CN108288738B - Method for recovering lithium ion battery electrolyte by using supercritical carbon dioxide fluid - Google Patents
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 67
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 32
- 239000012530 fluid Substances 0.000 title claims abstract description 29
- 238000000605 extraction Methods 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 22
- 239000002699 waste material Substances 0.000 claims abstract description 13
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000007774 positive electrode material Substances 0.000 claims abstract description 6
- 238000000194 supercritical-fluid extraction Methods 0.000 claims abstract description 6
- 239000007773 negative electrode material Substances 0.000 claims abstract description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- 230000001502 supplementing effect Effects 0.000 claims description 6
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 5
- 150000005678 chain carbonates Chemical class 0.000 claims description 5
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000006259 organic additive Substances 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims 1
- 229910013684 LiClO 4 Inorganic materials 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000012805 post-processing Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 9
- 238000004064 recycling Methods 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- -1 cyclic carbonate esters Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 230000001698 pyrogenic effect Effects 0.000 description 3
- 238000003815 supercritical carbon dioxide extraction Methods 0.000 description 3
- 238000007158 vacuum pyrolysis Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
Abstract
本发明提供了一种锂离子电池电解液的回收方法。将废旧锂离子电池充分放电后进行拆解，将电解液、带有正负极材料的集流体以及隔膜全部转移入超临界萃取装置中，选取乙基丁基甲酮为夹带剂，调整超临界二氧化碳流体的温度、压力、萃取时间和流量，然后进行有机溶剂的萃取，从而实现有机溶剂与电解质盐的分离。本发明的整个工艺流程简单易操作，萃取分离速度快，且无需繁琐的后期处理。The invention provides a method for recovering electrolyte of lithium ion battery. The waste lithium-ion battery is fully discharged and disassembled, and the electrolyte, current collector with positive and negative electrode materials, and diaphragm are all transferred into the supercritical extraction device, and ethyl butyl ketone is selected as the entrainer to adjust the supercritical carbon dioxide fluid. The temperature, pressure, extraction time and flow rate are adjusted, and then the organic solvent is extracted, so as to realize the separation of the organic solvent and the electrolyte salt. The whole technological process of the invention is simple and easy to operate, the extraction and separation speed is fast, and complicated post-processing is not required.
Description
Technical Field
The invention belongs to the technical field of recycling of lithium ion battery electrolyte, and particularly relates to a method for recycling lithium ion battery electrolyte by using supercritical carbon dioxide fluid.
Background
Sony corporation released the first commercial lithium ion battery in 1991, and subsequently, lithium ion batteries revolutionized the appearance of consumer electronics and rapidly developed in increasingly diverse forms in human social and economic lives. With the development of electric automobiles, power lithium ion batteries develop very rapidly, and a large number of lithium ion batteries face the problem of scrapping treatment after being used for 2 to 3 years. By the estimated 2020, the accumulated scrappage of the power batteries of electric vehicles in China can reach 12-17 ten thousand tons, and the problems of energy exhaustion and environmental pollution are seriously brought to people. In this case, people are forced to find a suitable recycling route. Although large-scale recycling enterprises in China are gradually appearing, the electrolyte is more complicated to treat, and the added value is low, so the enterprises mainly concentrate on recycling electrode materials and do not pay attention to recycling the electrolyte.
In the process of collecting, stacking and recovering the waste lithium ion battery, part of electrolyte leaks and volatilizes, and the surrounding atmosphere, soil and water can be polluted. If the electrolyte lithium salt enters the environment, chemical reactions such as hydrolysis, decomposition and combustion can occur to generate fluorine-containing, arsenic-containing and phosphorus-containing compounds, so that fluorine pollution, arsenic pollution and phosphorus pollution are caused; and for example, organic solvents undergo chemical reactions such as hydrolysis, combustion and decomposition to generate micromolecular organic matters such as formaldehyde, methanol, acetaldehyde, ethanol, formic acid and the like. If the materials are not treated or are not treated properly, the materials can cause great pollution to the environment and bring great threat to the health of human beings.
