CN112103591B - Harmless recycling method for waste lithium battery electrolyte - Google Patents

Harmless recycling method for waste lithium battery electrolyte Download PDF

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CN112103591B
CN112103591B CN202011122915.1A CN202011122915A CN112103591B CN 112103591 B CN112103591 B CN 112103591B CN 202011122915 A CN202011122915 A CN 202011122915A CN 112103591 B CN112103591 B CN 112103591B
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lithium battery
electrolyte
solution
filtering
waste lithium
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CN112103591A (en
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张燕
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Anhui Liyuan new energy Co.,Ltd.
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C21/00—Disintegrating plant with or without drying of the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/08—Separating or sorting of material, associated with crushing or disintegrating
    • B02C23/14—Separating or sorting of material, associated with crushing or disintegrating with more than one separator
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/02—Magnetic separation acting directly on the substance being separated
    • B03C1/30—Combinations with other devices, not otherwise provided for
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C2201/00—Codes relating to disintegrating devices adapted for specific materials
    • B02C2201/06—Codes relating to disintegrating devices adapted for specific materials for garbage, waste or sewage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Food Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a harmless recycling method of waste lithium battery electrolyte, which comprises the steps of discharging, crushing, binder separation and physical separation to obtain clean steel, plastic, diaphragm and copper materials without electrolyte residues. Transferring the obtained residual waste battery materials into a closed container, adding clear water used in the step (4), and filtering to obtain clear liquid 1 and residual solid materials; alkaline leaching and acid leaching; and recovering the clear liquid. The treatment method can effectively recover electrolyte components, can effectively separate and recover other components such as positive electrode materials, negative electrode materials and the like, realizes safety and reduces the pollution to the environment in the recovery process.

Description

Harmless recycling method for waste lithium battery electrolyte
Technical Field
The invention relates to a recovery treatment process, in particular to a pollution-free recovery method of waste lithium battery electrolyte.
Background
Since the commercialization of lithium ion batteries, lithium ion batteries have been widely used in industry and life due to their advantages of small size, light weight, fast charging speed, wide temperature range, and long cycle life. The outer layer of the lithium ion battery is wrapped by a plastic, aluminum and iron shell, and the inner layer is a positive active material, a negative active material, an aluminum or copper foil current collector, a binder, a polyethylene or polypropylene porous diaphragm material, an electrolyte (a carbonate organic solvent) and a dissolved electrolyte salt (generally LiPF)6) And the like. The positive active material is multi-position lithium manganate, nickel cobalt lithium manganate, lithium iron phosphate, lithium cobaltate and the like. The negative electrode active material is mostly graphite carbon powder, lithium titanate, and the like.
With the increasing demand for lithium ion batteries, especially for the electric transportation industry, a large number of lithium ion batteries must be retired in the near future, and lack of proper treatment, the waste lithium ion batteries may cause serious consequences, such as environmental pollution and resource waste.
The electrolyte contained in the lithium ion battery is 10-15 wt.%, and because the electrolyte in the waste lithium battery is in a wetting state with positive and negative pole pieces in a battery core in the charging and discharging process, the content of the liquid electrolyte is less after the electrolyte is used, the separation is difficult, and the separation cost is high. In the prior art, the residual waste lithium battery materials are subjected to pyrometallurgical treatment and high-temperature pyrolysis treatment, the residual electrolyte is often gasified and discharged, the electrolyte waste is caused, the serious environmental pollution is caused, and the full recovery requirement is not met.
Before the waste batteries are disassembled, the electrolyte is generally not collected, but is directly burnt with the waste batteries, so that the residual electrolyte is gasified and discharged or the waste lithium batteries are directly crushed, so that the residual electrolyte is mixed into a solid material and is discharged in a waste liquid form through subsequent treatment. Or the organic solvent is adopted for extraction after the organic solvent is directly crushed, however, the crushed powder contains a large amount of other anode and cathode material components, so that many uncertain factors are brought when the extracted organic solvent is separated and purified, the recovery process is complicated, and the recovery efficiency is also influenced.
