CN105594056B - The processing method of fluorine-containing electrolyte - Google Patents
The processing method of fluorine-containing electrolyte Download PDFInfo
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- CN105594056B CN105594056B CN201480052035.8A CN201480052035A CN105594056B CN 105594056 B CN105594056 B CN 105594056B CN 201480052035 A CN201480052035 A CN 201480052035A CN 105594056 B CN105594056 B CN 105594056B
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- containing electrolyte
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 97
- 239000011737 fluorine Substances 0.000 title claims abstract description 59
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 59
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000003672 processing method Methods 0.000 title claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 57
- 238000002309 gasification Methods 0.000 claims abstract description 43
- 239000003513 alkali Substances 0.000 claims abstract description 33
- 239000004615 ingredient Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 25
- 239000011575 calcium Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000007789 gas Substances 0.000 description 19
- 238000004140 cleaning Methods 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 150000002222 fluorine compounds Chemical class 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 229910001290 LiPF6 Inorganic materials 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000003682 fluorination reaction Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229940043430 calcium compound Drugs 0.000 description 3
- 150000001674 calcium compounds Chemical class 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012556 adjustment buffer Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4242—Regeneration of electrolyte or reactants
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/206—Organic halogen compounds
- B01D2257/2066—Fluorine
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0034—Fluorinated solvents
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Secondary Cells (AREA)
- Processing Of Solid Wastes (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The processing method of the fluorine-containing electrolyte of the present invention is heated for contained volatile ingredient in fluorine-containing electrolyte in the gasification Liquid Residue after being gasified, the processing method added alkali and neutralized, wherein, the fluorine-containing electrolyte is electrolyte before electrolyte in refuse battery, the electrolyte of the state that refuse battery is cut or crushed, use or the electrolyte that is extracted from refuse battery, and add alkali in the gasification Liquid Residue of the electrolyte and in carrying out and.
Description
Technical field
The present invention relates to a kind of security processings of the fluorine-containing electrolyte in lithium ion battery etc..
This application claims preferential based on the patent application in Japanese publication on the 30th of September in 2013 the 2013-204124th
Power, and its content is applied at this.
Background technology
Large-scale lithium ion battery is used in electric vehicle or electronic equipment mostly, to supply the electric power of high power capacity, with
The processing of large-scale old and useless battery that is universal and largely generating of electric vehicle and electronic equipment is increasingly becoming problem.
Contain the fluorine compounds (LiPF as electrolyte in the electrolyte for lithium ion battery etc.6、LiBF4Deng) and
Volatile organic solvent, organic solvent are mainly carbonates, and are flammable material.If also, LiPF6With water or vapor
It is reacted, then toxic hydrogen fluoride can be generated due to hydrolysis.It is therefore desirable to a kind of safe processing method.
In the past, the processing method as lithium ion battery He its electrolyte, it is known to following processing method.(A) by lithium from
Sub- battery etc. is refrigerated to the temperature below the fusing point of electrolyte, and disassembles crushing battery, in organic solvent, is detached from grinding bodies
The electrolyte of extraction is distilled the processing method (patent document 1) to be separated into electrolyte and organic solvent by electrolyte；(B) it roasts
Burn waste lithium cell, crush the calcining matter and divide into magnetic material and nonmagnetics, with recycle the useful metals such as aluminium or copper amount compared with
The processing method (patent document 2) of more substances；(C) lithium battery is opened using high-pressure water, and utilizes organic solvent recycling electricity
Solve the processing method (patent document 3) of liquid；(D) pulverizing waste battery, through washing after stripping anode with recycle Al, Cu, Ni,
Co, and Li and the processing method (patent document 4) recycled are extracted with solvent state from remaining liq；And (E) is crushed and is given up
Used batteries elute LiPF after washing6, and remove anode and recycle cobalt acid lithium, on the other hand, in liquid after cleaning
The acid of high temperature is added by LiPF6Phosphoric acid and fluorine are resolved into, and adds in white lime herein to recycle the mixed of fluorination Ca and phosphoric acid Ca
Close the processing method (patent document 5) of object.
Patent document 1：No. 3935594 bulletins of Japanese Patent No.
Patent document 2：No. 3079285 bulletins of Japanese Patent No.
Patent document 3：No. 2721467 bulletins of Japanese Patent No.
