CN110311186A - A method of recycling valuable element from waste and old lithium ion battery - Google Patents
A method of recycling valuable element from waste and old lithium ion battery Download PDFInfo
- Publication number
- CN110311186A CN110311186A CN201910166801.8A CN201910166801A CN110311186A CN 110311186 A CN110311186 A CN 110311186A CN 201910166801 A CN201910166801 A CN 201910166801A CN 110311186 A CN110311186 A CN 110311186A
- Authority
- CN
- China
- Prior art keywords
- pole piece
- solution
- sodium
- potassium
- lithium ion
- Prior art date
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Links
- 238000000034 method Methods 0.000 title claims abstract description 51
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002699 waste material Substances 0.000 title claims abstract description 20
- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 22
- 239000004411 aluminium Substances 0.000 claims description 22
- 230000004044 response Effects 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 239000011737 fluorine Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 239000011149 active material Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 230000001131 transforming effect Effects 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 8
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 claims description 8
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims description 7
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 150000001447 alkali salts Chemical class 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 4
- 229910013361 LiNixCoyAl1-x-yO2 Inorganic materials 0.000 claims description 4
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 4
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910003005 LiNiO2 Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 230000010358 mechanical oscillation Effects 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims 1
- 235000019797 dipotassium phosphate Nutrition 0.000 claims 1
- 229960001484 edetic acid Drugs 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 abstract description 16
- 230000009467 reduction Effects 0.000 abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 9
- 239000007774 positive electrode material Substances 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000007773 negative electrode material Substances 0.000 abstract description 2
- 238000002386 leaching Methods 0.000 description 40
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 18
- 238000006722 reduction reaction Methods 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 10
- 238000000227 grinding Methods 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 10
- 239000012634 fragment Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- 239000007767 bonding agent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
- C22B15/0004—Preliminary treatment without modification of the copper constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The present invention relates to recycling of WEEE processing, resource technology field, more particularly to a kind of method for recycling valuable element from waste and old lithium ion battery, this method by carrying out electric discharge dismantling for battery in advance, anode pole piece and cathode pole piece are recycled respectively again, the removal process of the anode pole piece includes broken, reaction, separation, recycling, and the removal process of the cathode pole piece includes heat treatment, vibration.The present invention realizes the recycling of positive electrode and negative electrode material to waste and old lithium ion battery, and adaptability to raw materials is wide, the reduction of transition metal element and the conversion of lithium not only have been synchronously completed in the case where not needing and additionally adding reducing agent, has been convenient for its subsequent separation and recovery；And the separation process of positive active material and collector is avoided, enormously simplify the recovery process of valuable element.
Description
Technical field
The present invention relates to recycling of WEEE processing, resource technology field, and in particular to a kind of from applying waste lithium ionic
The method of valuable element is recycled in battery.
Background technique
Since the nineties in last century, lithium ion battery is widely used in various portable electronic products, such as digital phase
Machine, laptop etc..In recent years, the demand cumulative year after year with people to environmental protection, China start the new energy of large-scale popularization
Also there is explosive growth in source automobile, and power resources of the lithium ion battery as new-energy automobile, application.However,
It is the small-scale lithium ion cell in portable electronic product or the power battery in new-energy automobile, the service life is limited.Quotient
It is typically less than the number of 1000 times with lithium ion battery is recyclable.Therefore, the large-scale application of lithium ion battery also implies that largely
The generation of waste and old lithium ion battery.The environmental problem and resource reutilization problem caused by waste and old lithium ion battery is increasingly severe.
Therefore, valuable element is recycled in cleaning from waste and old lithium ion battery at low cost has very important economic value and environmentally friendly valence
Value.