The recovery technology of lithium ion batteries can be divided into a pyrogenic process, a wet process, a biological process and the like. Currently, most of the used are still traditional pyrogenic or wet processing techniques. The electrolyte organic solvent is volatilized or burnt to decompose into water vapor and carbon dioxide to be discharged during pyrogenic process, and LiPF6Exposed to air and heated, the PF can be quickly decomposed5And finally forming fluorine-containing flue gas and smoke dust, and discharging the fluorine-containing flue gas and the smoke dust outwards. The wet process is a process capable of dissolving an electrolyte lithium salt in a solution when dissolving a current collector aluminum foil using an alkaline solution or dissolving a positive electrode active material using an acidic solution. With electrolyte lithium salt LiPF6Decomposition into, for example, HF and PF5Soluble fluoride is easily generated in the alkali dissolution process, so that fluorine pollution of water is caused, and the water directly or indirectly harms human bodies. Therefore, it is necessary to establish a recovery technique of the electrolyte, and the vacuum pyrolysis method and the extraction method are effective methods for treating the electrolyte.
Sun et al [ Sun L., Qiu K. vacuum pyrolysis and hydraulic process for the recovery of usable metals from lithium batteries. J Hazard Mater, 2011,194,378-384] adopt vacuum pyrolysis technology to separate organic binders and electrolytes in waste lithium ion batteries, and avoid environmental pollution and resource waste caused by the emission of fluorides. Steven (Steven E S.System and method for removing an electrolyte from an energy storage and/or conversion using a supercritical fluid. US:200300186110A1,2003-10-02.) utilizes the excellent solubility of non-polar materials in liquid carbon dioxide and supercritical carbon dioxide to separate the electrolyte from the spent lithium ion battery. However, this method is not very efficient in recovering the organic solvent in the electrolyte.
Disclosure of Invention
In order to solve the problems of environmental pollution and low organic solvent recovery rate in the recovery and reuse of lithium ion battery electrolyte, the invention provides a carbon dioxide supercritical extraction method of waste lithium ion battery electrolyte, which realizes the separation of organic solvent and electrolyte lithium salt and improves the recovery efficiency of the electrolyte.
In order to furthest improve the application range of the lithium ion battery, the organic solvent in the lithium ion battery at least comprises two cyclic carbonate esters with larger dielectric constants and smaller chain carbonate esters, the solubility of the cyclic carbonate esters in the carbon dioxide fluid is lower due to the weak polarity of the supercritical carbon dioxide fluid, and in order to improve the solubility of the solvents in the carbon dioxide fluid, the invention finds that the extraction efficiency of the carbon dioxide fluid on the organic solvent in the electrolyte can be effectively improved by taking the ethyl butyl ketone as an entrainer through continuous trial.
The method for recycling the battery electrolyte through the supercritical carbon dioxide extraction is realized by the following steps:
(1) fully discharging the waste lithium ion battery, then disassembling, and removing the shell, the positive and negative terminals, the sealing ring and the cover plate;
(2) transferring the disassembled electrolyte, the current collectors with the positive and negative electrode materials and the diaphragm into a carbon dioxide supercritical extraction device with ethyl butyl ketone as an entrainer;
(3) adjusting the temperature, pressure, extraction time and flow of the supercritical carbon dioxide fluid to extract the organic solvent, so that the solvent in the electrolyte is effectively separated from the electrolyte;
(4) rectifying the obtained solvent, removing entrainer, analyzing components, supplementing electrolyte salt, organic solvent and additive according to the analysis result, and adjusting the mixture ratio to prepare the electrolyte.
Wherein, the amount of the entrainer ethyl butyl ketone in the step (2) is 5-10%;
and (3) adjusting the temperature of the supercritical carbon dioxide fluid to be 30-60 ℃, the pressure to be 8-20MPa, and the extraction time and the flow of the supercritical carbon dioxide fluid to be in inverse proportion.