Patent document 4：Japanese Patent Publication 2007-122885 bulletins
Patent document 5：Japanese Patent Publication 2000-106221 bulletins
In above-mentioned processing method (A), due to needing refrigeration equipment to disassemble crushing lithium battery under freezing conditions, because
This is difficult to carry out.In above-mentioned processing method (B), fluorine is treated as burning gases in the calcining process of lithium battery, therefore, it is impossible to
The fluorine ingredient of high-purity is recycled, and fluorine can not be recycled.In above-mentioned processing method (C), the processing of the electrolyte of recycling
As problem.Containing flammable organic solvent in electrolyte, also, after the fluorine compounds in electrolyte are reacted with water
Toxic hydrogen fluoride is generated, it is therefore desirable to safely be handled.In above-mentioned processing method (D), the cleaning containing organic solvent
Liquid afterwards is treated as problem.In above-mentioned processing method (E), the acid of high temperature is added in liquid after cleaning to make
LiPF6Resolve into phosphoric acid and fluorine, and add in white lime herein and generate fluorination Ca and phosphoric acid Ca, but the solid generated due to
It is the mixture for being fluorinated Ca and phosphoric acid Ca, therefore, it is difficult to recycle.
Invention content
The present invention is completed to solve the above problem in existing processing method, and its purpose is to provide a kind of peaces
Full processing has volatile fluorine compounds (LiPF6Deng) and electrolyte containing organic solvent method.
The present invention is the processing method of fluorine-containing electrolyte by being formed with lower structure.
[1] a kind of processing method of fluorine-containing electrolyte adds for contained volatile ingredient in fluorine-containing electrolyte
Heat and in gasification Liquid Residue after gasifying, add alkali and the processing method that is neutralized, wherein, the fluorine-containing electrolyte is useless electricity
Electrolyte before the electrolyte of electrolyte, the state that refuse battery is cut or crushed in pond, use or from refuse battery
The electrolyte of extraction, and add in the gasification Liquid Residue of the electrolyte alkali and in carrying out and.
[2] processing method of the fluorine-containing electrolyte according to above-mentioned [1], wherein, it is volatilized into the electrolyte
When the refuse battery divided after being gasified crushes processing, alkali is added, so as to be carried out at the same time neutralisation treatment and crushing.
[3] processing method of the fluorine-containing electrolyte according to above-mentioned [1], wherein, it is volatilized into the electrolyte
Divide in the crushed material of the refuse battery after being gasified, add alkali and neutralized.
[4] processing method of the fluorine-containing electrolyte according to above-mentioned [1] or [2], wherein, recycle the volatile ingredient
The gasifying gas of gasification, and contained fluorine ingredient is made in the gasifying gas to be reacted with calcium and is returned after becoming calcirm-fluoride
It receives.
[5] processing method of the fluorine-containing electrolyte according to any one of above-mentioned [1]~[3], wherein, it is waved described in recycling
The gasifying gas that hair ingredient has gasified, and fluorine ingredient contained in the gasifying gas is made to be reacted with calcium and becomes calcirm-fluoride
After recycled, on the other hand, cool down and condense collect the gasifying gas, so as to recycle Elements in Organic Solvents.
Processing method according to the present invention, due to being gasified to electrolyte and being taken out, there is no need to be freezed or high
Temperature burns and can safely handle refuse battery.
Also, by the alkali process for the Liquid Residue that gasifies, the gasification Liquid Residue of highly acid is neutralized, thus the corrosion of electrode or
Deterioration is inhibited.As a result, it is possible to recycle the material for being suitable for recycling.Moreover, it can safely crush work and divide
Class work etc., and the corrosion of reducing mechanism and sorting unit can be prevented.Also, alkali neutralization processing is in the laggard of gasification process
Row, therefore, alkali neutralization processing will not have an impact gasification process.Also, it is carried out by adding alkali in the Liquid Residue that gasifies
It neutralizes, fluorine contained in gasification Liquid Residue can be fixed.
Moreover, processing method according to the present invention, can from gasifying gas using fluorine as the calcirm-fluoride of high-purity come into
Row recycling.Such as the calcirm-fluoride that purity is more than 80% can be obtained.It can be using the calcirm-fluoride as the raw material of manufacture hydrofluoric acid
Or cement raw material and recycled.
Further, it is possible to the Elements in Organic Solvents recycled is utilized as fuel or substitute fuel.Pass through the present invention
Processing method recycling Elements in Organic Solvents in, since fluorine is detached, when accordingly acting as fuel, it is harmful not generate hydrogen fluoride etc.
