CN117374443A - Pretreatment method for improving performance of positive electrode material in battery material regeneration process - Google Patents
Pretreatment method for improving performance of positive electrode material in battery material regeneration process Download PDFInfo
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- CN117374443A CN117374443A CN202311218446.7A CN202311218446A CN117374443A CN 117374443 A CN117374443 A CN 117374443A CN 202311218446 A CN202311218446 A CN 202311218446A CN 117374443 A CN117374443 A CN 117374443A
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- Prior art keywords
- lithium
- positive electrode
- sodium
- electrode material
- battery
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 89
- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000011069 regeneration method Methods 0.000 title claims abstract description 32
- 230000008929 regeneration Effects 0.000 title claims abstract description 31
- 230000008569 process Effects 0.000 title claims abstract description 21
- 238000002203 pretreatment Methods 0.000 title claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 83
- 230000007797 corrosion Effects 0.000 claims abstract description 49
- 238000005260 corrosion Methods 0.000 claims abstract description 49
- 238000001354 calcination Methods 0.000 claims abstract description 47
- 239000003112 inhibitor Substances 0.000 claims abstract description 43
- 239000011734 sodium Substances 0.000 claims abstract description 41
- 239000011230 binding agent Substances 0.000 claims abstract description 36
- 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 abstract description 34
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 34
- 239000007787 solid Substances 0.000 claims abstract description 32
- 239000006258 conductive agent Substances 0.000 claims abstract description 24
- 239000010926 waste battery Substances 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000002699 waste material Substances 0.000 claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011888 foil Substances 0.000 claims abstract description 11
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 11
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 10
- 239000011149 active material Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000002033 PVDF binder Substances 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 10
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 9
- -1 Polytetrafluoroethylene Polymers 0.000 claims description 8
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 5
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 5
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 4
- WFSRWJJESXWWSH-UHFFFAOYSA-N [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] Chemical compound [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] WFSRWJJESXWWSH-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 3
- XLCPLIJTRIGVDU-UHFFFAOYSA-N [O-2].[Mn+2].[Ni+2].[Na+] Chemical compound [O-2].[Mn+2].[Ni+2].[Na+] XLCPLIJTRIGVDU-UHFFFAOYSA-N 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 3
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 2
- CQPZCUVAECLXTC-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[Na+].[Ni+2] Chemical compound [Mn](=O)(=O)([O-])[O-].[Na+].[Ni+2] CQPZCUVAECLXTC-UHFFFAOYSA-N 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 description 57
- 230000001502 supplementing effect Effects 0.000 description 19
- 238000009616 inductively coupled plasma Methods 0.000 description 18
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000010405 anode material Substances 0.000 description 9
- 230000006378 damage Effects 0.000 description 9
- 230000007812 deficiency Effects 0.000 description 9
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 230000008439 repair process Effects 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000001172 regenerating effect Effects 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910000863 Ferronickel Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 230000009469 supplementation Effects 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent 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
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention belongs to the field of recovery of waste power lithium ion batteries and sodium ion batteries, and discloses a pretreatment method for improving the performance of a positive electrode material in the regeneration process of the battery material, which comprises the following steps: (1) disassembling waste batteries to obtain positive pole pieces; separating the aluminum foil to obtain a positive electrode material; (2) Mixing the positive electrode material with a solid corrosion inhibitor to obtain a mixture, and calcining at the temperature of 450-700 ℃ to obtain a positive electrode active material with the conductive agent and the binder removed, thereby completing pretreatment; wherein the solid corrosion inhibitor is a solid lithium-containing compound or a solid sodium-containing compound, which are alkaline by themselves and/or as decomposition products under calcination. According to the invention, the corrosion inhibitor is added into the positive electrode material in the process of removing the conductive agent and the binder, and reacts with the decomposition products of the conductive agent and the binder, so that the corrosion to the positive electrode material is reduced, and the electrochemical performance of the regenerated material obtained by the subsequent regeneration treatment can be effectively improved.
Description
Technical Field
The invention belongs to the field of recovery of waste power lithium ion batteries and sodium ion batteries, and particularly relates to a pretreatment method for improving the performance of a positive electrode material in the regeneration process of a battery material.