The electrolyte salt supplemented in the electrolyte in the step (4) is LiPF6、LiBF4、LiClO4Or LiAsF6Any one or a combination of several of them.
And (4) supplementing an organic solvent into the electrolyte in the step (4) into cyclic carbonate and chain carbonate.
The cyclic carbonate is one or two of ethylene carbonate EC or propylene carbonate PC.
The chain carbonate is one or a combination of more of dimethyl carbonate DMC, diethyl carbonate DEC, methyl ethyl carbonate EMC, methyl propyl carbonate MPC or ethyl propyl carbonate EPC.
The additives are mainly used to improve SEI film properties, improve conductivity, overcharge protection, improve low-temperature properties of an electrolyte, thermal stability, safety, cycle stability, and the like. The supplementary additive is one or a combination of more of vinylene carbonate VC, biphenyl BP and dimethyl sulfoxide DMSO.
The invention has the advantages that:
1. avoids the pollution of the recovered components and the environment caused by ethers and acids generated by vacuum high-temperature pyrolysis.
2. The carbon dioxide fluid is gas when being recovered to the normal state, and can be naturally separated from the organic solvent, and other multi-component solvents can be simply separated through rectification, or the solvents are directly prepared into new electrolyte.
3. The method has the advantages of mild operating temperature and pressure conditions, easy control of operation, integration of extraction, separation and recovery, no need of complex post-treatment, higher resource utilization rate and contribution to large-scale application.
4. The dielectric constant of the selected ethyl butyl ketone is 12.9F/m (22 ℃), the boiling point is 146-.
Drawings
FIG. 1 shows the recovery of electrolyte by the method of the present invention.
Detailed Description
The following examples further illustrate the method for recycling the electrolyte of the waste lithium ion battery by supercritical carbon dioxide extraction.
Examples
Firstly, the waste lithium ion battery is fully discharged and then disassembled, and the shell, the positive and negative terminals, the sealing ring and the cover plate are removed. Then transferring the electrolyte, the current collectors with the positive and negative electrode materials and the diaphragm into a supercritical extraction device using ethyl butyl ketone as an entrainer, adjusting the temperature, the pressure, the extraction time and the flow of supercritical carbon dioxide fluid, then extracting an organic solvent, rectifying the obtained solvent, removing the entrainer, performing component analysis, supplementing electrolyte salt, the organic solvent and an additive according to the analysis result, and adjusting the mixture ratio to prepare the electrolyte.
The method for recycling the waste lithium ion battery electrolyte through supercritical carbon dioxide extraction comprises the steps of adjusting the temperature range of supercritical carbon dioxide fluid to be 30-60 ℃, adjusting the pressure range to be 8-20MPa, and enabling the extraction time and the flow of the supercritical fluid to be in an inverse proportion relation. The electrolyte salt in the electrolyte is LiPF6、LiBF4、LiClO4Or LiAsF6Any one or a combination of several of them. The organic solvent in the electrolyte is the combination of any two or more of cyclic carbonate (ethylene carbonate EC and propylene carbonate PC) and chain carbonate (dimethyl carbonate DMC, diethyl carbonate DEC, ethyl methyl carbonate EMC, methyl propyl carbonate MPC or ethyl propyl carbonate EPC).
The specific implementation and effects of the present invention will be described in conjunction with the following applications.
The waste lithium ion battery is discharged and then disassembled, and an aluminum shell, a positive electrode terminal, a negative electrode terminal, a sealing ring and a cover plate are removed, if the waste lithium ion battery is a power battery, the polyolefin microporous membrane can be used for absorbing the flowing electrolyte, if the waste lithium ion battery is other batteries, the mode of absorbing the electrolyte can be selected according to actual requirements, and the polyolefin microporous membrane absorbing the electrolyte, the current collectors with the positive electrode material and the negative electrode material and the diaphragm are quickly transferred to the supercritical extraction device. According to the capacity of an extraction kettle and the characteristics of extracted materials, 5-10% of entrainer ethyl butyl ketone is added into a 100mL extraction kettle, carbon dioxide is used as an extraction fluid, the temperature range is set to be 30-60 ℃, the pressure range is set to be 8-20MPa, static extraction is carried out for 5-10min, dynamic extraction is carried out for 5-20min, the flow rate is 0.5-5L/min, the extraction time is related to the flow rate of the supercritical fluid, the relation of inverse proportion is formed, and the optimum combination can be adjusted according to specific conditions and requirements.