Substance can be used safely.
Description of the drawings
Fig. 1 is the process chart of the outline for the processing method for representing embodiments of the present invention.
Fig. 2 is the XRD diagram of embodiment 2.
Specific embodiment
(illustrating)
Hereinafter, one embodiment of the present invention is specifically described.In addition, without illustrate when, % represent quality %,
Ppm represents quality ppm.
The processing method of present embodiment is heated for contained volatile ingredient in fluorine-containing electrolyte gasified after
Gasification Liquid Residue in, add alkali and the processing method that is neutralized, wherein, the fluorine-containing electrolyte is the electrolysis in refuse battery
Electrolyte before liquid, the electrolyte for the state that refuse battery is cut or crushed, use or the electrolysis extracted from refuse battery
Liquid, and add in the gasification Liquid Residue of the electrolyte alkali and in carrying out and.
The process of the outline for the processing method for representing present embodiment is illustrated in Fig. 1.
The processing method of present embodiment can be in the electrolyte used lithium battery etc..In lithium ion battery etc.
In the middle electrolyte used, fluorine compounds and organic solvent containing electrolyte.Fluorine compounds are mainly lithium hexafluoro phosphate
(LiPF6), organic solvent is dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC), propene carbonate
(PC), the carbonates such as ethylene carbonate (EC).DMC, EMC and DEC are flammable material.
Also, the processing method of present embodiment be to this fluorine-containing electrolyte, i.e., in refuse battery electrolyte,
Electrolyte before electrolyte, use obtained from refuse battery is cut or crushed or the electrolyte that is extracted from refuse battery etc.
It carries out in the gasification Liquid Residue after gasification process, the processing method added alkali and neutralized.
(gasification process)
In gasification process, by heating fluorine-containing electrolyte, gasify to volatile ingredient contained in fluorine-containing electrolyte (step
Rapid S1).
When handling the electrolyte in refuse battery, first, heated after being discharged the refuse battery used, so as to
The volatile ingredient of electrolyte is made to gasify.In general, safety valve is set in order to reduce superfluous internal pressure in the battery, therefore,
The safety valve and connecting line are opened, and heats the refuse battery to make volatile ingredient gasification contained in electrolyte.
Alternatively, can also handle refuse battery is cut or is crushed obtained from electrolyte.At this point, that cuts or crush is useless
The electrolyte of the inside battery of battery becomes exposes external state, therefore can handle electrolyte together with electrode material.It is right
It when refuse battery is cut or crushed, carries out, burns to prevent electrolyte under inert gas atmosphere.
The electrolysis that the processing method of present embodiment can also be extracted suitable for the electrolyte before use or from refuse battery
Liquid.In order to extract electrolyte from refuse battery, refuse battery is cleaned with cleaning solvent to extract electrolyte.As cleaning solvent, energy
Enough using the organic solvent that water or boiling point are less than 150 DEG C.In addition, carbonates contained in electrolyte can be recycled as clear
Solvent is washed to be recycled.
In this gasification process, electrolyte is heated to the higher temperature of boiling point of the organic solvent more contained than in electrolyte
Degree, so as to the volatile ingredient for the organic solvent that gasifies.LiPF is heated under conditions of being coexisted with water6, then it is decomposed, and fluorine ingredient gas
It is melted into hydrogen fluoride.
It opens the safety-valve and connecting line is come when making the volatile ingredient volatilize, if being depressurized to inside battery and heating electrolysis
Liquid, then internal temperature increases and volatile ingredient easily gasifies.If it is heated to 80 DEG C for example, inside battery is decompressed to after 5kPa
~150 DEG C, then atmospheric pressure reduced temperature become 170 DEG C~251 DEG C of state.Also 1kPa~0.1kPa can be decompressed to heat later
To 80 DEG C~120 DEG C.
When refuse battery being cut or crushed in the container of inert gas atmosphere, directly heated to come with the container
Volatile ingredient is made to gasify.In addition, also the inside of the container can be depressurized to heat.
Such as following formula (1), by heating the electrolyte added with a small amount of water or a small amount of diluted mineral acid at reduced pressure conditions, make
LiPF6It is reacted to be hydrolyzed into phosphoric acid and hydrogen fluoride successively with water.Thereby, it is possible to promote based on LiPF6Decomposition gasification.