Background
Lithium ion batteries and sodium ion batteries are the current common rechargeable battery technology, have the advantages of high energy density, long cycle life, low self-discharge rate and the like, and are widely applied to portable electronic equipment, large-scale energy storage systems, electric vehicles, aerospace and other applications. Materials contained in the battery, such as metals (e.g., lithium, cobalt, nickel, etc.) and other rare elements, are limited resources and have high value. Waste batteries that are not properly treated may cause serious environmental pollution. Chemical and toxic substances in the battery, if entering soil, water sources or air, may cause harm to the ecosystem and human health. The chemicals in the waste batteries pose potential fire and explosion risks. Battery recycling is important for resource utilization, environmental protection, and safety. By recycling and reusing the batteries, sustainable development can be achieved and demand for limited resources reduced, while reducing environmental pollution and safety risks.
The invention relates to a method for regenerating NCMA positive electrode material by retired NCM positive electrode material, which mainly relies on high-temperature calcination technology to recover the positive electrode material of a battery, and has the application number of CN202111328619.1, and discloses a regeneration method for the positive electrode material of a lithium battery, wherein a retired ternary lithium ion battery is discharged and disassembled to obtain a positive electrode plate, and the positive electrode plate is treated by adopting an air current crushing method to obtain recovered coarse powder; grinding the recovered coarse powder to obtain recovered fine powder, and roasting for the first time to obtain a first mixed material; and sieving the first mixed material for three times to remove aluminum particles, grinding, supplementing lithium and roasting to obtain the NCMA anode material. The method does not add a lithium source during the first roasting, and aims to remove the conductive agent and the binder, and damage to the positive electrode material in the removing process is not considered. The second firing is preceded by lithium addition, and in order to compensate for the missing lithium for regeneration, the amount of lithium addition is usually 1.05 times or more the molar amount of missing lithium.
The invention discloses a regeneration repair treatment method of a ternary positive electrode material of a lithium ion battery, which is named as a regeneration repair treatment method of the ternary positive electrode material of the lithium ion battery and has the application number of CN 202010934418.5. Firstly, adding a dead ternary positive electrode material of a lithium ion battery into DMF to remove electrolyte, soaking and washing the electrolyte by NMP to ensure that the thickness of a CEI film on the surface is less than or equal to 10nm so as to remove PVDF on the surface and organic lithium salt components in the CEI film, and then, carrying out annealing treatment to further remove redundant PVDF; and after hydrothermal lithium supplementing treatment, determining the high-temperature calcination temperature and time according to the thickness of the CEI film, so that LiOH remained on the surface and inorganic lithium salt in the CEI film react with carbon dioxide in the air to generate lithium carbonate molten salt, and further react with rock salt on the surface of the material to generate the repaired layered ternary material. In order to remove the conductive agent and the binder PVDF, the method firstly uses an organic reagent for soaking, then carries out annealing treatment to remove thoroughly, has a complex process, and also does not consider the damage of the binder to the anode material in the annealing process.
Disclosure of Invention
In order to overcome the defect or improvement requirement of the prior art, the invention aims to provide a pretreatment method for improving the performance of a positive electrode material in the regeneration process of the battery material, and the main binder used by the positive electrode plate of the battery is a fluorine-containing binder (such as polyvinylidene fluoride (PVDF) and Polytetrafluoroethylene (PTFE)), so as to overcome the defect that decomposition products can corrode the positive electrode material in the binder removal process and damage the structure of the positive electrode material and influence the regeneration effect of the positive electrode active material. The pretreatment method can effectively improve the electrochemical performance of the regenerated battery anode material.
In order to achieve the above object, according to the present invention, there is provided a pretreatment method for improving the performance of a regenerated positive electrode material in a process of regenerating a battery material, comprising the steps of:
(1) Disassembling the waste batteries to obtain positive pole pieces; then, separating an aluminum foil in the positive electrode plate from a material layer on the positive electrode plate to obtain a positive electrode material; wherein the waste battery is a waste lithium ion battery or a waste sodium ion battery;
(2) Mixing the positive electrode material obtained in the step (1) with a solid corrosion inhibitor to obtain a mixture, and calcining at the temperature of 450-700 ℃ to obtain a positive electrode active material with the conductive agent and the binder removed, thereby completing pretreatment;
wherein, when the waste battery is a waste lithium ion battery, the solid corrosion inhibitor is a solid lithium-containing compound, and the solid lithium-containing compound itself and/or decomposition products under calcination are alkaline;
when the waste battery is a waste sodium ion battery, the solid corrosion inhibitor is a solid sodium-containing compound, which is alkaline in itself and/or the decomposition products upon calcination.