Valuable element in waste and old lithium ion battery is concentrated mainly among positive electrode, and positive electrode mainly includes anode
Active material (LiCoO2, LiMn2O4,LiNixCoyMn1-x-yO2,LiNixCoyAl1-x-yO2Deng), collector (aluminium foil), bonding agent
(PVDF) and conductive agent (acetylene black).The process that valuable element is recycled from positive electrode can be roughly classified into the pre- of positive electrode
Two steps of extraction of processing and valuable element.For pre-treatment step, difficult point is the height of active material and collector
Effect separation.Currently, the method industrially used is mainly heat treating process, the decomposition temperature of bonding agent PVDF 450~600 DEG C it
Between, research shows that heat treatment temperature can be obtained at 600 DEG C optimal separating effect (Hydrometallurgy, 2016,165,
390-396；Journal of Hazardous Materials, 2011,194,378-384), therefore, locate in advance at 600 DEG C
Reason, can be such that positive electrode active materials efficiently separate with collector.Such as patent application CN200910304134, at 400 DEG C~600 DEG C
Anaerobic roasting, is destroyed bonding agent, to realize efficiently separating for active material and collector.High temperature pretreatment means pre-
Although efficiently separating for active material and collector may be implemented in the high energy consumption for the treatment of process, therefore, high temperature preprocess method, but
Also increase the totle drilling cost of recovery method and the complexity of method.
For the leaching step of valuable element, difficult point is that active material configuration is highly stable, it is necessary to destroy its structure
Just it is able to achieve the leaching of valuable element.Transition metal element in active material is generally in higher valence state (>+2), and in solution
The stable state of middle transition metal element is+divalent, and therefore, the method for destroying active material configuration essentially passes through redox
Reaction, makes the chemical valence of transition metal element lower (≤+ 2), to achieve the purpose that destroy active substance crystals structure.Activity
The restoring method of transition metal element in substance can be divided into two classes: before reducing agent reduction and Ore Leaching are added during Ore Leaching
It is restored using carbothermic method.
It for sulfuric acid+mass percent of 2~4mol/L is 30% that Chinese patent CN200910304134, which uses concentration,
H2O2, the extraction that transition metal element realizes valuable element is restored in sulfuric acid solution.Due to needing to consume a large amount of H2O2, so that
The cost of this method greatly improves.In addition, in the leaching process, valuable element Li and transition metal element enter acid molten together
In liquid, during subsequent extracted and separation transition metal element, the entrainment of Li element is inevitable, its rate of recovery is made to be difficult to protect
Card.
Compared with H2O2Reduction method, carbon thermal reduction rule are widely studied because reducing agent cost is cheaper.Chinese patent
CN201610479966 carries out reduction treatment to positive active material before leaching using carbothermic method, to avoid leaching
H in journey2O2Consumption.In this method, select the carbonaceous materials such as lignite, bituminous coal, anthracite as reducing agent, at 500~750 DEG C
Down so that LiNixCoyMn1-x-yO2In transition metal element be reduced to simple substance Ni, simple substance Co and MnO respectively.It is delivered from it
It is found that reduction temperature needs to reach 650 DEG C in article (Journal of Power Sources, 2017,351,192-199.)
Satisfied reduction effect can be reached.Positive and negative anodes pole piece is not sorted in Chinese patent application 201711268988.X, is directly utilized
Carbon in cathode pole piece restores the transition metal element in cathode pole piece, to avoid the consumption of reducing agent in leaching process.
It is this kind of whether to use cheap lignite etc. or directly use the graphite in waste and old lithium ion battery cathode pole piece as reduction
The method of agent, due to the limitation of carbothermic reduction reaction, the amount of allocating of reducing agent carbon usually needs significantly excessive, the temperature of reduction process
It is also required to reach 600 DEG C or more the effective reduction for being just able to achieve transition metal element.This kind of pyroreaction not only needs to consume greatly
The energy is measured, also more stringent requirements are proposed to equipment needed for reaction process.In addition, carbon thermal reduction product is CO2Have with CO etc.
Evil gas, this proposes extra demand to the gas emission treatment of removal process again.In addition, in carbothermic reduction process Li mainly with
Sl. sol. Li2CO3Form exists, if CO need to be passed through using pressurization by thinking individually to extract2Gas can be realized, keep extraction process complicated
Change.
To sum up, there is positive electrode active materials for the recycling of valuable element in current waste lithium ion cell anode material
Matter and collector separation process are complicated, and the rate of recovery of valuable element lithium is low and removal process is complicated, leaching process needs largely disappear
The problems such as reducing agent or carbothermic reduction process temperature high energy consumption are big, there are toxic noxious gas emissions is consumed, these all restrict
The economic cleaning recycling of valuable element in positive electrode.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of more systematic, processes simply, the valuable element rate of recovery
The high and more energy-efficient method that valuable element is recycled from waste and old lithium ion battery.