In the prior art, the lithium ion battery shell is usually and independently recovered, the waste lithium battery needs to be disassembled after discharge pretreatment before the shell is recovered, and the disassembled plastic and iron shell can be recovered. Considering the condition of injury to human bodies, manual disassembly is not adopted as much as possible, and the efficiency is low, but no mature automatic disassembly equipment exists in the industry. On the other hand, a part of residual electrolyte is soaked in the electrode plates and the diaphragm after disassembly and separation, and the part of residual electrolyte is not considered in most electrode plate recovery processes, so that incomplete recovery is caused, and part of electrolyte ions pollute the follow-up process.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a harmless recycling method for waste lithium battery electrolyte, which can effectively recycle electrolyte components, effectively separate and recycle other components such as positive electrode materials, negative electrode materials and the like, realize safety and reduce the pollution to the environment in the recycling process.
The technical problem to be solved by the invention can be realized by adopting the following technical scheme:
a harmless recycling method of waste lithium battery electrolyte comprises the following steps:
step 1, discharging: placing the waste lithium battery in 5-10 wt.% of sodium carbonate aqueous solution, soaking for 8-12h, taking out, spraying and washing with clear water, drying at 40-50 ℃, and storing the washed clear water.
Step 2, crushing: filling mixed gas of argon and carbon dioxide into the closed environment, and mechanically crushing the waste lithium battery to obtain crushed materials; then the gas is discharged and passed into the clear water in step 1.
Step 3, binder separation: putting the crushed material into NMP solvent at 60-70 ℃ for ultrasonic treatment for 0.5-1h, drying for 1-2h after centrifugal separation, and heating the solvent to 150-200 ℃.
Step 4, physical separation: sorting the crushed materials in the step (2) by adopting a wind power sorting machine, a magnetic sorting machine and a gravity sorting machine to separate steel, plastics, diaphragms and copper; and respectively placing the steel, the plastic, the diaphragm and the copper into a small amount of clear water for ultrasonic cleaning to obtain clean steel, plastic, diaphragm and copper materials without electrolyte residues.
Step 5, transferring the residual waste battery materials obtained in the step 4 into a closed container, adding the clean water used in the step 4, stirring for 10-30min, discharging gas and introducing into the clean water in the step 1; filtering to obtain clear liquid 1 and residual solid materials.
Step 6, alkaline leaching and acid leaching: treating the residual solid material in the step (5) by using 20-30g/L sodium hydroxide solution, stirring for 10-30min, and filtering to obtain clear liquid 2 and residual solid material; and (3) treating the residual solid material by using a mixed solution of citric acid and hydrogen peroxide, filtering to obtain a clear solution 3 and graphite particles, and drying the graphite particles.
And 7, respectively recovering the clear liquid 1, the clear liquid 2 and the clear liquid 3.
Further, the step 2 adopts multi-stage crushing, specifically, the physical particle size of the waste lithium battery is 60-100mm by the first coarse crushing, and then the particle size is 10-20mm by the second fine crushing.
Further, adding sodium carbonate into the clear liquid 1 in the step 5, heating to 45 ℃, stirring, standing for 10-30min, and filtering to obtain lithium carbonate precipitate. The minimum amount of sodium carbonate added is such that crystallization of the solution occurs.
According to the principle that organic matters are dissolved by organic matters, organic binder polyvinylidene fluoride (PVDF) in the anode material is dissolved by organic solvent N-methylpyrrolidone (NMP), so that active substances are stripped from the aluminum foil. The active substances can be completely stripped by soaking the positive electrode cobalt lithium film, and the used NMP organic solvent can remove the binder by a heating distillation method so as to realize recycling. The organic solvents of ethylene carbonate and dimethyl carbonate existing in the electrolyte can be recovered by heating and distillation in the process.
Further, adding sodium carbonate into the clear liquid 3 in the step 6, heating to 45 ℃, stirring, standing for 10-30min, and filtering to obtain lithium carbonate precipitate. The minimum amount of sodium carbonate added is such that crystallization of the solution occurs. Then electrolytic recovery of metal cobalt and chemical precipitation recovery of metal nickel and manganese are carried out in sequence.