As a further preferred aspect of the present invention, in the step (2), when the solid corrosion inhibitor is a solid lithium-containing compound, the molar ratio of the lithium content of the solid corrosion inhibitor to the active material contained in the battery positive electrode material corresponding to the waste battery is 0.5% to 10%;
when the solid corrosion inhibitor is a solid sodium-containing compound, the molar ratio of the sodium content of the solid corrosion inhibitor to the active material contained in the battery positive electrode material corresponding to the waste battery is 0.5-10%.
In a further preferred aspect of the present invention, in the step (1), the binder in the positive electrode sheet is at least one of polyvinylidene fluoride (PVDF) and Polytetrafluoroethylene (PTFE).
As a further preferred aspect of the present invention, in the step (1), the waste battery is a waste lithium ion battery, and the positive electrode material includes lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium cobalt oxide, lithium nickel manganese oxide, and lithium manganese oxide;
or the waste battery is a waste sodium ion battery, and correspondingly, the positive electrode material comprises sodium vanadium phosphate, sodium nickel manganese oxide and sodium nickel iron manganese oxide.
As a further preferred aspect of the present invention, in the step (2), the calcination atmosphere in which the calcination is performed is one or more of air, oxygen, argon, and hydrogen;
preferably, when the positive electrode material is nickel cobalt lithium manganate, nickel cobalt lithium aluminate, lithium cobaltate, nickel lithium manganate, nickel sodium manganate or nickel iron sodium manganate, the calcining atmosphere in which the calcining is performed is one or more of air or oxygen;
when the positive electrode material is lithium iron phosphate or sodium vanadium phosphate, the calcining atmosphere in which the calcination is performed is one or more of argon or hydrogen.
As a further preferred aspect of the present invention, in the step (2), the time of the calcination is not more than 3 hours.
As a further preferred aspect of the present invention, in the step (2), the solid lithium-containing compound is selected from one or more of lithium hydroxide and its hydrate, lithium carbonate, lithium oxide, lithium oxalate, lithium acetate and its hydrate;
the solid sodium-containing compound is selected from one or more of sodium hydroxide, sodium carbonate, sodium oxide, sodium oxalate, sodium acetate and hydrates thereof.
Compared with the prior art, the technical scheme of the invention is characterized in that the corrosion inhibitor (such as lithium-containing compound and sodium-containing compound) is introduced and the pretreatment is carried out at the combustion temperature of 450-700 ℃, so that corrosive hydrogen fluoride generated in the calcining process of the conductive agent and the binder (such as polyvinylidene fluoride PVDF and polytetrafluoroethylene PTFE) can be effectively inhibited, holes and cracks are prevented from being generated by the hydrogen fluoride etching material, the structure of the active material is seriously damaged, and the electrochemical performance of the finally regenerated anode active material is improved. The invention uses lithium-containing compounds (such as lithium hydroxide, lithium carbonate, lithium oxide, lithium oxalate, lithium acetate) or sodium-containing compounds (sodium hydroxide, sodium carbonate, sodium oxide, sodium oxalate, sodium acetate) as corrosion inhibitors, and these materials themselves or their products after decomposition at high temperature (i.e. 450 ℃ to 700 ℃) are alkaline and are easily reacted with hydrogen fluoride (fluorine-containing binder decomposition products), so that they can be used as positive electrode corrosion inhibitors. Calcination temperatures of 450-700 ℃ are used because currently commercial conductive agents are carbon materials that decompose at 450 ℃ (in the case of conductive agent carbon black, the starting decomposition temperature of the carbon black is 450 ℃), and therefore the temperature is a lower limit; and when the temperature exceeds 700 c, the crystal structure of the active material is greatly changed, so that the temperature is an upper limit.
In the pretreatment method of the present invention, the amount of corrosion inhibitor introduced (the amount of the substance) may preferably be 0.5% -10% of the nominal value of the amount of active material substance (i.e., the active material contained in the original battery positive electrode material corresponding to the waste battery), and the amount is very small (while the amount of new lithium source or sodium source which is often required to be introduced in the conventional regeneration treatment is generally 1.05 times or more of the amount of the substance of the missing lithium or sodium so as to perform lithium and sodium supplementation, and the amount of missing lithium or sodium is generally more than 10%, even 20% for the positive electrode of the waste lithium ion battery or sodium ion battery, which is significantly higher than the corrosion inhibitor used in the pretreatment process of the present invention). The corrosion inhibitor of the present invention is used in small amounts because it is not used for the purpose of directly repairing the positive electrode material, but for reducing corrosion to the positive electrode material during binder removal (of course, this will also objectively achieve preliminary lithium/sodium supplementation).