To achieve the goals above, technical solution of the present invention is as follows:
A method of it recycling valuable element from waste and old lithium ion battery, includes the following steps:
S1: Mechanical Crushing is carried out after waste and old lithium ion battery is discharged, obtains anode pole piece and cathode pole piece；
S2: the anode pole piece is crushed and obtains positive electrode powder；By the positive electrode powder in non-oxidizing gas
Atmosphere is reacted at 400 DEG C~750 DEG C, and thermal response product is obtained；
The cathode pole piece is placed at 450~600 DEG C after being heat-treated, obtains copper foil and graphite powder by mechanical oscillation.
It is a discovery of the invention that not needing to carry out active material and aluminium foil separation, directly by positive pole when recycling valuable element
After piece is broken, when being reacted at the temperature disclosed above, it is not only able to achieve the conversion to lithium, passes through aqueous solution convenient for the lithium after conversion
Or alkaline solution dissolution, avoid the subsequent loss problem to lithium in transition metal element extraction process；And it can complete pair
The reduction of transition metal element destroys its stability in order to further recycle.And the reaction temperature is lower than traditional carbon thermal reduction
Required temperature greatly reduces process energy consumption.
When recycling the recoverable substance in cathode pole piece, can simply and efficiently be realized by the above method higher
The rate of recovery.
As a preferred solution of the present invention, the reaction temperature of positive electrode powder described in S2 step is 400~600
℃。
When reaction temperature is lower, reduzate is oxide, it is easier to which by Ore Leaching, and when temperature is high is then simple substance, phase
To being difficult to leach, for the effect of different materials control temperature, there are difference, in technological accumulation and inheritance of the invention, when S2 step
When reaction temperature is 400~600 DEG C, most of substance in lithium ion battery can be made to be in easily by the transition of Ore Leaching.
As a preferred solution of the present invention, in S2 step, after the positive electrode powder is mixed with alkali salt,
Non-oxidizing atmosphere is reacted at 300 DEG C~750 DEG C, and thermal response product is obtained；It is preferred that being reacted at 300~550 DEG C.
The present invention promotes the reaction in S2 that can go on smoothly at lower temperatures by introducing alkali salt.After alkali salt is added,
It is reacted at 300~550 DEG C, most of substance in lithium ion battery can be made to be in easily by the transition of Ore Leaching.
As a preferred solution of the present invention, the reaction time in S2 step is 0.1~5 hour.
As a preferred solution of the present invention, the heat treatment time of negative electrode material is 30min in S2 step.
As a preferred solution of the present invention, further include S3 after the S2 step:
The thermal response product is mixed with water or alkaline solution, makes therein to dissolve containing lithium and aluminium-containing substance；Through solid-liquid
Solution and alkali leached mud containing lithium and aluminium are obtained after separation.
As a preferred solution of the present invention, further include S3 ' after the S2 step:
The thermal response product is mixed with water or alkaline solution and fluorine transforming agent, makes aluminium-containing substance and fluoride therein
It is dissolved, solution and alkali leached mud containing aluminium and fluorine is obtained after being separated by solid-liquid separation.
As a preferred solution of the present invention, fluorine transforming agent can be directly dissolved in alkaline solution or alkaline molten
It is added dropwise and is entered in the form of powder or solution when liquid dissolves position containing aluminium.
As a preferred solution of the present invention, the fluorine transforming agent is preferably sodium phosphate, potassium phosphate, dibastic sodium phosphate, phosphorus
One of potassium hydrogen phthalate or more than one mixture.
When fluoride is more in electrode material, consider that fluorine transforming agent is added, by the introducing of fluorine transforming agent, by waste and old lithium
The insoluble LiF generated in ion battery raw material and in treatment process is converted into soluble NaF or KF enters in aqueous slkali, thus
The generation of toxic and harmful gas HF in classical acid leaching process is avoided, production environment is optimized.
As a preferred solution of the present invention, the valuable element is one of Li, Ni, Co and Mn or a variety of.
