manganese Mn and 8.26% of lithium Li, and recovery rates of valuable metals are shown in Table 1 after recovery operations of the waste lithium batteries are performed according to the methods of examples 1 to 5 and comparative examples 1 to 2.
From table 1, it is known that recovery rate of valuable metals can be significantly improved by microwave pyrolysis and microwave acid leaching, the method adopted in example 1 is the optimal method, and recovery rates of Ni, co, mn, li obtained are 99.72%, 99.28%, 98.35% and 100%, respectively, which shows that the recovery rate of valuable metals is high and the method has strong applicability.
Table 1 recovery of each valuable metal in examples and comparative examples
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for separating and purifying valuable metals of waste lithium batteries is characterized by comprising the following steps: the method comprises the following steps:
crushing and screening the positive plate of the waste lithium battery, wherein the undersize material of the last-stage screen is positive black powder;
carrying out microwave pyrolysis on the positive electrode black powder at 300-600 ℃ for 30-60min;
alkaline leaching is carried out on the anode material powder subjected to microwave pyrolysis by adopting alkaline solution, and an Al simple substance is removed, so that alkaline leaching solution is obtained;
after primary filter pressing of alkaline leaching liquid, a filter cake a is reserved;
carrying out acid leaching treatment on the filter cake a under the microwave heating condition, wherein the microwave heating temperature is 55-65 ℃, the heat preservation time is 20-40min, the acid leaching solution is a mixed solution of citric acid and hydrogen peroxide, the molar ratio of the citric acid to the hydrogen peroxide is 2-4:1, and the mass fraction of solute in the mixed solution is not less than 10wt%;
cooling the acid leached solution, performing secondary filter pressing, and adding NH into the chlorine solution 3 ·H 2 O, precipitating metal ions in the filtrate, and then performing three times of filter pressing to obtain a filter cake c and filtrate;
dissolving filter cake c, and then adopting NaHSO 3 Ethanol solution of dimethylglyoxime and NH 3 ·H 2 O is precipitated step by step to obtain MnSO respectively 3 、Ni(C 4 H 7 N 2 O 2 ) 2 And Co (OH) 2 。
2. The method for separating and purifying valuable metals from waste lithium batteries according to claim 1, which is characterized in that: the alkali solution for alkaline leaching is sodium hydroxide or potassium hydroxide.
3. The method for separating and purifying valuable metals from waste lithium batteries according to claim 1, which is characterized in that: after secondary filter pressing, NH is added into the chlorine liquid 3 ·H 2 And O, when metal ions in the filtrate are precipitated, controlling the pH value of the solution to be more than 10.
4. The method for separating and purifying valuable metals from waste lithium batteries according to claim 1, which is characterized in that: the concentration of the dimethylglyoxime in the dimethylglyoxime ethanol solution is not lower than 20g/L.
5. The method for separating and purifying valuable metals from waste lithium batteries according to claim 1, which is characterized in that: when the positive plate of the waste lithium battery is obtained, the waste lithium battery is subjected to discharge treatment, and after the waste lithium battery is completely dried, the battery core is manually disassembled, and the positive plate is obtained.
6. The method for separating and purifying valuable metals from waste lithium batteries according to claim 1, which is characterized in that: the discharging treatment process is to put the waste lithium battery into brine for soaking for more than 24 hours so as to completely discharge.
7. The method for separating and purifying valuable metals from waste lithium batteries according to claim 5, which is characterized in that: when the positive plate is crushed and screened, a multi-stage crushing mode is adopted, a linear screen is arranged after each stage of crushing, and the screening specification of the last stage of linear screen is 100 meshes.
8. The method for separating and purifying valuable metals from waste lithium batteries according to claim 5, which is characterized in that: the step-by-step precipitation comprises the following steps: mixing the filter cake c with NaHSO 3 The solution is mixed and dissolved, and then NaHSO is continuously added into the solution 3 Regulating pH value of the solution to be 2-3, stirring and precipitating for 20-30min, separating solid from liquid to obtain clear solution a and precipitate a, and collecting precipitate a to obtain MnSO 3 ；
Adding ethanol solution of dimethylglyoxime and NH into the clear solution a 3 ·H 2 O, adjusting the pH value of the solution to be4.5-5, stirring and precipitating for 20-30min, separating solid and liquid to obtain clear liquid b and precipitate b, and collecting precipitate b to obtain Ni (C) 4 H 7 N 2 O 2 ) 2 ；
Adding NH to the supernatant b 3 ·H 2 O, when pH is more than 10, stirring for 5-15min, collecting precipitate to obtain Co (OH) 2 。
9. The method for separating and purifying valuable metals from waste lithium batteries according to claim 1, which is characterized in that: naHSO (NaHSO) 3 The concentration of the solution is not lower than 50g/L.
10. The method for separating and purifying valuable metals from waste lithium batteries according to claim 1, which is characterized in that: the method also comprises the step of waste gas treatment, and a small amount of waste gas generated by the reaction in the microwave pyrolysis process is collected and treated.
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