In particular, the invention can achieve the following beneficial technical effects:
1. the invention can reduce the corrosion of the fluorine-containing binder to the anode material in the heat treatment removal process,
2. the invention carries out simple pre-repair on the material, and the pre-repair enables the active material to show better electrochemical performance through subsequent regeneration operation.
3. The positive electrode active material obtained by the pretreatment method and after the conductive agent and the binder are removed can be used as a precursor and applied to the subsequent lithium supplementing calcination post-treatment. The precursor crystal for regeneration obtained by the invention has an intact structure and is beneficial to subsequent further repair.
By utilizing the pretreatment method disclosed by the invention, the subsequent regenerated product has better electrochemical performance in cooperation with the regeneration treatment (namely, the post-treatment) of the existing lithium/sodium ion battery anode active material in the prior art.
Taking the recycling of lithium ion batteries as an example, active substances, conductive agents and organic binders mixed in the positive electrode materials need to be effectively removed before the materials are regenerated after the retired positive electrode materials of the lithium ion batteries are separated from the pole pieces. The conventional method is to remove the conductive agent and the binder by high temperature calcination pretreatment. The current binder commonly used for the positive electrode plate of the battery is a fluorine-containing binder (such as polyvinylidene fluoride PVDF and polytetrafluoroethylene PTFE), the conductive agent is carbon black, after the battery is retired, the valuable part in the positive electrode plate is a positive electrode active material (such as lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium cobalt oxide, lithium nickel manganese oxide, lithium manganese oxide, sodium vanadium phosphate, sodium nickel manganese oxide, sodium nickel iron manganese oxide and the like), the conductive agent and the binder are all required to be cleaned to regenerate the subsequent positive electrode material, and the conventional common pretreatment removal method comprises the following three steps: 1. the PVDF is dissolved by the organic solvent (the organic solvent is toxic and expensive), but the carbon black cannot be dissolved, and the regeneration is realized by carrying out lithium supplementing calcination after the carbon black is removed by subsequent calcination treatment. 2. The method comprises the steps of crushing and sorting, namely separating part of active matters from the conductive agent and the binder, wherein the active matters cannot be completely separated due to the bonding effect of the binder, and if pure active matters are required to be obtained, the subsequent calcination is required to remove impurities, and then the lithium supplementing calcination is carried out to realize regeneration. 3. The direct calcination treatment, the direct calcination conductive carbon black is oxidized into carbon dioxide, and the fluorine-containing organic binder is completely decomposed.
The inventor finds that carbon black and fluorine-containing organic binder are remained in the anode material separated from the retired battery in research and development, carbon dioxide is generated by the carbon black in the calcining process, meanwhile, corrosive hydrogen fluoride is generated by the fluorine-containing organic binder, the gaseous hydrogen fluoride has extremely high reactivity and can react with the anode active material, holes and cracks are generated by etching the material, the structure of the active material is seriously damaged, and the subsequent material regeneration is not facilitated. The present invention has found that since the substance that corrodes the positive electrode active material is hydrogen fluoride, it preferentially reacts with the alkaline substance; based on this, the present invention reacts with the generated hydrogen fluoride by adding a small amount of alkaline lithium source or sodium source as a corrosion inhibitor to the positive electrode material, which has two benefits: 1. the corrosion of the positive electrode active material by hydrogen fluoride can be reduced. 2. While reducing corrosion, the material is subjected to a simple pre-repair that results in the active material exhibiting better electrochemical performance through subsequent regeneration operations.
Compared with the recovery of the electrode material into the original upstream material (such as lithium carbonate material, lithium hydroxide material, cobalt oxide, manganese oxide and other transition metal oxide materials), the step of directly repairing and regenerating the electrode material is simpler, the performance repairing can be realized through simple lithium supplementing and regenerating, the existing repairing research is satisfied that compared with the waste material, the electrochemical performance of the regenerated material is improved, and the careful research on each step is lacking, so that even the performance is improved, the improvement space still exists.