As a preferred solution of the present invention, the active material in the anode pole piece is LiCoO2、LiNiO2、
LiMn2O4、LiNixCoyMn1-x-yO2、LiNixCoyAl1-x-yO2One of or more than one mixture.
As a preferred solution of the present invention, the average grain diameter of positive electrode powder particle described in S2 is micro- less than 150
Rice.
As a preferred solution of the present invention, the non-oxidizing atmosphere is nitrogen, helium, neon, one in argon gas
Kind or more than one mixed gas are vacuum.
As a preferred solution of the present invention, the alkali salt is sodium hydroxide, sodium oxide molybdena, sodium peroxide, sodium carbonate, carbon
One of sour hydrogen sodium, potassium hydroxide, potassium oxide, potassium peroxide, potassium carbonate, saleratus or more than one mixture.
As a preferred solution of the present invention, the alkaline solution is sodium hydroxide, sodium oxide molybdena, sodium peroxide, hydrogen-oxygen
Change one of potassium, potassium oxide, potassium peroxide or more than one solution.
As a preferred solution of the present invention, the concentration of the alkaline solution is 0.1~5.0mol/L.
By the introducing of fluorine transforming agent, the insoluble LiF that will be generated in waste and old lithium ion battery raw material and in treatment process
It is converted into soluble NaF or KF enters in aqueous slkali, so that the generation of toxic and harmful gas HF in classical acid leaching process is avoided,
Optimize production environment.
As a preferred solution of the present invention, it is dissolved at 50~95 DEG C and carries out described in S3 or S3 ' step.
As a preferred solution of the present invention, dissolution time is 0.1~10 hour in S3 or S3 ' step.
As a preferred solution of the present invention, the method also includes S4:
The alkali leached mud is mixed with acidic aqueous solution, dissolves valuable element.
As a preferred solution of the present invention, the acidic aqueous solution is hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, second
The aqueous solution of one of ethylenediamine tetraacetic acid (EDTA) or more than one mixtures.
As a preferred solution of the present invention, the ratio of the alkali leached mud and the acidic aqueous solution is 1:3~1:
20。
As a preferred solution of the present invention, the temperature dissolved in S4 is 0 DEG C~100 DEG C.
As a preferred solution of the present invention, the time dissolved in S4 is 0.1~20 hour.
As a preferred solution of the present invention, the additional amount of acidic aqueous solution is the 1.0~10.0 of theoretical amount in S4
Times.
On the basis of common knowledge of the art, above-mentioned each preferred embodiment can be combined with each other each preferably to get the present invention
Example.
The present invention has the beneficial effect that:
(1) the present invention provides a kind of methods for recycling valuable element in waste and old lithium ion battery of system, complete
The recycling of anode pole piece and cathode pole piece, and adaptability to raw materials is wide, not only in the case where not needing additionally to add reducing agent
The reduction of transition metal element and the conversion of lithium have been synchronously completed, its subsequent separation and recovery is convenient for；And avoid positive-active
The separation process of substance and collector enormously simplifies the recovery process of valuable element；
(2) present invention further reduced reaction temperature, so that reaction required temperature is well below biography by introducing alkali salt
System carbon thermal reduction required temperature, greatly reduces process energy consumption；It, can be by the mistake in active material and by control reaction temperature
That crosses metallic element selectivity is reduced to metal simple-substance or low oxide, optionally makes transition golden with optimal conditions
Belonging to element reduction is to be easier by oxides such as NiO, CoO and MnO of Ore Leaching, adds reducing agent without additional, and valuable
The leaching rate of element greatly optimizes Ore Leaching process more than 99.95%.
(3) noxious gas emission is had no in reaction process of the invention, and passes through the introducing of fluorine transforming agent, can also be avoided
The generation of toxic and harmful gas HF, optimizes production environment during subsequent Ore Leaching.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
The lithium ion battery packet scrapped from new-energy automobile, after impregnating electric discharge 24 hours in NaCl salt water, lazy
Mechanical shearing in property environment, by respectively obtaining anode pole piece and cathode pole piece.Dismantling is obtained into LiNixCoyMn1-x-yO2
Anode pole piece is cut into the fragment of size about 2 × 2cm, which is placed in vibration grinding 4 minutes in vibration sample grinding machine, is obtained
Positive electrode powder, the mass percent of each element is as follows in the powder: Li 6.47%, Ni 16.94%, Co 16.53, Mn
13.14%, Al 13.28%, C 3.91%.By positive electrode powder and sodium hydroxide be in mass ratio 10:1 after evenly mixing,
It is placed in electric furnace and is warming up to 450 DEG C under protection of argon gas with 8 DEG C of rates per minute, keep the temperature 60 minutes, obtain thermal response product.