Sampling the obtained solvent, rectifying to remove entrainer ethyl butyl ketone, carrying out quantitative analysis on each component of the obtained solvent by adopting gas chromatography, supplementing electrolyte salt, organic solvent and functional additive according to the analysis result, preparing a new electrolyte of the lithium ion battery, and reassembling the lithium ion battery for use.
When the extraction temperature is 35 ℃, the pressure is 8MPa, the static extraction is 10min, the dynamic extraction is 20min, and the flow is 3L/min, when the entrainer, namely ethyl butyl ketone is not used, the extraction rate of the carbon dioxide fluid to the electrolyte organic solvent is 62.3 percent; under the same extraction conditions, when 1mL of entrainer ethyl butyl ketone is added into a 100mL extraction kettle, the extraction rate of the electrolyte organic solvent by the carbon dioxide fluid is 92.8%. It can be seen that the electrolyte recovery rate is very high with the method of the present invention.
Claims (6)
1. A method for recovering lithium ion battery electrolyte by adopting supercritical carbon dioxide fluid is characterized by comprising the following steps: the method comprises the following steps:
(1) fully discharging the waste lithium ion battery, then disassembling, and removing the shell, the positive and negative terminals, the sealing ring and the cover plate;
(2) transferring the disassembled electrolyte, the current collectors with the positive and negative electrode materials and the diaphragm into a carbon dioxide supercritical extraction device with ethyl butyl ketone as an entrainer; the dosage of the ethyl butyl ketone is 5-10 percent;
(3) adjusting the temperature, pressure, extraction time and flow of the supercritical carbon dioxide fluid to extract the organic solvent, so that the solvent in the electrolyte is effectively separated from the electrolyte; the temperature of the supercritical carbon dioxide fluid is adjusted to be 30-60 ℃, the pressure is adjusted to be 8-20MPa, and the extraction time and the flow of the supercritical carbon dioxide fluid are in inverse proportion;
(4) rectifying the obtained solvent, removing entrainer, analyzing components, supplementing electrolyte salt, organic solvent and additive according to the analysis result, and adjusting the mixture ratio to prepare the electrolyte.
2. The method of claim 1 for recovering lithium ion battery electrolyte using supercritical carbon dioxide fluid, wherein: the electrolyte salt supplemented in the electrolyte in the step (4) is LiPF6、LiBF 4、LiClO 4Or LiAsF6Any one or a combination of several of them.
3. The method of claim 1 for recovering lithium ion battery electrolyte using supercritical carbon dioxide fluid, wherein: and (4) supplementing an organic solvent into the electrolyte in the step (4) into cyclic carbonate and chain carbonate.
4. The method of claim 3 for recovering lithium ion battery electrolyte using supercritical carbon dioxide fluid, wherein: and (4) the cyclic carbonate is one or two of ethylene carbonate EC or propylene carbonate PC.
5. The method of claim 3 for recovering lithium ion battery electrolyte using supercritical carbon dioxide fluid, wherein: and (4) the chain carbonate is any one or a combination of more of dimethyl carbonate DMC, diethyl carbonate DEC, methyl ethyl carbonate EMC, methyl propyl carbonate MPC or ethyl propyl carbonate EPC.
6. The method of claim 1 for recovering lithium ion battery electrolyte using supercritical carbon dioxide fluid, wherein: and (4) adding additives into the electrolyte in the step (4) into one or more of vinylene carbonate VC, biphenyl BP and dimethyl sulfoxide DMSO.
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