The prior art generally comprises the following links for repairing and regenerating the battery, namely: separating positive electrode material, removing impurities, supplementing lithium, mixing and regenerating. The invention focuses on the impurity removal stage, and improves the performance of the subsequent regenerated material by reducing the damage of the impurity removal stage to the structure of the anode material. The impurity removal stage is a stage which is easy to neglect, and damage caused by the impurity removal process in morphology can be eliminated in the subsequent lithium supplementing regeneration process. The invention discovers that if the crystal structure morphology of the original material is damaged in the impurity removal stage, even if the subsequent lithium supplementing regeneration process compensates the morphology damage (the damage cannot be observed from the morphology), the damage is reflected on the electrochemical performance of the regenerated material, and the lithium supplementing efficiency is influenced. The invention uses the calcination pretreatment under the participation of the corrosion inhibitor at 450-700 ℃ to preserve the crystal structure of the anode material as much as possible, and the regenerated material obtained by conventional lithium supplementing calcination post-treatment has better electrochemical performance and improves the lithium supplementing efficiency.
Drawings
FIG. 1 is an XRD pattern of a treated lithium iron phosphate precursor material of example one and an XRD pattern of a treated lithium iron phosphate precursor material without corrosion inhibitor at the same temperature.
FIG. 2 is an XRD pattern of a ternary nickel cobalt manganese precursor material treated in example two and a ternary nickel cobalt manganese precursor material treated at the same temperature without corrosion inhibitor.
FIG. 3 is a scanning electron micrograph of a precursor material treated at 700℃and a scanning electron micrograph of a precursor material treated at the same temperature without corrosion inhibitor for example two. Wherein (a) in fig. 3 corresponds to the morphology of the positive electrode active material after conventional pretreatment without the use of a corrosion inhibitor, and (b) in fig. 3 corresponds to the morphology of the positive electrode active material after pretreatment with the addition of a corrosion inhibitor; the scales in the figures all represent 1 μm.
Fig. 4 is a charge-discharge curve of a nickel cobalt manganese ternary positive electrode material regenerated with the precursor treated in example two and a charge-discharge curve of a nickel cobalt manganese ternary positive electrode material regenerated with the precursor treated at the same temperature without corrosion inhibitor.
Fig. 5 is a charge-discharge curve of a lithium iron phosphate positive electrode material regenerated with the precursor treated in example one and a lithium iron phosphate positive electrode material regenerated with the precursor without corrosion inhibitor treated at the same temperature.
Fig. 6 is a charge-discharge curve of a lithium nickel manganese oxide cathode material regenerated with the precursor treated in example six and a lithium nickel manganese oxide cathode material regenerated with the precursor without corrosion inhibitor treated at the same temperature.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
In general, the pretreatment method for improving the performance of the regenerated positive electrode material in the regeneration process of the battery material according to the present invention may comprise the steps of:
(1) Disassembling waste batteries to obtain a positive electrode: and disassembling the waste batteries to obtain positive pole pieces, and separating the aluminum foil from a material layer on the positive pole.
(2) Pretreatment: and (3) mixing the positive electrode material obtained in the step (1) with a lithium-containing compound or a sodium-containing compound to obtain a mixture, and calcining the mixture at a high temperature to obtain the active material with the conductive agent and the binder removed.
The active material obtained by the pretreatment method can be used as a precursor and directly used for post-treatment for regeneration, so that the electrochemical performance of a regenerated product can be improved (that is, the pretreatment product obtained by the pretreatment method can be used for subsequent regeneration treatment, and the subsequent regenerated product has better electrochemical performance). For example, the steps may further comprise:
(3) Post-treatment: the method can be referred to the prior art, and lithium (or sodium) is supplemented first, and then high-temperature calcination treatment is performed (the calcination temperature is often equal to or higher than 750 ℃).
The following are specific examples:
example 1
And disassembling the waste lithium iron phosphate battery, taking out the positive electrode plate and the negative electrode plate wrapped by the internal diaphragm, extracting the diaphragm to obtain the positive electrode plate, and separating the aluminum foil from the active material on the positive electrode plate. 300g of a positive electrode material was obtained, and the positive electrode parameters of the battery were as follows: the mass ratio of the lithium iron phosphate active material to the conductive agent to the binder is 94:3:3, and the element ratio Li:Fe:P=0.850:1:1 (namely, li 1- x FePO 4 X=0.150), the actual mass ratio of the active material is about 93.9% taking into account the mass change due to lithium loss (see below for a specific calculation procedure), the mass is 281.7g, calculated from Li 1-x FePO 4 The amount of lithium iron phosphate material calculated by molar mass was 1.79mol.