The chemical reaction equation of adding sodium carbonate into the clear liquid 1 and the clear liquid 3 is as follows:
2Li++Na2C03→Li2C03↓+2Na+
Li2C03the precipitates of (A) are also all endothermic, increasing the temperature favouring the obtaining of Li2C03Is also advantageous for Li2C03Dissolution of the precipitate in solution. At a temperature below 50 ℃, Li2C03The precipitation of (2) dominates the above chemical reaction, and the recovery efficiency of Li ions is remarkably improved with the increase of temperature. The reaction temperature is raised to over 50 ℃, Li2C03Precipitation and Li2C03The precipitate dissolved becomes an equilibrium state, and the recovery efficiency of Li ions hardly changes with an increase in temperature. Because of CO3 2-Is easy to react with H+Combine to form HCO3 -,H+Is in favor of Li2C03I.e. the recovery efficiency of Li ions increases with increasing equilibrium pH.
Further, the above solution was mixed with the clear solution 3.
Further, the clear liquids of steps 5 and 6 are subjected to an evaporative concentration operation in order to reduce the processing cost and to improve the subsequent recovery.
Further, the technological parameters for recovering the metallic cobalt by electrolysis are as follows: placing the Pd-Zn composite anode and the stainless steel cathode in an electrolytic cell, adjusting the pH to 3.2-3.8, the temperature to 25-35 ℃, and the cathode current density to 80-200 mA/cm2The electroplating time is 10-30 minutes, and the distance between the Pd-Zn composite anode and the stainless steel cathode is 5-10 cm.
Further, the chemical precipitation method for recovering metal nickel and manganese comprises adding 1.5-3.5g/L NaOH solution into the electrolyzed solution, adjusting pH to 7.2-7.5, filtering Ni (OH)2Precipitating, adding NaOH solution to adjust pH to 8.5-13, filtering Mn (OH)2And (4) precipitating.
The positive current collector of the lithium ion battery is composed of an aluminum foil, the aluminum foil reacts with an alkaline solution, so that the aluminum foil can be dissolved into the alkaline solution, and the positive active substance cannot be dissolved in the alkaline solution, so that the separation of the positive active substance and the alkaline solution is realized. The reaction of aluminum and sodium hydroxide is Al + NaOH + H2O→NaAlO2+H2And ×) and the filtered clear liquid 2 can be recycled to obtain metal aluminum by adopting the existing method, and the active substances are recycled and reused by post-treatment. Further, the pH of the clear solution 2 was adjusted to form Al (OH)3Precipitating, filtering and heating to obtain the alumina.
As the crushed waste battery materials are accompanied by electrolyte, lithium hexafluorophosphate in the electrolyte and water are subjected to chemical reaction to generate harmful gas of hydrogen fluoride, the gas is discharged and introduced into the clean water in the step 1, so that the hydrogen fluoride and the sodium carbonate can react to generate sodium fluoride. During the process of generating sodium fluoride from hydrogen fluoride, a certain amount of 5-10 wt.% sodium carbonate aqueous solution or a certain amount of sodium hydroxide can be added into the washed clean water.
