CN102496752B - Method for recycling electrolyte of waste lithium ion battery - Google Patents

Method for recycling electrolyte of waste lithium ion battery Download PDF

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Publication number
CN102496752B
CN102496752B CN2011104274312A CN201110427431A CN102496752B CN 102496752 B CN102496752 B CN 102496752B CN 2011104274312 A CN2011104274312 A CN 2011104274312A CN 201110427431 A CN201110427431 A CN 201110427431A CN 102496752 B CN102496752 B CN 102496752B
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China
Prior art keywords
lithium
battery
hexafluoro phosphate
ion battery
electrolyte
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CN2011104274312A
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Chinese (zh)
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CN102496752A (en
Inventor
周立山
刘红光
叶学海
郭西凤
刘大凡
张洪源
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中国海洋石油总公司
中海油天津化工研究设计院
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

Abstract

The invention discloses a method for recycling the electrolyte of a waste lithium ion battery. The method mainly comprises the following steps of: collecting and cleaning the lithium ion battery; after discharge, putting the lithium ion battery in a drying room or a glove box under protection of inert gas; opening the battery, carefully taking out the electrolyte and placing in a material tank; performing high-vacuum decompressed rectification and separation to obtain the organic solvent contained in the electrolyte; performing rectification and purification for recycling; putting a rough product of lithium hexafluorophate into a dissolution kettle, and adding a hydrogen fluoride solution for dissolving the recycled lithium hexafluorophate; filtering the solution and then putting into a crystallization kettle for crystallization and purification; and screening, drying, packaging and recycling to obtain the product lithium hexafluorophate. The method has simple technology, is practical, efficient, clean and environment-friendly and easy to control, and realizes close integration of economic benefits and environmental social benefits.