The positive electrode material was uniformly mixed with 0.456g (0.004475 mol) of lithium oxalate, at which time the lithium content in the lithium oxalate was 0.5% of the amount of the positive electrode material substance (0.004475 ×2 ≡1.79×100% =0.5%), using H 2 the/Ar (volume ratio 5:95) mixture was calcined at 450℃for 2 hours to give 275g of precursor.
Calibrating the content of lithium missing in the precursor by using an inductively coupled plasma spectrometer (ICP) again, determining the element ratio Li:Fe:P=0.853:1:1 (the influence of lithium oxalate in the pretreatment on the content of Li is negligible), mixing 275g of the precursor with 13.80g (0.135 mol) of lithium oxalate, wherein the content of lithium-containing substances in the lithium oxalate is 1.05 times of the content of lithium missing (wherein the content of lithium missing is 275 g/mol (157.8 g/mol-6.9g/mol multiplied by 0.147) ×0.147), and wherein LiFePO is prepared by mixing the precursor with 13.80g (0.135 mol) of lithium oxalate, wherein the content of lithium missing is 275 g/mol-6.9g/mol multiplied by 0.147) 4 Is 157.8g/mol; the molar mass of Li is 6.9g/mol;0.147 =1-0.853, which is the amount of lithium deficiency), the mixture was calcined at 750 ℃ for 8 hours in an atmosphere of argon, to obtain a regenerated lithium iron phosphate positive electrode material.
Among these, ICP testing in the pretreatment step is an optional step, since the amount of lithium loss has little effect on the actual mass ratio of the active material. In the above embodiment, liFePO 4 The molar mass of (C) is denoted as M 0 ，Li 1-x FePO 4 The molar mass of (C) is denoted as M 1 Then, the actual mass ratio of the active material is calculated as follows:
(94×M 1 /M 0 )÷(94×M 1 /M 0 +3+3)
of course, for the waste batteries with unclear battery anode parameters, the aluminum foil in the anode plate and the material layer on the anode plate can be separated to obtain the anode material, and then the mass ratio of the active material in the anode material is determined by thermogravimetric TG-DSC.
Example two
And disassembling the waste nickel-cobalt-manganese ternary battery, taking out the positive electrode plate and the negative electrode plate wrapped by the internal diaphragm, extracting the diaphragm to obtain the positive electrode plate, and separating the aluminum foil from the active material on the positive electrode plate. 500g of a positive electrode material was obtained, and the positive electrode parameters of the battery were as follows: the mass ratio of the nickel-cobalt-manganese ternary active material to the conductive agent to the binder is 92:4:4, the inductively coupled plasma spectrometer (ICP) test is carried out, the element ratio Li:Ni:Co:Mn=0.8:0.6:0.2:0.2 in the active material is determined, the actual mass ratio of the active material is about 91.9 percent in consideration of the mass change caused by lithium loss, the mass is 459.5g, the amount of the ternary nickel-cobalt-manganese active material obtained by calculation is 4.81mol, the positive electrode material is uniformly mixed with 2.018g (4.81 x 0.01= 0.0481 mol) of lithium hydroxide monohydrate, the lithium content in the lithium hydroxide monohydrate is 1 percent of the amount of the positive electrode material, and the precursor is obtained by calcining for 2h at 700 ℃ by using air.
Calibrating the content of lithium missing in the precursor by using an inductively coupled plasma spectrometer (ICP), wherein the element ratio of the precursor is Li: ni: co: mn=0.8:0.6:0.2:0.2, mixing 458g of the precursor with 42.2g (1.007 mol) of lithium hydroxide monohydrate, and the lithium content in the lithium hydroxide monohydrate is 1.05 times of the lithium missing (wherein the lithium missing amount is 458 g/mol-96.9 g/mol multiplied by 0.2), wherein the LiNi is LiNi 0.6 Co 0.2 Mn 0.2 O 2 The molar mass of (2) is 96.9g/mol; the molar mass of Li is 6.9g/mol;0.2 =1-0.8, lithium deficiency), and calcining the mixture in air at 800 ℃ for 8 hours to obtain the regenerated ternary nickel-cobalt-manganese positive electrode material.
