CN111416168A - Method for recycling waste power lithium battery electrolyte - Google Patents

Method for recycling waste power lithium battery electrolyte Download PDF

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Publication number
CN111416168A
CN111416168A CN202010165898.3A CN202010165898A CN111416168A CN 111416168 A CN111416168 A CN 111416168A CN 202010165898 A CN202010165898 A CN 202010165898A CN 111416168 A CN111416168 A CN 111416168A
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China
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electrolyte
waste power
power lithium
gas
lithium battery
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CN202010165898.3A
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Inventor
戴学瑜
周向阳
甘红祥
唐晶晶
陈欢欢
杨娟
严浩
王恒辉
马亚赟
刘晓剑
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Central South University
CINF Engineering Corp Ltd
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Central South University
CINF Engineering Corp Ltd
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Priority to CN202010165898.3A priority Critical patent/CN111416168A/en
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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
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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

Abstract

The invention discloses a method for recycling waste power lithium battery electrolyte, which comprises the following steps: 1) under an inert atmosphere, mixing waste power lithium batteries and dry ice, and adding the mixture into a fixed reaction kettle with a crushing device inside to obtain a mixture for later use; 2) crushing the mixture by a crushing device, adjusting the temperature of a fixed reaction kettle to be 40-60 ℃ and the pressure to be 10-40MPa, collecting to obtain mixed liquid, filtering to obtain filtrate, and transferring the filtrate to an electrolyte collection kettle; 3) adjusting the temperature of the electrolyte collection kettle to 20-30 ℃ and the pressure to 0.1-0.5MPa, so that carbon dioxide in the filtrate is volatilized into gas, and the residual liquid is the regenerated electrolyte. According to the invention, the waste power lithium batteries are mixed and disassembled by dry ice and the waste power lithium batteries in an inert atmosphere without discharge treatment, so that a large amount of heat generated in the process of disassembling the waste batteries is absorbed, the electrolyte is prevented from being decomposed in the air to generate toxic gas when meeting water, and the recovered electrolyte can be reused.