Description

A kind of method that reclaims waste and old lithium ionic cell electrolyte
Technical field
The invention belongs to lithium ion battery recovery technology field, be specifically related to a kind of method that from waste and old lithium ionic cell electrolyte, reclaims lithium hexafluoro phosphate and solvent.
Background technology
Lithium ion battery is since the nineteen ninety commercialization, with its voltage height, capacity is big, quality is light etc., and advantage replaces the main flow that the traditional secondary battery becomes market gradually, in electronic products such as mobile phone, digital camera, Digital Video, notebook computer, used widely.The consumption figure of world's lithium ion battery in 2000 is 500,000,000, reaches 2,800,000,000 in 2008, along with the progress in development of science and technology and epoch, and the fast development of electric automobile industry, people sharply increase the demand of lithium ion battery.Lithium ion battery belongs to easily-consumed products, estimates that will produce the waste and old lithium ion battery more than 100,000 tons following every year.Lithium ion battery mainly is made up of positive pole, negative pole, barrier film, electrolyte, contain useful components such as cobalt, manganese, aluminium, copper, lithium, phosphorus, fluorine, if the contained useful component of lithium ion battery is not reclaimed, not only cause the significant wastage of useful resources, and will cause severe contamination to environment.Therefore, the recycling lithium ion battery becomes the very urgent problem of the whole society.
Lithium ion battery is single through disassembling the shell, the diaphragm material composition that obtain, is easy to reclaim.It is more that the positive pole of relevant battery, negative material reclaim the document patent in field, and anodal recovery method mainly contains: 1. hydrometallurgy; 2. pyrometallurgy; 3. electrochemical process etc.The negative pole recovery method mainly contains: 1. high temperature method; 2. than retransmitting; 3. comminuting method; 4. infusion method etc.Patents such as CN200910017377.7, CN200910040963.3, CN201010262198.2, CN201010295586.0 have been introduced the useful component recovery method that contains in the lithium ion battery, but and the recovery of not mentioned electrolyte lithium hexafluoro phosphate.
Lithium-ion battery electrolytes mainly is the solution that various organic solvent dissolution lithium hexafluoro phosphates form.The research that recycle in relevant lithium-ion battery electrolytes field reports that seldom we know, contain lithium hexafluoro phosphate and little molecular organic compound in the lithium-ion battery electrolytes, if do not add processing with its random placement, and easy contaminated environment, even cause fire.
At present, carried out relevant research work at the recovery method of lithium ion battery.CN201010523257.7 has reported a kind of method that reclaims lithium from waste and old lithium ion battery and pole piece, and by with battery and pole piece fragmentation, high temperature is removed binding agent, adds acid, alkali reaction removal of impurities, obtains lithium compound with the villiaumite precipitation at last.CN201010605151.1 has reported the recovery method of lithium in a kind of old and useless battery, contains the lithium raffinate by adopting organic solvent to handle in the waste and old lithium ion battery wet treatment process, and lithium is reclaimed.CN201010141128.1 introduces and adopts sour molten lithium ion battery cell fragment, adds alkali precipitating metal hydroxide respectively, will contain at last to add sodium carbonate generation lithium carbonate precipitation in the lithium filtrate, thereby reclaim the lithium compound in the electrode.These methods exist following shortcoming: 1) waste raw material, energy consumption height, low, the complex process of efficient; 2) some electrokinetic cell volume is bigger, handles not with great difficulty catching fire, and is relatively more dangerous; 3) handle electrolyte simultaneously in reclaiming the electrode material process, the lithium hexafluoro phosphate that contains in the electrolyte is decomposed, and generates fluoride, phosphorus compound and lithium compound and other metal ion and mixes, and the subsequent treatment difficulty causes environmental pollution easily.Therefore, the lithium hexafluoro phosphate that contains of a kind of lithium-ion battery electrolytes of necessary exploitation and the recovery method of solvent solve this problem.
This patent is at lithium ion battery resource present situation, adopts eco-friendly method to realize that the resource of electrolyte useful component lithium hexafluoro phosphate and solvent separates recovery.Lithium hexafluoro phosphate is heat sensitive material, be easy to decompose when temperature is higher, and its character is very active, be easy to air, moisture etc. side reaction take place, so this patent adopts the lithium hexafluoro phosphate solution of high vacuum rectification technical finesse recovery.
Summary of the invention
The object of the present invention is to provide the recovery method of simple, with low cost, the effective lithium-ion battery electrolytes material of a kind of operation, to realize the lithium hexafluoro phosphate that contained in the electrolyte and the recycling of solvent.
Therefore, at above-mentioned technical problem, the invention provides a kind of method that from waste and old lithium ion battery, effectively reclaims lithium hexafluoro phosphate and solvent, reclaim technology to simplify tradition, alleviate the pollution that natural environment to external world causes.
The present invention is a kind of method that reclaims waste and old lithium ionic cell electrolyte; It is characterized in that:
May further comprise the steps:
1) the various lithium ion batteries that will collect comprise cobalt acid lithium battery, ferrous phosphate lithium battery, lithium manganate battery, ternary material battery; And the defect ware lithium ion battery of the use standard that do not meet that in lithium ion battery manufacturing process, produces; All clean clean; Before using lithium ion battery is fully discharged;
2) battery and ready batch can are put into the glove box of drying room or inert gas shielding together; Battery is opened, the careful taking-up of electrolyte wherein put into batch can; Drying room moisture is between 1%-2%; Employed inert gas comprises in the glove box: high pure nitrogen, high-purity helium, high-purity neon, high-purity argon gas, and its moisture is between 100ppm-10000ppm; For the protection of electrolyte, prevent hydrolysis and oxidation reaction;
3) high vacuum rectification under vacuum separation obtains the contained organic solvent of electrolyte then; With an organic solvent wash battery, the lithium hexafluoro phosphate solution that adopts the high vacuum rectification technical finesse to reclaim effectively prevents reducing side reaction of lithium hexafluoro phosphate; The condition of distillation operation: 0 to 20 kPa of vacuum degree, temperature adopt the operation of continuous rectification or batch fractionating method between 20 to 120 degree; The organic solvent that reclaims is one or more mixtures in ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, oxolane, the vinylene carbonate;
4) will obtain solid lithium hexafluoro phosphate material and add in the lithium hexafluoro phosphate dissolution kettle, add the lithium hexafluoro phosphate that the hydrogen fluoride solution dissolving is reclaimed; Employed hydrogen fluoride adopts hydrogen fluoride or this method commercially available, that distill after purifying to produce the mother liquor of getting in the lithium hexafluoro phosphate crystallization process in the dissolving lithium hexafluoro phosphate crude product process; When in hydrogen fluoride solution, dissolving the lithium hexafluoro phosphate crude product; Temperature does not have specific (special) requirements, between-30 ° of C to 20 ° of C;
5) carry out crystallization and purification with putting into crystallization kettle after this solution filtration; Between ° of C to 10 ° C of temperature-80; Crystallization time is between 4 hours to 48 hours; The Crystallization Separation method adopts natural filtration, pressure filtration, centrifugal filtering method;
6) screening, drying, the temperature in the drying process process is between 40 ° of C to 140 ° of C; The dry time is between 4 hours to 48 hours; Packing obtains the lithium hexafluoro phosphate product then.
Compare with prior art, the invention has the advantages that:
1. the present invention has realized the simple process to lithium-ion battery electrolytes, does not need complicated chemical process.Whole technology is simple, efficient, be easy to control and clean environment firendly.
The lithium hexafluoro phosphate of 2 technology recovery can directly use through behind the purifying.
The organic solvent of 3 technology recovery can directly use through behind the purifying.
The mentioned waste and old lithium ion battery of the present invention reclaims the method for electrolyte active ingredient, obtain electrolytic salt lithium hexafluoro phosphate and various organic solvent respectively, compound through the said method acquisition, can directly be used as lithium ion battery material, realize the recycling of electrolytic salt, organic solvent resource effectively.This method technology is simple, and the equipment less investment is with short production cycle, cost recovery is low, the organic efficiency height, and removal process can not cause secondary pollution.For reducing the battery production cost, economizing on resources, protect environment all can play a positive role.
Embodiment
Below by concrete execution mode, the method for recovery waste and old lithium ionic cell electrolyte active ingredient lithium hexafluoro phosphate of the present invention and solvent is further described in detail.
Described waste and old lithium ion battery comprises the lithium ion battery of kinds such as cobalt acid lithium, LiFePO 4, LiMn2O4, ternary material.
Described organic solvent removal process comprises intermittently or modes such as continuous rectification under vacuum, high vacuum rectification.
Described method recovered solvent comprises as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, oxolane, ethylene carbonate etc.
Embodiment
Embodiment one,
The lithium ion battery cleaning is clean, carry out complete discharge process.Battery and ready batch can are put into the glove box of high pure nitrogen protection together, battery is opened, carefully take out electrolyte and put into batch can; The rectification under vacuum separation obtains the contained organic solvent of electrolyte then, recycles.Obtain 2.9 kilograms of solid materials and shift out glove box, put into the lithium hexafluoro phosphate dissolution kettle, add 16 kilograms of lithium hexafluoro phosphates of producing the mother liquor dissolving recovery of getting in the lithium hexafluoro phosphate crystallization process; Carried out crystallization and purification with putting into crystallization kettle after this solution filtration in 24 hours at subzero 50 degree; Crush and screen, high pure nitrogen protection is 120 degree in drying machine dry 8 hours down, and packing obtains 2.4 kilograms of product lithium hexafluoro phosphates, the rate of recovery 82.7%.
Embodiment two,
The lithium ion battery cleaning is clean, carry out complete discharge process.Battery is opened at drying room, carefully taken out electrolyte and put into batch can; Decompression separation obtains the contained organic solvent of electrolyte then, recycles.Obtain 3.1 kilograms of solid materials and put into the lithium hexafluoro phosphate dissolution kettle, add the hydrogen fluoride mother liquor that obtains in 1 operation of 17 kilograms of examples, the lithium hexafluoro phosphate that dissolving is reclaimed; Carried out crystallization and purification with putting into crystallization kettle after this solution filtration in 36 hours at subzero 65 degree; Crush and screen, high pure nitrogen protection is 130 degree in drying machine dry 12 hours down, and packing obtains 2.5 kilograms of product lithium hexafluoro phosphates, the rate of recovery 80.6%.
Description of drawings
Fig. 1 is schematic flow sheet of the present invention:
1, lithium ion battery discharge cleaning; 2, open battery, take out electrolyte; 3, rectification under vacuum; 4, organic solvent; 5 rectifying; 6, purifying is recycled; 7, dissolving lithium hexafluoro phosphate; 8, crystallization, filtration; 9, mother liquor reuse; 10, crystalline mother solution; 11, pulverizing, screening, drying; 12, finished product.