Thermal response product is added in 85 DEG C of 2.5mol/L NaOH solution, is leached 2 hours, the leaching rate of aluminium is up to 100%, the leaching of lithium
Extracting rate is greater than 99.5%, and solution and alkali leached mud containing lithium and aluminium is obtained by filtration.Gained alkali leached mud is added 60 DEG C
In the sulfuric acid solution of 2.5mol/L, 30 minutes are kept the temperature, transition metal element can efficiently be leached, the leaching rate point of Ni, Co and Mn
It Wei 98.62%, 99.29% and 99.91%.Gained cathode pole piece is then placed in hot at 560 DEG C in the tube furnace of argon gas protection
Processing 15 minutes is tapped by machinery, so that graphite powder is fallen off from copper foil, to obtain copper foil and graphite powder.
Embodiment 2
The old and useless battery of mobile phone was impregnated to electric discharge 32 as a child in NaOH aqueous solution, was disassembled by hand in glove box
Obtain just positive piece and cathode pole piece.By resulting LiNixCoyMn1-x-yO2Anode pole piece is cut into the fragment of size about 1 × 4cm,
The anode fragment is placed in vibration grinding 3.5 minutes in vibration sample grinding machine, obtains positive electrode powder, each element in the powder
Mass percent is as follows: Li 7.01%, Ni 15.32%, Co 15.23, Mn15.14%, Al 10.57%, C 4.91%.It will
Positive electrode powder, which is placed in electric furnace, is warming up to 460 DEG C under protection of argon gas with 5 DEG C of rates per minute, keeps the temperature 180 minutes, obtains
To thermal response product.Thermal response product is added to 85 DEG C of 3.5mol/L KOH, is leached 1.5 hours, the leaching rate of aluminium reaches
100%, the leaching rate of lithium is greater than 95.8%, and solution and alkali leached mud containing lithium and aluminium is obtained by filtration.Gained alkali leached mud is added
In the hydrochloric acid solution for entering 80 DEG C of 1.5mol/L, 30 minutes are kept the temperature, transition metal element can efficiently be leached, Ni, Co and Mn's
Leaching rate is respectively 98.92%, 99.09% and 99.05%.Gained cathode pole piece be then placed in argon gas protection tube furnace in
It is heat-treated 15 minutes at 550 DEG C, is tapped by machinery, so that graphite powder is fallen off from copper foil, to obtain copper foil and graphite powder.
Embodiment 3
The LiCoO disassembled in disused mobile battery2Anode pole piece leftover pieces, by the pole piece be cut into size about 0.5 ×
The anode fragment is placed in vibration grinding 4.5 minutes in vibration sample grinding machine, obtains positive electrode powder, the powder by the fragment of 5.0cm
The mass percent of each element is as follows in end: Li 7.01%, Co 45.23, Al 10.91%, C 5.83%.By positive electrode
Powder and potassium hydroxide 20:1 in mass ratio after evenly mixing, are placed in electric furnace under protection of argon gas with 10 DEG C of rates per minute
420 DEG C are warming up to, 120 minutes is kept the temperature, obtains thermal response product.Thermal response product is added in 95 DEG C of water, it is small to leach 1.5
When, for the leaching rate of aluminium up to 100%, the leaching rate of lithium is greater than 98.0%, and solution and alkali leached mud containing lithium and aluminium is obtained by filtration.It will
Gained alkali leached mud is added in the nitric acid solution of 80 DEG C of 1.5mol/L, keeps the temperature 30 minutes, can efficiently leach valuable element, Co
Leaching rate be respectively 99.71%.