Description

Method for recycling waste power lithium battery electrolyte
Technical Field
The invention belongs to the technical field of resource recycling, and particularly relates to a method for recycling waste power lithium battery electrolyte.
Background
In recent years, with the increasing consumption of fossil fuels and the increasing awareness of environmental protection, chemical power sources have been widely used as alternative energy sources, especially in the field of electric vehicles. According to the forecast of the research center of automobile technology in China, the accumulated scrappage of the power battery of only hybrid power and pure electric (including plug-in type) passenger vehicles in China can reach 12-17 ten thousand tons by estimating according to 30 more than ten thousand new energy automobile sales in 2015 and about 500 ten thousand new energy automobile reserves in 2020 to reach 2020.
The main components of the lithium ion battery comprise a shell, a positive electrode material, a negative electrode material, a current collector, a diaphragm and electrolyte, and many of the components are valuable components which are worthy of recovery. Wherein the proportion of the anode material and the diaphragm in the cost is the largest, and respectively reaches 33 percent and 30 percent of the total costIn contrast, the negative electrode material accounts for a relatively small proportion of 10% and the electrolyte accounts for 12%, but because the production capacity of the electrolyte in China is insufficient and the production technology of high-purity lithium salt is monopolized by Japan enterprises, the profit of the electrolyte is high and can reach 40%, and the electrolyte is one of the components with relatively high profitability in the material cost of all lithium ion batteries6Has strong corrosiveness, can be decomposed to generate corrosive HF when meeting water, and can generate P during combustion2O5. Organic solvents such as ethylene carbonate, methyl ethyl carbonate and the like in the electrolyte are difficult to degrade in nature, and toxic and harmful substances such as formic acid, methanol, dimethoxyethane and the like which cause serious pollution to water sources, atmosphere and soil can be generated in the self hydrolysis process.
Although the recovery technology of waste lithium ion batteries is continuously perfected and standardized battery recovery enterprises are gradually formed, most of the waste lithium ion batteries mainly recover battery materials and neglect the treatment and recovery work of electrolyte. The reason is that the recovery technology of the electrolyte is difficult and the recovery cost is high, and in view of the above situation, the applicant of the present application thinks that it is urgent to develop a simple, effective, low-cost and perfect-process recovery method of the electrolyte of the lithium ion battery. Therefore, it is important to recover the electrolyte from the waste lithium battery safely and effectively from the viewpoints of recycling economy and sustainable development, as well as production safety and environmental protection.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for recycling waste power lithium battery electrolyte, the waste power lithium battery does not need to be subjected to discharge treatment, and dry ice and the waste power lithium battery are mixed and disassembled under the inert gas protective atmosphere, so that a large amount of heat generated in the disassembling process of the waste power lithium battery is absorbed, the electrolyte is prevented from being decomposed in the presence of water in the air to generate toxic gas, the whole process flow is simple, the large-scale production is easy, the recycled electrolyte can be reused, and the recycling and high-value utilization of wastes are realized.
In order to achieve the above purpose, the invention provides the following technical scheme:
a method for recycling waste power lithium battery electrolyte comprises the following steps:
first, mixing the materials
Under the protection of inert gas, mixing the waste power lithium battery and dry ice, and adding the mixture into a fixed reaction kettle with a crushing device inside to obtain a mixture for later use;
second, mix and crush
Crushing the mixture by a crushing device, adjusting the temperature of a fixed reaction kettle to be 40-60 ℃ and the pressure to be 10-40MPa, collecting to obtain mixed liquid, and transferring filtrate obtained by filtering to an electrolyte collection kettle;
third step, gas-liquid separation
Adjusting the temperature of the electrolyte collection kettle to 20-30 ℃ and the pressure to 0.1-0.5MPa, so that carbon dioxide in the filtrate is volatilized into gas, and the residual liquid is the regenerated electrolyte.
The invention relates to a method for recycling electrolyte of waste power lithium batteries.
According to the method for recycling the electrolyte of the waste power lithium battery, in the first step, the waste power lithium battery does not need to be subjected to discharge pretreatment.
The invention relates to a method for recycling waste power lithium battery electrolyte.
The invention relates to a method for recycling electrolyte of waste power lithium batteries, which comprises the following steps of in the first step, the mass ratio of the waste power lithium batteries to dry ice is 1: 1 to 10.
The invention relates to a method for recycling waste power lithium battery electrolyte.
Compared with the prior art, the invention has the beneficial effects that:
the waste power lithium batteries do not need to be subjected to discharge treatment, and are disassembled by mixing dry ice and the waste power lithium batteries under the inert gas protective atmosphere, so that a large amount of heat generated in the disassembling process of the waste batteries is absorbed, and the electrolyte is prevented from being decomposed in the air when encountering water to generate toxic gas; CO relative to other fluids2Has the characteristics of abundant reserves, easy acquisition, low price, stable property, no toxicity, nonflammability and the like, is particularly suitable for extracting volatile and thermosensitive substances, and can effectively prevent thermosensitive lithium salt (L iPF) particularly in the extraction of lithium ion battery electrolyte6) The functional components of the electrolyte are retained to the maximum extent and the volatile organic solvent is prevented from escaping; the whole process flow is simple, the large-scale production is easy, the recycled electrolyte can be reused, and the resource and high-value utilization of wastes is realized.
Drawings
FIG. 1 is a schematic structural diagram of a specific process unit for recycling electrolyte of waste power lithium batteries according to the present invention;
wherein: 11. inert gas source, 12, air inlet valve, 13, air inlet machine, 2, fixed reaction kettle, 3, negative pressure suction filter, 4, electrolyte collection kettle, 51, air outlet valve, 52, air extractor, 61, feed plate, 62, feed hopper, 7, double-roller shearing machine, 81, 1#Automatic shutter, 82, 2#Automatic baffle, 9, waste power lithium battery, 10 and dry ice.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific examples, but the present invention is not limited to the following examples.
As shown in fig. 1, the specific process device for recycling waste power lithium battery electrolyte of the present invention comprises an air inlet system, a fixed reaction kettle 2, a filtering device, an electrolyte collection kettle 4 and an air outlet system, which are connected in sequence.
The air inlet system comprises an inert gas source 11, an air inlet valve 12 and an air inlet machine 13, wherein the inert gas provided by the inert gas source 11 enters the fixed reaction kettle through the air inlet valve 12 and the air inlet machine 13 and is used for providing inert atmosphere and adjusting the pressure in the fixed reaction kettle.
The fixed reaction kettle 2 is a fully-sealed device, the inner wall of the fixed reaction kettle is coated with a fluorine-resistant material to prevent electrolyte corrosion, an inclined feed hopper 62 is arranged at the top in the fixed reaction kettle, the inclination angle is 45 degrees, a feed plate 61 is detachably arranged above the feed hopper 62, and when a mixture of waste power lithium batteries 9 (such as at least one of lithium cobaltate, lithium manganate, lithium nickelate, lithium nickel manganese nickelate, lithium nickel cobalt manganese oxide and lithium iron phosphate batteries, which do not need to undergo discharge pretreatment) and dry ice 10 is fed, the feed plate 61 is opened; after the mixture is fed, the feeding plate 61 is closed to keep the fixed reaction kettle 2 in a sealed environment. A double-roller shearing machine 7 is vertically connected below the feed hopper 62 and is used for crushing the mixture.
The mixture enters a double-roller shearing machine 7 through a feed hopper 62, the temperature in the fixed reaction kettle 2 is adjusted to be 40-60 ℃ after crushing, the pressure is 10-40MPa, and the mixture is collected at the bottom of the fixed reaction kettle 2 after 30-90min to obtain a mixed liquid.
The filter device is a negative pressure suction filter 3 provided with a filter membrane, the aperture of the filter membrane is 0.3-1.5 mu m, and a lifting device 1 is arranged between the fixed reaction kettle 2 and the negative pressure suction filter 3# Automatic baffle 81 for fixing mixed liquid collected at the bottom of reaction kettle 2 to pass through 1#After being adjusted by the automatic baffle 81, the mixture is filtered by the negative pressure suction filter 3.
Electrolyte collection kettle 4 is a full-sealing device, the inner wall is coated with fluorine-resistant materials to prevent electrolyte corrosion, and a lifting 2 is arranged between negative pressure suction filter 3 and electrolyte collection kettle 4#An automatic baffle 82, the mixed liquid is filtered and passes through the filter 2#The automatic baffle 82 is adjusted and transferred into the electrolyte collection kettle 4, the temperature in the electrolyte collection kettle 4 is adjusted to be 20-30 ℃, and the pressure is adjusted to be 0.1-0.5MPa, so that the carbon dioxide is recovered to be in a gas state, the gas-liquid separation of the electrolyte and the carbon dioxide is realized, and the residual liquid is regenerated electrolyte, dried, sealed and stored.
The gas outlet system comprises a gas outlet valve 51 and a gas extractor 52, the outlet of the gas extractor 52 is connected to the fixed reaction kettle 2 in a return mode and is used for controlling the gas outlet amount and the pressure in the electrolyte collection kettle 4, and carbon dioxide and inert gas separated in the electrolyte collection kettle 4 can be returned to the fixed reaction kettle 2 for continuous use.
Fixed reation kettle 2 and 4 lateral walls of electrolyte collection cauldron all are equipped with manometer and thermometer to be connected with warm-pressing control system, realize automated control.
Example 1
① mixing, opening the feeding plate, and discharging the waste power L iCoO without pre-treatment2Mixing the batteries and the dry ice in a mass ratio of 1:2, feeding the mixture through a feed hopper, closing a feeding plate after the feeding is finished, and simultaneously lifting 1#Automatic baffle and 2#An automatic baffle plate opens an air outlet valve and an air pump, and the fixed reaction kettle and the electrolyte collection kettle are in a fully sealed state at the moment; the inert gas source is argon, the gas inlet valve and the gas inlet machine are opened, the gas inlet machine, the gas pump, the gas inlet valve and the gas outlet valve are closed after the inert gas source is introduced for a period of time, and the inert gas source 1#Automatic baffle and 2#An automatic baffle plate, wherein the fixed reaction kettle is filled with argon gas;