[chemical formula 1]
LiPF6+4H2O→LiF+5HF(↑)+H3PO4……(1)
(alkali neutralization treatment process)
After the gasification process (step S1) for carrying out refuse battery, a small amount of fluorine compounds or organic solvent not by gasification and with
The remaining situation of Liquid Residue that gasifies is more.As an example, about the 30% of electrolyte is remained.
The gasification Liquid Residue is included as the phosphate cpd of strong acidic liquid, fluorine compounds, lithium compound and higher boiling
Carbonates.The gasification Liquid Residue is attached to battery material, causes the corrosion or deterioration of material.Useless electricity is extracted with cleaning solvent
During the electrolyte in pond, it is also possible to remain these fluorine compounds or organic solvent.
In the processing method of present embodiment, after gasification process in remaining gasification Liquid Residue, add alkali and carry out
(step S2).Specifically, liquid component (the attachment residual for remaining on inside refuse battery and adhering to after to gasification process
Liquid) or in the Liquid Residue (the gasification Liquid Residue after cleaning) after the liquid progress gasification process after cleaning, adding alkali and carrying out
It neutralizes, so as to become innocuous substance.Additionally, it is preferred that neutralize after Liquid Residue pH be more than 4 and 10 hereinafter, more preferably
More than 6 and less than 8.
As the alkali added in the Liquid Residue that gasifies, sodium hydroxide (NaOH), Ca classes neutralizer (Ca (OH) can be used2、
CaCO3, CaO), Mg classes neutralizer (MgO, Mg (OH)2) etc..Or their mixture can also be used.Ca class neutralizers are cheap,
And if using Ca class neutralizers, fluorine or phosphorus can be immobilized as indissoluble salt, therefore advantageously.
These alkali can be used with the state of powder, solution or slurry.It is carried out with solution or slurry in use, excellent
Select alkali a concentration of solution or slurry total weight 0.1~20%.Relative to electrolyte weight contained in refuse battery, preferably alkali
Usage amount be 0.5~30%.
If adding alkali in the gasification Liquid Residue of refuse battery in carrying out and, can be by fluorine contained in the Liquid Residue that gasifies
It immobilizes (solid state).If for example, in the Liquid Residue that gasifies add NaOH and carry out in and, generate containing NaF,
NaHF2, LiF etc. precipitation.
By being added in gasification Liquid Residue as described above (including the gasification Liquid Residue after cleaning and attachment Liquid Residue)
Alkali and neutralized to become innocuous substance, the corrosion or deterioration of electrode can be inhibited, and can recycle be suitable for recycle
Material.Further, it is possible to safely crush work or classification work etc., and reducing mechanism or sorting unit can be prevented
Corrosion.Moreover, and, fluorine contained in Liquid Residue can be fixed in being carried out by adding alkali in above-mentioned Liquid Residue.
It is crushed in addition, usually having extracted the refuse battery of electrolyte, thus obtained crushed material is classified by using material
And it is recycled.In Fig. 1, alkali is added before the pulverization process of refuse battery, but also can be after the pulverization process of refuse battery or powder
Alkali is added in broken processing.That is, alkali can be added before processing is crushed to refuse battery or when crushing processing to refuse battery,
In being carried out so as to be carried out at the same time neutralisation treatment and crushing or also add alkali in the crushed material of refuse battery and.
(recovery process)
By the gasification process of the electrolyte of the gasification process or cleaning extraction of the electrolyte of refuse battery, gas can be recycled
The gas (gasifying gas) of change, and contained fluorine ingredient can be made to be reacted with alkali in the gasifying gas and after becoming calcirm-fluoride
It is recycled (step S3).Moreover, while fluorine is recycled as calcirm-fluoride, the gasification is collected by cooling down and condensing
Gas, so as to recycle the condensate liquid (step S4) containing Elements in Organic Solvents.
Specifically, the gas of gasification is imported into organic solvent and the fluorination collected in water cooling collector in gas
Hydrogen.These are separated into water phase and organic phase this two layers.Containing the fluorine ingredient in gasifying gas in water phase, and it is 2 for substantially pH
Following acidity.Addition calcium compound (calcium carbonate, white lime, quick lime etc.) is neutralized in the water phase (fluorine-containing water),
And the fluorine in liquid is made to be reacted with calcium, so as to make calcium fluoride precipitate.Separation of solid and liquid is carried out to the calcirm-fluoride and is recycled
(step S3).