Embodiment 4
The LiNi of certain Battery PlantxCoyMn1-x-yO2The pole piece is cut into the broken of size about 2 × 1.5cm by anode pole piece leftover pieces
The anode fragment is placed in vibration grinding 5.5 minutes in vibration sample grinding machine, obtains positive electrode powder, each member in the powder by piece
The mass percent of element is as follows: Li7.01%, Ni 15.32%, Co 15.23%, Mn 15.14%, Al 10.57%, C
4.91%.After evenly mixing by positive electrode powder and potassium carbonate 5:1 in mass ratio, it is placed in electric furnace under protection of argon gas with 5
DEG C rate per minute is warming up to 500 DEG C, keeps the temperature 60 minutes, obtains thermal response product.Thermal response product is added 85 DEG C
3.5mol/L NaOH and 0.2mol/L Na3PO4Mixed solution in, leach 1.5 hours, the leaching rate of aluminium up to 100%, fluorine
Leaching rate is greater than 98.5%, is obtained by filtration containing aluminium and fluorine-containing solution and alkali leached mud.Gained alkali leached mud is added 80 DEG C
In the sulfuric acid solution of 1.5mol/L, 30 minutes are kept the temperature, valuable element can efficiently be leached, the leaching rate difference of Li, Ni, Co and Mn
It is 99.61%, 98.92%, 99.09% and 99.05%.
Embodiment 5
The waste and old LiMn that certain Battery Plant provides2O4Battery, by battery after the molten discharge in liquid of KCl 24 hours, machinery is split,
Obtain battery case, diaphragm, electrolyte, just positive piece and cathode pole piece.Anode pole piece is cut into the fragment of size about 2 × 2cm,
The mass percent of each element is as follows in the pole piece: Li 3.92%, Mn 52.59%, Al 12.11%, C 3.984%.It should
Positive fragment and sodium hydroxide are that 6:1 is placed in vibration grinding 4.0 minutes in vibration sample grinding machine in mass ratio, obtain positive electrode powder
The mixture at end and sodium hydroxide, gained powder is placed in electric furnace and is warming up under protection of argon gas with 6 DEG C of rates per minute
380 DEG C, 60 minutes are kept the temperature, thermal response product is obtained.Thermal response product is added to 85 DEG C of 1.5mol/L NaOH and 0.2mol/L
Na3PO4Mixed solution in, leach 2.5 hours, up to 100%, the leaching rate of fluorine is 95.5% for the leaching rate of aluminium, is obtained by filtration and contains
Aluminium and fluorine-containing solution and alkali leached mud.Gained alkali leached mud is added in the sulfuric acid solution of 40 DEG C of 1.5mol/L, keeps the temperature 30 points
Clock can efficiently leach valuable element, and the leaching rate of Li and Mn are respectively 99.89% and 99.76%.Gained cathode pole piece is then set
It is heat-treated 45 minutes at 500 DEG C in the tube furnace of nitrogen protection, by vibrosieve, graphite powder is made to fall off from copper foil,
Obtain copper foil and graphite powder.
Embodiment 6
Certain old and useless battery disassembles the old and useless battery positive electrode that workshop provides, and composition includes LiCoO2、LiNiO2、
LiMn2O4、LiNixCoyMn1-x-yO2、LiNixCoyAl1-x-yO2Etc. a variety of anodes, while also containing a small amount of cathode pole piece, by these
Pole piece is ground to powder of the partial size less than 2 microns.Positive electrode powder is placed in electric furnace per minute with 6 DEG C under protection of argon gas
Rate be warming up to 550 DEG C, keep the temperature 60 minutes, obtain thermal response product.Thermal response product is added to 85 DEG C of 1.5mol/L
NaOH and 0.2mol/L Na3PO4Mixed solution in, leach 2.5 hours, the leaching rate of aluminium is up to 100%, the leaching rate of fluorine
96.7%, it is obtained by filtration containing aluminum solutions and alkali leached mud.Gained alkali leached mud is added to the phosphoric acid solution of 80 DEG C of 2.5mol/L
In, 60 minutes are kept the temperature, valuable element can efficiently be leached, the leaching rate of Li, Ni, Co and Mn are respectively 99.93%, 99.77%,
99.58% and 99.29%.Acid leaching slag is graphite, can be recycled and recycles.