Because the inorganic acid can generate toxic gases such as sulfur oxides, nitrogen oxides, chlorides and the like in the process of leaching metal ions, secondary environmental pollution is generated, and the sulfuric acid, the nitric acid and the hydrochloric acid are strong acids, have high corrosivity and oxidability and have high requirements on equipment. To this end, the inventors have used mineral acid instead to leach lithium cobaltate to recover the cobalt and lithium metals therein. Further, the process conditions of acid leaching in the step 6 are as follows:the temperature is 80-90 deg.C, the time is 20-30min, the citric acid concentration is 1.0-2.0mol/L, and the hydrogen peroxide concentration is 1.5-3.0 mol/L. The reaction of acid leaching is as follows: LiCoO2+C6H8O7+H2O2→Li3C6H5O7+Co3(C6H5O7)2+H2O+O2↑。
According to the principle of precipitation-dissolution equilibrium, metal ions precipitate in an alkaline environment, and the reaction equation is as follows:
Ni2++OH-→Ni(OH)2↓+H2O；
Co2++OH-→Co(OH)2↓+H2O；
Mn2++OH-→Mn(OH)2↓+H2O；
Ni(OH)2、Co(OH)2、Mn(OH)2respectively has a solubility product constant Ksp of 10-14.7、10-43.7、10-12.72. Due to Co (OH)2Has a solubility product constant Ksp that is too small to readily react with OH over a wide pH range-And (3) carrying out precipitation reaction so as to coprecipitate with other metal ions, and in order to better separate the metal ions, the cobalt ions are removed from the clear liquid 3 by electrodeposition after the step 6. Ni (OH)2、Co(OH)2、Mn(OH)2The solubility product constants Ksp of (A) and (B) differ by two orders of magnitude, and although there is an overlap in the pH range in which precipitates are formed, there is a certain shift, so that in order to separate nickel ions and manganese ions in sequence, the pH is first adjusted to 7.2-7.5 and then to 8.5-13. Therefore, the influence of the nickel ion and manganese ion coprecipitation on the subsequent recovery of the simple substance metal can be avoided.
Further, the method also comprises the step 8: the solution of step 7 is subjected to an electrolytic process to remove residual metal ions. After the treatment of the previous steps, most of lithium battery materials are recovered, but a small amount of metal ions such as Ni, Mn, Co and the like exist, and because the content of the ions is very low and the respective recovery meanings are not great, electrolysis parallel connection is adoptedThe current density is continuously changed to deposit the materials together. The specific technological parameters of the electrolytic recovery are as follows: the Pd-Zn composite anode and the stainless steel cathode are placed in an electrolytic bath at the temperature of 25-35 ℃, and the current density of the cathode is 150-200 mA/cm2The electroplating time is 5-10 minutes; the cathode current density is 250-300 mA/cm2The electroplating time is 5-10 minutes; the cathode current density is 350-400 mA/cm2The electroplating time is 5-10 minutes; the distance between the Pd-Zn composite anode and the stainless steel cathode is 5-10 cm.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention can ensure that the electrolyte is recovered safely, environment-friendly, efficiently and economically, avoids the environmental harm caused by directly discarding the electrolyte in the waste lithium battery,
2. meanwhile, the binder, the positive and negative electrode materials, the copper foil, the aluminum foil and the plastic in the lithium battery can be efficiently recycled, and the method has good industrial recycling feasibility.
3. The recovery rate of lithium, cobalt, nickel and manganese in the waste lithium ion battery can reach 99.8 percent, and toxic gases HF and SO are not discharged to the atmosphere in the recovery process2、NO2And the like.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to specific examples.
Example 1
A harmless recycling method of waste lithium battery electrolyte comprises the following steps:
step 1, discharging: the waste lithium battery is placed in a 5 wt.% sodium carbonate aqueous solution to be soaked for 9h for discharging treatment, then the waste lithium battery is taken out and sprayed and washed by clean water, the waste lithium battery is dried at the temperature of 45 ℃, and the washed clean water is stored.
Step 2, crushing: filling mixed gas of argon and carbon dioxide into the closed environment, and mechanically crushing the waste lithium battery to obtain crushed materials; then the gas is discharged and passed into the clear water in step 1. The particle size of the waste lithium battery is 60mm by the first coarse crushing, and then 10mm by the second fine crushing.
Step 3, binder separation: putting the crushed material into NMP solvent at 60 ℃ for ultrasonic treatment for 0.5h, drying for 1h after centrifugal separation, and heating the solvent to 150 ℃.
Step 4, physical separation: sorting the crushed materials in the step (2) by adopting a wind power sorting machine, a magnetic sorting machine and a gravity sorting machine to separate steel, plastics, diaphragms and copper; and respectively placing the steel, the plastic, the diaphragm and the copper into a small amount of clear water for ultrasonic cleaning to obtain clean steel, plastic, diaphragm and copper materials without electrolyte residues.