Compared with the organic solvent of gasification, when water (fluorine-containing water) is micro, organic solvent is mutually dissolved with hydrogen fluoride
And only become organic phase.Calcium compound can be added in the organic phase, and the calcirm-fluoride generated to addition calcium compound is consolidated
Liquid detaches, so as to recycle the organic phase of fluorine removal.Also, gasifying gas can also be imported into calcium filled layer to generate fluorination
Calcium, and cooling is carried out to the gas by the filled layer and is used as condensate liquid, so as to recycle organic solution (step S4).
Embodiment
Then, the embodiment involved by embodiments of the present invention is illustrated below.In addition, by glass electrode method to liquid
PH analyzed.Specifically, the Horiba pH electrodes 9625-10D manufactured are used as pH electrodes, and will survey
The temperature for determining object liquid is set as 20 DEG C to determine pH.Also, Funing tablet is analyzed by fluoride ion electrode method.
Specifically, ionic strength regulator (KANTO CHEMICAL CO., the INC. systems of 5ml are added in measure object liquid 100ml
The TISAB (A total ionic strength adjustment buffer) made), and determine fluorine under 20 DEG C of liquid temperature
Concentration.The fluoride ion electrode 6561-10C of Horiba manufactures has been used as fluoride ion electrode.
(embodiment 1)
After discharging lithium ion refuse battery (electrolyte containing 100mL), safety valve is unlocked, and be added to from its opening
The water of 20g.The connecting line in above-mentioned opening, and under the pressure of 20kPa, the refuse battery is heated 2 hours with 120 DEG C, so as to
The electrolyte of inside battery is made to gasify.Later, refuse battery is crushed to below 3cm.Gasification is attached in the entire crushed material
Liquid Residue.The Ca (OH) of 5g (the 5% of crushed material weight) is added in crushed material 100g2And it mixes 10 minutes.It soaks in water
The stain mixture 1 hour.The pH of water after dipping is 10.2, Funing tablet 31ppm.
(embodiment 2)
After discharging lithium ion refuse battery (electrolyte containing 100mL), safety valve is unlocked, and note as cleaning solvent
Enter the mixed solvent (1 of DEC and EMC:1) it is discharged after 100mL, repeats 5 this cleaning operations to extract electrolyte.
The water of 20g is added in liquid after the cleaning of recycling, and under the pressure of 20kPa, heated 2 hours with 120 DEG C, so as to make to wave
Send out ingredient gasification.The Liquid Residue that the gasifies liquid higher for viscosity, and weight is 34.5g, pH 1.8.In the gasification Liquid Residue
24 mass % the NaOH aqueous solutions of 10mL is added as a result, carrying out kickback and generating white precipitate, so as to Liquid Residue into
For white gels shape.The pH of the spawn is 8.3, weight 42.3g.The white gels shape substance is dried in vacuo
Processing, and carried out XRD (X-ray diffraction) measure.Obtained XRD diagram (X ray collection of illustrative plates) is shown in Fig. 2.Such as XRD diagram institute
Show, confirm containing NaF, NaHF and LiF in the spawn, and the fluorine in Liquid Residue is fixed.
(embodiment 3)
The gas to gasify in embodiment 1 is imported and recycled with the sequence of cooling tube (4 DEG C), condensing collector
The aggegation liquid of 70mL.The Funing tablet of the water phase is 50200g/L, pH 1.2.Addition 9.30g calcium carbonate is heavy to generate wherein
It forms sediment.The ingredient of the precipitation of recycling is analyzed by powder x-ray diffraction, confirms its ingredient as calcirm-fluoride.Calcirm-fluoride
Yield is 7.49g, purity 87%.On the other hand, to organic principle analyzed as a result, the ingredient of solution for DMC,
MEC and DEC.
(comparative example 1)
The water of 20g is added in refuse battery same as Example 1, and under the pressure of 20kPa, it is useless to heat this with 120 DEG C
Battery 2 hours, so as to be gasified to the electrolyte of inside battery.Later, the plain battery dried is taken out from refuse battery,
And it crushes and is cut to below 3cm.The crushed material of dipping 100g 1 hour in water.The pH of water after dipping is 2.3, Funing tablet
For 410ppm.
More than, preferred embodiments of the present invention have been disclosed for illustrative, but the present invention is not limited to the embodiments.It is not taking off
In the range of spirit of the invention, the additional of inscape, omission, displacement and other changes can be carried out.The present invention is not
Preceding description is defined in, and is only defined by appended claims.