Comparative example 1
The LiNi of certain Battery PlantxCoyMn1-x-yO2Anode pole piece leftover pieces, the mass percent of each essential element is such as in pole piece
Under: Li 7.01%, Ni 15.32%, Co 15.23%, Mn 15.14%, Al 10.57%, C 4.91%.Not by the pole piece
560 DEG C are warming up to 5 DEG C of rates per minute under protection of argon gas through broken be placed directly in electric furnace, 60 minutes is kept the temperature, obtains hot
Reaction product.The thermal response product is added in 85 DEG C of 3.5mol/L NaOH solution after broken, is leached 1.5 hours, the leaching of aluminium
For extracting rate up to 100%, the leaching rate of lithium is 11.3%, and solution and alkali leached mud containing lithium and aluminium is obtained by filtration.Gained was contained
In the sulfuric acid solution for the 1.5mol/L that the alkali leached mud for crossing metallic element is added 80 DEG C, 30 minutes are kept the temperature, the leaching of Ni, Co and Mn
Rate is respectively 38.79%, 39.93% and 49.11%.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of method for recycling valuable element from waste and old lithium ion battery, which comprises the steps of:
S1: Mechanical Crushing is carried out after waste and old lithium ion battery is discharged, obtains anode pole piece and cathode pole piece；
S2: the anode pole piece is crushed and obtains positive electrode powder；By the positive electrode powder non-oxidizing atmosphere,
It is reacted at 400 DEG C~750 DEG C, obtains thermal response product；
The cathode pole piece is placed at 450~600 DEG C after being heat-treated, obtains copper foil and graphite powder by mechanical oscillation.
2. the method according to claim 1, wherein the reaction temperature of positive electrode powder described in S2 step is
400~600 DEG C.
3. the method according to claim 1, wherein in S2 step, by the positive electrode powder and alkali salt
After mixing, is reacted at non-oxidizing atmosphere, 300 DEG C~750 DEG C, obtain thermal response product；It is preferred that at 300~550 DEG C
It is reacted.
4. method described in any one of claim 1 to 3, which is characterized in that further include S3 after the S2 step:
The thermal response product is mixed with water or alkaline solution, makes therein to dissolve containing lithium and aluminium-containing substance；Through being separated by solid-liquid separation
Solution and alkali leached mud containing lithium and aluminium are obtained afterwards.
5. method described in any one of claim 1 to 3, which is characterized in that further include S3 ' after the S2 step:
The thermal response product is mixed with water or alkaline solution and fluorine transforming agent, obtains aluminium-containing substance and fluoride therein
Dissolution, obtains after being separated by solid-liquid separation containing aluminium and fluorine-containing solution and alkali leached mud；
The fluorine transforming agent is preferably one of sodium phosphate, potassium phosphate, dibastic sodium phosphate, potassium hydrogen phosphate or more than one mixing
Object.
6. the method according to any one of claim 3~5, which is characterized in that the alkali salt is sodium hydroxide, oxygen
Change sodium, sodium peroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium oxide, potassium peroxide, potassium carbonate, one in saleratus
Kind or more than one mixture.
7. the method according to any one of claim 4~6, which is characterized in that the alkaline solution is sodium hydroxide, oxygen
Change one of sodium, sodium peroxide, potassium hydroxide, potassium oxide, potassium peroxide or more than one solution；It is preferred that the alkalinity is molten
The concentration of liquid is 0.1~5.0mol/L.
8. the method according to any one of claim 4~7, which is characterized in that be dissolved in 50 described in S3 or S3 ' step
It is carried out at~95 DEG C.
9. the method according to any one of claim 4~8, which is characterized in that further include S4:
The alkali leached mud is mixed with acidic aqueous solution, dissolves valuable element；
It is preferred that the acidic aqueous solution be one of hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, ethylenediamine tetra-acetic acid or it is a kind of with
The aqueous solution of upper mixture；
It is preferred that the ratio of the alkali leached mud and the acidic aqueous solution is 1:3~1:20.
10. method according to claim 1 to 9, which is characterized in that the valuable element be Li, Ni, Co with
And one of Mn or a variety of；It is preferred that the active material in the anode pole piece is LiCoO2、LiNiO2、LiMn2O4、
LiNixCoyMn1-x-yO2、LiNixCoyAl1-x-yO2One of or more than one mixture.
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Application publication date: 20191008 |