Step 5, transferring the residual waste battery materials obtained in the step 4 into a closed container, adding the clean water used in the step 4, stirring for 10min, discharging gas and introducing into the clean water in the step 1; filtering to obtain clear liquid 1 and residual solid materials.
Step 6, alkaline leaching and acid leaching: treating the residual solid material in the step 5 by using 20g/L sodium hydroxide solution, stirring for 10min, and filtering to obtain a clear liquid 2 and the residual solid material; and (3) treating the residual solid material by using a mixed solution of citric acid and hydrogen peroxide, filtering to obtain a clear solution 3 and graphite particles, and drying the graphite particles.
And 7, respectively recovering the clear liquid 1, the clear liquid 2 and the clear liquid 3. And (3) adding sodium carbonate into the clear liquid 1 in the step (5), heating to 45 ℃, stirring, standing for 15min, and filtering to obtain lithium carbonate precipitate. Adjusting the pH of the clear solution 2 to form Al (OH)3Precipitating, filtering and heating to obtain the alumina. And (3) adding sodium carbonate into the clear liquid 3 in the step 6, heating to 45 ℃, stirring, standing for 10min, and filtering to obtain lithium carbonate precipitate. The minimum amount of sodium carbonate added is such that crystallization of the solution occurs. Then electrolytic recovery of metal cobalt and chemical precipitation recovery of metal nickel and manganese are carried out in sequence. The technological parameters for recovering the metallic cobalt by electrolysis are as follows: placing the Pd-Zn composite anode and the stainless steel cathode in an electrolytic cell, adjusting the pH to 3.8 at 35 ℃, and controlling the cathode current density to 80mA/cm2The electroplating time is 30 minutes, and the distance between the Pd-Zn composite anode and the stainless steel cathode is 10 centimeters. The chemical precipitation method for recovering metal nickel and manganese is to add 3.5g/L NaOH solution into the electrolyzed solution and regulatepH to 7.5, filtration of Ni (OH)2Precipitating, adding NaOH solution to adjust pH to 8.5, filtering Mn (OH)2And (4) precipitating.
Example 2
A harmless recycling method of waste lithium battery electrolyte comprises the following steps:
step 1, discharging: the waste lithium battery is placed in 10 wt.% sodium carbonate aqueous solution to be soaked for 8h for discharging treatment, then the waste lithium battery is taken out to be sprayed and washed by clean water, the waste lithium battery is dried at the temperature of 50 ℃, and the washed clean water is stored.
Step 2, crushing: filling mixed gas of argon and carbon dioxide into the closed environment, and mechanically crushing the waste lithium battery to obtain crushed materials; then the gas is discharged and passed into the clear water in step 1. The particle size of the waste lithium battery is 100mm by the first coarse crushing, and is 20mm by the second fine crushing.
Step 3, binder separation: putting the crushed material into NMP solvent at 70 ℃ for ultrasonic treatment for 1h, drying for 1.5h after centrifugal separation, and heating the solvent to 200 ℃.
Step 4, physical separation: sorting the crushed materials in the step (2) by adopting a wind power sorting machine, a magnetic sorting machine and a gravity sorting machine to separate steel, plastics, diaphragms and copper; and respectively placing the steel, the plastic, the diaphragm and the copper into a small amount of clear water for ultrasonic cleaning to obtain clean steel, plastic, diaphragm and copper materials without electrolyte residues.
Step 5, transferring the residual waste battery materials obtained in the step 4 into a closed container, adding the clean water used in the step 4, stirring for 30min, discharging gas and introducing into the clean water in the step 1; filtering to obtain clear liquid 1 and residual solid materials.
Step 6, alkaline leaching and acid leaching: treating the residual solid material in the step 5 by using 30g/L sodium hydroxide solution, stirring for 30min, and filtering to obtain a clear liquid 2 and the residual solid material; and (3) treating the residual solid material by using a mixed solution of citric acid and hydrogen peroxide, filtering to obtain a clear solution 3 and graphite particles, and drying the graphite particles.