② mixing and crushing, starting the double-roller shearing machine to crush, adjusting the temperature of the fixed reaction kettle to 40 ℃ and the pressure to 30MPa after crushing, collecting the obtained mixed liquid after 90min, and slowly opening 1#Automatic baffle and 2#Automatic baffle, the aperture of the filter membrane in the negative pressure suction filter is 0.45 μm, the mixed liquid is filtered and transferred to the electrolyte collection kettle by pressure difference, and the 1 is closed after the filtration is finished#Automatic baffle and 2#An automatic baffle plate, wherein the electrolyte and the carbon dioxide are mixed together;
③ gas-liquid separation, namely, slowly opening the gas outlet valve and the air extractor, adjusting the temperature of the electrolyte collection kettle to 20 ℃ and the pressure to 0.1MPa, so that the carbon dioxide is recovered to be in a gas state, realizing the gas-liquid separation of the regenerated electrolyte and the carbon dioxide, and separating CO after the separation2The gas and Ar gas can be returned to the fixed reaction kettle for continuous use, and the obtained regenerated electrolyte is dried, sealed and stored.
Example 2
① mixing, opening the feeding plate, and discharging the waste power L iMnO without pre-treatment2Mixing the batteries and the dry ice in a mass ratio of 1:3, feeding the mixture through a feed hopper, closing a feeding plate after the feeding is finished, and simultaneously lifting 1#Automatic gearBoards and 2#An automatic baffle plate opens an air outlet valve and an air pump, and the fixed reaction kettle and the electrolyte collection kettle are in a fully sealed state at the moment; the inert gas source is argon, the gas inlet valve and the gas inlet machine are opened, the gas inlet machine, the gas pump, the gas inlet valve and the gas outlet valve are closed after the inert gas source is introduced for a period of time, and the inert gas source 1#Automatic baffle and 2#An automatic baffle plate, wherein the fixed reaction kettle is filled with nitrogen;
② mixing and crushing, starting the double-roller shearing equipment to crush, adjusting the temperature of the fixed reaction kettle to 50 ℃ and the pressure to 40MPa after crushing, collecting the obtained mixed liquid after 70min, and slowly opening 1#Automatic baffle and 2#Automatic baffle, the aperture of the filter membrane in the negative pressure suction filter is 0.45 μm, the mixed liquid is filtered and transferred to the electrolyte collection kettle by pressure difference, and the 1 is closed after the filtration is finished#Automatic baffle and 2#An automatic baffle plate, wherein the electrolyte and the carbon dioxide are mixed together;
③ gas-liquid separation, namely, slowly opening the gas outlet valve and the air extractor, adjusting the temperature of the electrolyte collection kettle to 30 ℃ and the pressure to 0.2MPa, so that the carbon dioxide is recovered to be in a gas state, realizing the gas-liquid separation of the regenerated electrolyte and the carbon dioxide, and separating CO2Gas and N2The gas can be returned to the fixed reaction kettle for continuous use, and the obtained regenerated electrolyte is dried, sealed and stored.
Example 3
① mixing, opening the feeding plate, and discharging the waste power L iNiO without pre-treatment2Mixing the batteries and the dry ice in a mass ratio of 1:6, feeding the mixture through a feed hopper, closing a feeding plate after the feeding is finished, and simultaneously lifting 1#Automatic baffle and 2#An automatic baffle plate opens an air outlet valve and an air pump, and the fixed reaction kettle and the electrolyte collection kettle are in a fully sealed state at the moment; the inert gas source is argon, the gas inlet valve and the gas inlet machine are opened, the gas inlet machine, the gas pump, the gas inlet valve and the gas outlet valve are closed after the inert gas source is introduced for a period of time, and the inert gas source 1#Automatic baffle and 2#An automatic baffle plate, wherein the fixed reaction kettle is filled with nitrogen;
② mixing and crushing, starting the double-roller shearing equipment to crush, adjusting the temperature of the fixed reaction kettle to 45 ℃ after crushing, and adjusting the pressureIs 35MPa, and the mixed liquid is collected after 80min and is slowly opened by 1#Automatic baffle and 2#Automatic baffle, the aperture of the filter membrane in the negative pressure suction filter is 0.45 μm, the mixed liquid is filtered and transferred to the electrolyte collection kettle by pressure difference, and the 1 is closed after the filtration is finished#Automatic baffle and 2#An automatic baffle plate, wherein the electrolyte and the carbon dioxide are mixed together;
③ gas-liquid separation, namely, slowly opening the gas outlet valve and the air extractor, adjusting the temperature of the electrolyte collection kettle to 25 ℃ and the pressure to 0.1MPa, so that the carbon dioxide is recovered to be in a gas state, realizing the gas-liquid separation of the regenerated electrolyte and the carbon dioxide, and separating CO after the separation2Gas and N2Gas can return to 1#The regenerated electrolyte is continuously used in the closed reaction kettle, and the obtained regenerated electrolyte is dried, sealed and stored.
Example 4