Claims (1)

1. method that reclaims waste and old lithium ionic cell electrolyte; It is characterized in that:
May further comprise the steps:
1) the various lithium ion batteries that will collect comprise cobalt acid lithium battery, ferrous phosphate lithium battery, lithium manganate battery, ternary material battery; And the defect ware lithium ion battery of the use standard that do not meet that in lithium ion battery manufacturing process, produces; All clean clean; Before using lithium ion battery is fully discharged;
2) battery and ready batch can are put into the glove box of drying room or inert gas shielding together; Battery is opened, the careful taking-up of electrolyte wherein put into batch can; Drying room moisture is between 1%-2%; Employed inert gas comprises in the glove box: high pure nitrogen, high-purity helium, high-purity neon, high-purity argon gas, and its moisture is between 100ppm-10000ppm; For the protection of electrolyte, prevent hydrolysis and oxidation reaction;
3) high vacuum rectification under vacuum separation obtains the contained organic solvent of electrolyte then; With an organic solvent wash battery, the lithium hexafluoro phosphate solution that adopts the high vacuum rectification technical finesse to reclaim effectively prevents reducing side reaction of lithium hexafluoro phosphate; The condition of distillation operation: 0 to 20 kPa of vacuum degree, temperature adopt the operation of continuous rectification or batch fractionating method between 20 to 120 ° of C; The organic solvent that reclaims is one or more mixtures in ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, oxolane, the vinylene carbonate;
4) will obtain solid lithium hexafluoro phosphate material and add in the lithium hexafluoro phosphate dissolution kettle, add the lithium hexafluoro phosphate that the hydrogen fluoride solution dissolving is reclaimed; Employed hydrogen fluoride adopts hydrogen fluoride or this method commercially available, that distill after purifying to produce the mother liquor of getting in the lithium hexafluoro phosphate crystallization process in the dissolving lithium hexafluoro phosphate crude product process; When in hydrogen fluoride solution, dissolving the lithium hexafluoro phosphate crude product; Temperature does not have specific (special) requirements, between-30 ° of C to 20 ° of C;
5) carry out crystallization and purification with putting into crystallization kettle after this solution filtration; Between ° of C to 10 ° C of temperature-80; Crystallization time is between 4 hours to 48 hours; The Crystallization Separation method adopts natural filtration or pressure filtration or centrifugal filtering method;
6) screening, drying, the temperature in the drying process process is between 40 ° of C to 140 ° of C; The dry time is between 4 hours to 48 hours; Packing obtains the lithium hexafluoro phosphate product then.
CN2011104274312A 2011-12-19 2011-12-19 Method for recycling electrolyte of waste lithium ion battery CN102496752B (en)