Step 7, respectively recovering the clear liquidLiquid 1, clear liquid 2 and clear liquid 3. And (3) adding sodium carbonate into the clear liquid 1 in the step (5), heating to 45 ℃, stirring, standing for 30min, and filtering to obtain lithium carbonate precipitate. Adjusting the pH of the clear solution 2 to form Al (OH)3Precipitating, filtering and heating to obtain the alumina.
And (3) adding sodium carbonate into the clear liquid 3 in the step 6, heating to 45 ℃, stirring, standing for 30min, and filtering to obtain lithium carbonate precipitate. The minimum amount of sodium carbonate added is such that crystallization of the solution occurs. Then electrolytic recovery of metal cobalt and chemical precipitation recovery of metal nickel and manganese are carried out in sequence. The technological parameters for recovering the metallic cobalt by electrolysis are as follows: placing the Pd-Zn composite anode and the stainless steel cathode in an electrolytic cell, adjusting the pH to 3.5 at 30 ℃, and controlling the cathode current density to 150mA/cm2The electroplating time is 20 minutes, and the distance between the Pd-Zn composite anode and the stainless steel cathode is 8 centimeters. The chemical precipitation method for recovering metal nickel and manganese comprises adding 2.0g/L NaOH solution into the electrolyzed solution, adjusting pH to 7.3, filtering Ni (OH)2Precipitating, adjusting the pH to 10 by further addition of NaOH solution, filtering off Mn (OH)2And (4) precipitating.
And 8, performing an electrolytic process on the solution in the step 7 to remove residual metal ions. The specific technological parameters of the electrolytic recovery are as follows: the Pd-Zn composite anode and the stainless steel cathode are arranged in an electrolytic bath at the temperature of 25 ℃ and the cathode current density of 150mA/cm2The electroplating time is 5 minutes; the cathode current density is 250mA/cm2The electroplating time is 5 minutes; the cathode current density is 350mA/cm2The electroplating time is 10 minutes; the distance between the Pd-Zn composite anode and the stainless steel cathode is 10 cm.
The content of metal ions in the recovered solution treated in steps 7 and 8 in example 1-2 was measured by inductively coupled plasma atomic emission spectrometry. The results are reported in table 1.
Li(g/L) Al(g/L) Cu(g/L) Co(g/L) Ni(g/L) Mn(g/L)
Example 1(7) 1.2×10-3 1.6×10-3 5.4×10-3 2.7×10-3 3.8×10-3 6.9×10-3
Example 1(8) 3.8×10-4 3.1×10-4 5.0×10-4 8.3×10-4 6.2×10-4 4.5×10-4
Example 2(7) 2.2×10-3 4.8×10-3 9.4×10-3 1.9×10-3 4.4×10-3 8.8×10-3
Example 2(8) 3.6×10-4 5.1×10-4 4.7×10-4 7.6×10-4 3.8×10-4 5.6×10-4
The waste lithium ion battery is effectively recycled through the treatment of the invention, the content of harmful metal ions in the treated wastewater is very low, and the harmful metal ions are more effectively removed through the electrolysis of the last step, thereby avoiding the pollution to the environment.
The above embodiments are only for illustrating the invention and are not to be construed as limiting the invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention, therefore, all equivalent technical solutions also belong to the scope of the invention, and the scope of the invention is defined by the claims.