Example III
And disassembling the waste lithium cobalt oxide battery, taking out the positive electrode plate and the negative electrode plate wrapped by the internal diaphragm, extracting the diaphragm to obtain the positive electrode plate, and separating the aluminum foil from the active material on the positive electrode plate. 300g of a positive electrode material was obtained, and the positive electrode parameters of the battery were as follows: the mass ratio of the lithium cobaltate active material, the conductive agent and the binder is 95:2:3, the element ratio Li:Co=0.75:1.0 in the active material is determined by an inductively coupled plasma spectrometer (ICP) test, the actual mass ratio of the active material is about 94.9 percent in consideration of the mass change caused by lithium loss, the mass is 284.7g, the lithium cobaltate active material is obtained by calculation, the positive electrode material is uniformly mixed with 10.94g (2.96 x 0.1/2=0.148 mol) of lithium carbonate, the lithium content in the lithium carbonate is 10 percent of the mass of the positive electrode material, and 285g of precursor is obtained by calcining for 2h at 500 ℃ by using air.
Calibrating the content of lithium missing in the precursor by using an Inductively Coupled Plasma (ICP) spectrometer, determining that the element ratio of the obtained precursor is Li: co=0.8:1.0, mixing 285g of the precursor with 23g of lithium carbonate,the amount of lithium contained in lithium carbonate was 1.05 times as much as that of lithium deficiency (wherein the amount of lithium deficiency was 285 g/mol-6.9 g/mol. Times.0.2; wherein LiCoO) 2 Is 97.9g/mol; the molar mass of Li is 6.9g/mol;0.2 =1-0.8, lithium deficiency), and calcining the mixture in oxygen at 900 ℃ for 8 hours to obtain the regenerated lithium cobalt oxide positive electrode material.
Example IV
And disassembling the waste sodium nickel iron manganate battery, taking out the positive electrode plate and the negative electrode plate wrapped by the internal diaphragm, extracting the diaphragm to obtain the positive electrode plate, and separating the aluminum foil from the active material on the positive electrode plate. 500g of a positive electrode material was obtained, and the positive electrode parameters of the battery were as follows: the mass ratio of the sodium ferronickel manganate ternary active material to the conductive agent to the binder is 94:3:3, the element ratio Na:Ni:Fe:Mn=0.85:0.33:0.33 in the active material is determined by an inductively coupled plasma spectroscope (ICP) test, the actual mass ratio of the active material is about 93.8 percent in consideration of the mass change caused by sodium loss, the mass is 469g, the amount of the sodium ferronickel manganate active material is 4.34mol according to calculation, the positive electrode material is uniformly mixed with 8.7g (4.34:0.05= 0.2172 mol) of sodium hydroxide, the sodium hydroxide content is 5 percent of the amount of the positive electrode material at the moment, and 470g of precursor is obtained by calcining for 2h at 600 ℃ by using air.
Calibrating the content of sodium missing in the precursor by using an Inductively Coupled Plasma (ICP) spectrometer, wherein the element ratio of Na to Ni to Fe to Mn=0.87:0.33:0.33:0.33, mixing 470g of precursor with 23.76g of sodium hydroxide, wherein the sodium content in the sodium hydroxide is 1.05 times of the sodium missing amount (wherein the sodium missing amount is 470 g/mol (111.4 g/mol-23.0g/mol multiplied by 0.13), and wherein the NaNi is prepared by mixing the precursor with the sodium hydroxide 0.333 Fe 0.333 Mn 0.333 O 2 Is 111.4g/mol; the molar mass of Na is 23.0g/mol;0.13 =1-0.87, sodium deficiency), and calcining the mixture in air at 800 ℃ for 8 hours to obtain the regenerated sodium nickel iron manganese oxide positive electrode material.
Example five
And disassembling the waste sodium vanadium phosphate battery, taking out the positive electrode plate and the negative electrode plate wrapped by the internal diaphragm, extracting the diaphragm to obtain the positive electrode plate, and separating the aluminum foil from the active material on the positive electrode plate. 300g of a positive electrode material was obtained, and the positive electrode parameters of the battery were as follows: the mass ratio of the active material to the conductive agent to the binder is 95:2.5:2.5, the element ratio Na:V:P=2.4:2.0:3.0 in the active material is determined by an inductively coupled plasma spectroscope (ICP) test, the actual mass ratio of the active material is about 94.9 percent in consideration of the mass change caused by sodium loss, the mass is 284.7g, the amount of the active material of vanadium sodium phosphate is calculated to be 0.64mol, the positive electrode material is uniformly mixed with 5.1g (0.64 x 3.0.05/2=0.048 mol) of sodium carbonate, at the moment, the sodium content in the sodium carbonate is 5 percent of the amount of the positive electrode material, and the precursor is obtained by calcining for 2h at 550 ℃ by using argon.