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CN105234147A (en) * 2015-10-22 2016-01-13 宁波南车新能源科技有限公司 Resource recycling method for super capacitor

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CN104282962B (en) * 2013-07-10 2017-03-08 万向一二三股份公司 The recovery method of waste and old lithium ionic cell electrolyte
CN104143667A (en) * 2013-08-23 2014-11-12 中航锂电(洛阳)有限公司 Method and device for collection of waste lithium ion battery electrolyte solution
CN104009269B (en) * 2013-12-10 2016-06-01 宁波维科电池股份有限公司 The recovery and treatment method of waste and old lithium ion battery
CN103825065B (en) * 2014-02-27 2016-11-16 北京工业大学 A kind of waste and old lithium ionic cell electrolyte recovery and treatment method
DE102015207843B4 (en) * 2015-04-28 2018-06-07 Duesenfeld Gmbh Method of treating used batteries and battery processing equipment
CN105355999A (en) * 2015-11-30 2016-02-24 马鞍山泓宇材料科技有限公司 Novel waste lithium battery recycling method
CN105390765A (en) * 2015-12-07 2016-03-09 深圳市沃特玛电池有限公司 Recovery method for electrolyte solution of lithium ion battery
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CN106025419A (en) * 2016-07-24 2016-10-12 芜湖格利特新能源科技有限公司 Method for echelon utilization and recycling of power lithium-ion batteries
CN106129513B (en) * 2016-08-22 2018-12-18 浙江伏打科技有限公司 A kind of recovery method of waste lithium cell
CN106654437B (en) * 2016-12-01 2020-02-18 沧州凯盛达新能源科技有限公司 Method for recovering lithium from lithium-containing battery
CN107634281B (en) * 2017-08-17 2020-04-14 深圳市泰力废旧电池回收技术有限公司 Method for recovering electrolyte in waste power lithium ion battery
CN108079617A (en) * 2017-10-10 2018-05-29 骆驼集团武汉光谷研发中心有限公司 Waste and old lithium ionic cell electrolyte supercritical CO 2 extraction technology and equipment
CN108288737B (en) * 2017-12-25 2020-01-03 衢州北斗星化学新材料有限公司 Method for recovering lithium hexafluorophosphate from waste lithium battery cathode material
CN108631017B (en) * 2018-04-09 2020-06-23 惠州亿纬锂能股份有限公司 Method for recovering electrolyte of waste lithium ion battery
CN108923092A (en) * 2018-06-29 2018-11-30 惠州市宙邦化工有限公司 A kind of waste and old lithium ionic cell electrolyte processing method
CN110176646B (en) * 2019-05-20 2020-07-24 代辉 Recovery processing method of waste lithium ion battery electrolyte
CN110289457A (en) * 2019-06-24 2019-09-27 中国科学院过程工程研究所 A kind of green waste and old lithium ionic cell electrolyte recovery system and method

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101984516A (en) * 2010-08-19 2011-03-09 江苏锐毕利实业有限公司 Lithium ion battery resource recovery method for mobile phones

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3257774B2 (en) * 1998-07-09 2002-02-18 森田化学工業株式会社 Method for treating organic electrolyte containing lithium hexafluorophosphate
JP4997771B2 (en) * 2006-02-03 2012-08-08 住友金属鉱山株式会社 Separation and recovery of hexafluorophosphate ion

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101984516A (en) * 2010-08-19 2011-03-09 江苏锐毕利实业有限公司 Lithium ion battery resource recovery method for mobile phones

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105234147A (en) * 2015-10-22 2016-01-13 宁波南车新能源科技有限公司 Resource recycling method for super capacitor

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