Claims (6)

1. A harmless recycling method of waste lithium battery electrolyte comprises the following steps:
step 1, discharging: placing the waste lithium battery in 5-10 wt% sodium carbonate aqueous solution, soaking for 8-12h, discharging, taking out, spraying and washing with clear water, drying at 40-50 deg.C, and storing the washed clear water;
step 2, crushing: filling mixed gas of argon and carbon dioxide into the closed environment, and mechanically crushing the waste lithium battery to obtain crushed materials; then discharging the gas and introducing into the clean water in the step 1;
step 3, binder separation: putting the crushed material into NMP solvent at 60-70 ℃ for ultrasonic treatment for 0.5-1h, drying for 1-2h after centrifugal separation, and heating the solvent to 150-200 ℃;
step 4, physical separation: sorting the crushed materials in the step (2) by adopting a wind power sorting machine, a magnetic sorting machine and a gravity sorting machine to separate steel, plastics, diaphragms and copper; respectively putting steel, plastic, a diaphragm and copper into a small amount of clear water for ultrasonic cleaning to obtain clean steel, plastic, diaphragm and copper materials without electrolyte residues;
step 5, transferring the residual waste battery materials obtained in the step 4 into a closed container, adding the clean water used in the step 4, stirring for 10-30min, discharging gas and introducing into the clean water in the step 1; filtering to obtain clear liquid 1 and residual solid materials;
step 6, alkaline leaching and acid leaching: treating the residual solid material in the step (5) by using 20-30g/L sodium hydroxide solution, stirring for 10-30min, and filtering to obtain clear liquid 2 and residual solid material; treating the residual solid material by using a mixed solution of citric acid and hydrogen peroxide, filtering to obtain a clear solution 3 and graphite particles, and drying the graphite particles;
step 7, respectively recovering the clear liquid 1, the clear liquid 2 and the clear liquid 3;
adding sodium carbonate into the clear liquid 1 obtained in the step 5, heating to 45 ℃, stirring, standing for 10-30min, and filtering to obtain lithium carbonate precipitate, wherein the lowest addition amount of the sodium carbonate ensures that the solution is crystallized;
adjusting the pH of the clear solution 2 to form Al (OH)3Precipitating, filtering and heating to obtain alumina;
adding sodium carbonate into the clear liquid 3 obtained in the step 6, heating to 45 ℃, stirring, standing for 10-30min, and filtering to obtain lithium carbonate precipitate; the minimum amount of sodium carbonate added is such that crystallization of the solution occurs; then electrolytic recovery of metal cobalt and chemical precipitation recovery of metal nickel and manganese are carried out in sequence.
2. The method for harmlessly recycling and treating the electrolyte of the waste lithium battery as claimed in claim 1, wherein the method comprises the following steps: and 2, adopting multi-stage crushing, specifically, carrying out primary coarse crushing to ensure that the physical particle size of the waste lithium battery is 60-100mm, and then carrying out secondary fine crushing to ensure that the particle size is 10-20 mm.
3. The method for harmlessly recycling and treating the electrolyte of the waste lithium battery as claimed in claim 1, wherein the method comprises the following steps: the technological parameters for recovering the metallic cobalt by electrolysis are as follows: placing the Pd-Zn composite anode and the stainless steel cathode in an electrolytic cell, adjusting the pH to 3.2-3.8, the temperature to 25-35 ℃, and the cathode current density to 80-200 mA/cm2The electroplating time is 10-30 minutes, and the distance between the Pd-Zn composite anode and the stainless steel cathode is 5-10 cm.
4. The method for harmlessly recycling and treating the electrolyte of the waste lithium battery as claimed in claim 1, wherein the method comprises the following steps: the chemical precipitation method for recovering metal nickel and manganese comprises adding 1.5-3.5g/L NaOH solution into electrolyzed solution, adjusting pH to 7.2-7.5, filtering Ni (OH)2Precipitating, adding NaOH solution to adjust pH to 8.5-13, filtering Mn (OH)2And (4) precipitating.
5. The method for harmlessly recycling and treating the electrolyte of the waste lithium battery as claimed in claim 1, wherein the method comprises the following steps: and (4) carrying out evaporation concentration operation on the clear liquids 1 and 2 in the step 6.
6. The method for harmlessly recycling and treating the electrolyte of the waste lithium battery as claimed in claim 1, wherein the method comprises the following steps: further comprising the step 8: and (3) carrying out an electrolysis process on the solution in the step (7) to remove residual metal ions, wherein the specific technological parameters of electrolysis recovery are as follows: the Pd-Zn composite anode and the stainless steel cathode are placed in an electrolytic bath at the temperature of 25-35 ℃, and the current density of the cathode is 150-200 mA/cm2The electroplating time is 5-10 minutes; the cathode current density is 250-300 mA/cm2The electroplating time is 5-10 minutes; the cathode current density is 350-400 mA/cm2The electroplating time is 5-10 minutes; the distance between the Pd-Zn composite anode and the stainless steel cathode is 510 cm.
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