Industrial availability
The processing method of fluorine-containing electrolyte according to the present invention can safely handle fluorine compounds and contain organic solvent
Electrolyte.Thereby, it is possible to safely handle the lithium battery containing fluorine-containing electrolyte.
Symbol description
S1- gasification process, S2- alkali addition process, S3- fluorine fixed steps, S4- Elements in Organic Solvents recovery process.
Claims (5)
1. a kind of processing method of fluorine-containing electrolyte, has：
Gasification process, for as in refuse battery electrolyte, the electrolyte for the state that refuse battery is cut or crushed, make
The fluorine-containing electrolyte of the electrolyte extracted with preceding electrolyte or from refuse battery, by heating the fluorine-containing electrolyte, to institute
Volatile ingredient contained in fluorine-containing electrolyte is stated to gasify；And
Alkali neutralization treatment process, after the gasification process in the gasification Liquid Residue of the remaining fluorine-containing electrolyte add alkali and
It is neutralized,
In the gasification process, the fluorine-containing electrolyte is decompressed to after 1kPa~0.1kPa and is heated to 80 DEG C~120 DEG C.
2. the processing method of fluorine-containing electrolyte according to claim 1, wherein,
When the refuse battery after the volatile ingredient to the fluorine-containing electrolyte gasifies crushes processing, alkali is added,
So as to be carried out at the same time neutralisation treatment and crushing.
3. the processing method of fluorine-containing electrolyte according to claim 1, wherein,
In the crushed material of the refuse battery after the volatile ingredient to the fluorine-containing electrolyte gasifies, add alkali and carry out
It neutralizes.
4. the processing method of fluorine-containing electrolyte according to claim 1 or 2, wherein,
The gasifying gas that the volatile ingredient has gasified is recycled, and it is anti-that fluorine ingredient contained in the gasifying gas is made to be carried out with calcium
Should and as being recycled after calcirm-fluoride.
5. the processing method of fluorine-containing electrolyte described in any one of claim 1 to 3, wherein,
The gasifying gas that the volatile ingredient has gasified is recycled, and it is anti-that fluorine ingredient contained in the gasifying gas is made to be carried out with calcium
Should and as being recycled after calcirm-fluoride, on the other hand, cool down and condense and collect the gasifying gas, so as to recycle organic solvent into
Point.
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| WO2019044042A1 (en) * | 2017-08-28 | 2019-03-07 | 杉山 修 | Battery having electrolytic solution containing alkaline mineral ionized water, electrolyte active material, and method for producing battery electrolytic solution |
| CN108682914B (en) * | 2018-04-09 | 2021-02-23 | 惠州亿纬锂能股份有限公司 | Recovery processing method of waste lithium ion battery electrolyte |
| CN108808156B (en) * | 2018-08-24 | 2020-10-16 | 广西师范大学 | Method for recovering electrolyte in waste lithium ion battery |
| CN110034351A (en) * | 2019-04-29 | 2019-07-19 | 浙江华友钴业股份有限公司 | A kind of innoxious minimizing technology of used Li ion cell electrolyte |
| WO2022032345A1 (en) * | 2020-08-12 | 2022-02-17 | Resource Conservation and Recycling Corporation Pty Ltd | Process for recovering values from batteries |
| CN112251604B (en) * | 2020-10-10 | 2022-06-28 | 昆明理工大学 | Method for recovering valuable metals from comprehensive recovery slag of waste lithium cobalt oxide batteries |
| JP7153245B2 (en) * | 2021-01-18 | 2022-10-14 | 住友大阪セメント株式会社 | Method for recovering valuables from used lithium-ion batteries |
| JP2024513015A (en) * | 2021-03-29 | 2024-03-21 | ポスコ カンパニー リミテッド | Processing method for recycling waste batteries |
| CN113363610B (en) * | 2021-06-18 | 2022-11-22 | 郑州中科新兴产业技术研究院 | Harmless treatment method for retired lithium ion battery electrolyte |
| KR102516189B1 (en) * | 2022-09-27 | 2023-03-30 | 주식회사 이알 | Waste Lithium Ion Battery Vacuum Pyrolysis Method |
| CN116081654A (en) * | 2023-01-13 | 2023-05-09 | 北京化工大学 | Method for safely and efficiently recycling lithium resources and fluorine resources in electrolyte and application thereof |
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