① mixing, opening the feeding plate, and discharging the waste power L iNi without pre-treatmentxCoyMnzO2The dry ice of the battery is mixed according to the mass ratio of 1:8 and then is fed through a feed hopper, after the feeding is finished, a feed plate is closed, and simultaneously, the dry ice of the battery is lifted by 1#Automatic baffle and 2#An automatic baffle plate opens an air outlet valve and an air pump, and the fixed reaction kettle and the electrolyte collection kettle are in a fully sealed state at the moment; the inert gas source is argon, the gas inlet valve and the gas inlet machine are opened, the gas inlet machine, the gas pump, the gas inlet valve and the gas outlet valve are closed after the inert gas source is introduced for a period of time, and the inert gas source 1#Automatic baffle and 2#An automatic baffle plate, wherein the fixed reaction kettle is filled with argon gas;
② mixing and crushing, starting the double-roller shearing equipment to crush, adjusting the temperature of the fixed reaction kettle to 50 ℃ and the pressure to 30MPa after crushing, collecting the obtained mixed liquid after 60min, and slowly opening 1#Automatic baffle and 2#Automatic baffle, the aperture of the filter membrane in the negative pressure suction filter is 0.45 μm, the mixed liquid is filtered and transferred to the electrolyte collection kettle by pressure difference, and the 1 is closed after the filtration is finished#Automatic baffle and 2#An automatic baffle plate, wherein the electrolyte and the carbon dioxide are mixed together;
③ gas-liquid separation by opening gas outlet valve and air extractor slowly and collecting electrolyteThe temperature of the kettle is 30 ℃, the pressure is 0.3MPa, so that the carbon dioxide is recovered to be in a gas state, the gas-liquid separation of the regenerated electrolyte and the carbon dioxide is realized, and the separated CO2The gas and Ar gas can be returned to the fixed reaction kettle for continuous use, and the obtained regenerated electrolyte is dried, sealed and stored.
Example 5
① mixing, opening the feeding plate, and discharging the waste power L iFePO without pre-treatment4Mixing the batteries and the dry ice in a mass ratio of 1:7, feeding the mixture through a feed hopper, closing a feeding plate after the feeding is finished, and simultaneously lifting 1#Automatic baffle and 2#An automatic baffle plate opens an air outlet valve and an air pump, and the fixed reaction kettle and the electrolyte collection kettle are in a fully sealed state at the moment; the inert gas source is argon, the gas inlet valve and the gas inlet machine are opened, the gas inlet machine, the gas pump, the gas inlet valve and the gas outlet valve are closed after the inert gas source is introduced for a period of time, and the inert gas source 1#Automatic baffle and 2#An automatic baffle plate, wherein the fixed reaction kettle is filled with nitrogen;
② mixing and crushing, starting the double-roller shearing equipment to crush, adjusting the temperature of the fixed reaction kettle to 60 ℃ and the pressure to 35MPa after crushing, collecting the obtained mixed liquid after 80min, and slowly opening 1#Automatic baffle and 2#Automatic baffle, the aperture of the filter membrane in the negative pressure suction filter is 0.45 μm, the mixed liquid is filtered and transferred to the electrolyte collection kettle by pressure difference, and the 1 is closed after the filtration is finished#Automatic baffle and 2#An automatic baffle plate, wherein the electrolyte and the carbon dioxide are mixed together;
③ gas-liquid separation, namely, slowly opening the gas outlet valve and the air extractor, adjusting the temperature of the electrolyte collection kettle to 25 ℃ and the pressure to 0.2MPa, so that the carbon dioxide is recovered to be in a gas state, realizing the gas-liquid separation of the regenerated electrolyte and the carbon dioxide, and separating CO after the separation2Gas and N2Gas can return to 1#The regenerated electrolyte is continuously used in the closed reaction kettle, and the obtained regenerated electrolyte is dried, sealed and stored.
Comparative example 1
The other conditions and steps are the same as those of the example 1, except that the waste power L iCoO is used in the mixing step2The mass ratio of the battery to the dry ice is 1:0.5,the dry ice was crushed in the amount of 1#The closed reaction kettle has serious heating phenomenon.
Comparative example 2
The other conditions and procedures were identical to those of example 1, except that: in the step of mixing and crushing, the temperature of the fixed reaction kettle is adjusted to be 25 ℃, the pressure is 8MPa, the mixed solution is transferred to the electrolyte collection kettle and then subjected to gas-liquid separation, and less electrolyte is obtained.
Comparative example 3
The other conditions and procedures were identical to those of example 1, except that: in the step of mixing and crushing, the temperature of the fixed reaction kettle is adjusted to be 30 ℃ and the pressure is 5MPa, the mixed solution is transferred to the electrolyte collection kettle and then subjected to gas-liquid separation, and less electrolyte is obtained.
Comparative example 4
The other conditions and procedures were identical to those of example 4, except that: and (3) after the mixed solution is transferred to an electrolyte collection kettle, carrying out gas-liquid separation, adjusting the temperature to be 30 ℃, and the pressure to be 5MPa, and finding that the gas-liquid separation is not thorough and the obtained electrolyte is less.
Comparative example 5
The other conditions and procedures were identical to those of example 4, except that: and (3) after the mixed solution is transferred to an electrolyte collection kettle, carrying out gas-liquid separation, adjusting the temperature to be 50 ℃ and the pressure to be 3MPa, and finding that the gas-liquid separation is incomplete and the obtained electrolyte is less.

Claims (6)

1. A method for recycling electrolyte of waste power lithium batteries is characterized by comprising the following steps:
first, mixing the materials
Under the protection of inert gas, mixing the waste power lithium battery and dry ice, and adding the mixture into a fixed reaction kettle with a crushing device inside to obtain a mixture for later use;
second, mix and crush
Crushing the mixture by a crushing device, adjusting the temperature of a fixed reaction kettle to be 40-60 ℃ and the pressure to be 10-40MPa, collecting to obtain mixed liquid, and transferring filtrate obtained by filtering to an electrolyte collection kettle;
third step, gas-liquid separation
Adjusting the temperature of the electrolyte collection kettle to 20-30 ℃ and the pressure to 0.1-0.5MPa, so that carbon dioxide in the filtrate is volatilized into gas, and the residual liquid is the regenerated electrolyte.
2. The method for recycling the electrolyte of the waste power lithium battery as claimed in claim 1, wherein the method comprises the following steps: in the first step, the waste power lithium battery is selected from at least one of lithium cobaltate, lithium manganate, lithium nickelate, lithium nickel manganate, lithium nickel cobalt manganate and lithium iron phosphate.
3. The method for recycling the electrolyte of the waste power lithium battery as claimed in claim 1, wherein the method comprises the following steps: in the first step, the waste power lithium battery does not need to be subjected to discharge pretreatment.
4. The method for recycling the electrolyte of the waste power lithium battery as claimed in claim 1, wherein the method comprises the following steps: in the first step, the inert gas is at least one of argon and nitrogen.
5. The method for recycling the electrolyte of the waste power lithium battery as claimed in claim 1, wherein the method comprises the following steps: in the first step, the mass ratio of the waste power lithium batteries to the dry ice is 1: 1 to 10.
6. The method for recycling the electrolyte of the waste power lithium battery as claimed in claim 1, wherein the method comprises the following steps: in the first step, the crushing device is a double-roller shearing machine.
CN202010165898.3A 2020-03-11 2020-03-11 Method for recycling waste power lithium battery electrolyte Pending CN111416168A (en)

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CN110635191A (en) * 2019-09-12 2019-12-31 金川集团股份有限公司 Method for cleanly recovering all components of waste power lithium battery

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114024051A (en) * 2021-10-28 2022-02-08 中国科学院广州能源研究所 Method for treating electrolyte of waste lithium battery through pyrolysis

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