Calibrating the content of sodium missing in the precursor by using an Inductively Coupled Plasma (ICP) spectrometer, wherein the element proportion in the precursor is Na: V: P=2.49:2.0:3.0, then mixing 285g of the precursor with 18.2g of sodium carbonate, and the content of sodium-containing substances in the sodium carbonate is 1.05 times of the content of sodium missing (wherein the content of sodium missing is 285 g/455.9 g/mol-23.0g/mol×0.51) ×0.51, wherein the content of Na 3 V 2 (PO 4 ) 3 Has a molar mass of 455.9g/mol; the molar mass of Na is 23.0g/mol;0.51 =3-2.49, sodium deficiency), and calcining the mixture in argon at 750 ℃ for 8 hours to obtain the regenerated sodium vanadium phosphate positive electrode material.
Example six
And disassembling the waste lithium nickel manganese oxide battery, taking out the positive electrode plate and the negative electrode plate wrapped by the internal diaphragm, extracting the diaphragm to obtain the positive electrode plate, and separating the aluminum foil from the active material on the positive electrode plate. 400g of positive electrode material was obtained, and the positive electrode parameters of the battery were as follows: the mass ratio of the active material to the conductive agent to the binder is 90:5:5, the Inductively Coupled Plasma (ICP) test shows that the element ratio Li:Ni:Mn=0.7:0.5:1.5 in the lithium nickel manganese oxide active material is determined, the actual mass ratio of the active material is about 89.9 percent in consideration of the mass change caused by lithium loss, the mass is 359.6g, the lithium nickel manganese oxide active material is obtained by calculation according to the calculated mass ratio of 1.99mol, the positive electrode material is uniformly mixed with 0.2974g (1.99:0.01/2=0.0099 mol) of lithium oxide, the lithium content in the lithium oxide is 1 percent of the mass of the positive electrode material at the moment, and 358g of precursor is obtained by calcining for 2h at 650 ℃.
Calibrating the content of the lithium missing in the precursor by using an Inductively Coupled Plasma (ICP) spectrometer, wherein the element proportion in the precursor is Li: ni: mn=0.7:0.5:1.5, mixing 358g of the precursor with 9.33g of lithium oxide, and the content of lithium-containing substances in the lithium oxide is 1.05 times of the content of the lithium missing (wherein the content of the lithium missing is 358 g/mol (182.7 g/mol-6.9g/mol×0.3) multiplied by 0.3), wherein the content of the lithium missing is LiNi 0.5 Mn 1.5 O 4 Is 182.7g/mol; the molar mass of Li is 6.9g/mol;0.3 =1-0.7, lithium deficiency), and calcining the mixture in oxygen at 900 ℃ for 8 hours to obtain the regenerated lithium nickel manganese oxide positive electrode material.
FIG. 1 shows XRD patterns of a precursor material treated in example I and XRD patterns of a precursor material treated at the same temperature without corrosion inhibitor, wherein the main peak intensity of the lithium iron phosphate material treated in the invention is higher than that of the lithium iron phosphate treated without corrosion inhibitor, and the peak shape is sharper, thus indicating that the crystal structure of the lithium iron phosphate recovered by the method is relatively better.
FIG. 2 shows XRD patterns of a precursor material treated in the second embodiment and XRD patterns of a precursor material treated at the same temperature and without corrosion inhibitor, wherein the XRD patterns of the ternary nickel-cobalt-manganese material treated in the invention have higher peak intensities and sharp peak shapes, and the XRD patterns of the ternary nickel-cobalt-manganese material treated without corrosion inhibitor are obviously weakened, so that the background noise is extremely high, and the crystal structure of the ternary nickel-cobalt-manganese material is destroyed to a certain extent.
FIG. 3 is a photograph of a second example of a scanning electron microscope of a precursor material treated at 700℃and a photograph of a precursor material treated at the same temperature without corrosion inhibitor, wherein the scale is 1. Mu.m, and it can be seen that after the ternary nickel cobalt manganese positive electrode material without corrosion inhibitor is calcined at 700℃to remove the conductive agent and the binder, obvious holes appear on the surface of each particle, which is caused by corrosion of gaseous hydrofluoric acid, and once 1% lithium hydroxide is added as a corrosion inhibitor, the lithium supplementing amount is far less than the lithium deficiency amount (20%) of the retired positive electrode material, but the integrity of the particles in the calcining process can be effectively maintained, which is beneficial to subsequent repair and regeneration.
FIG. 4 shows a charge-discharge curve of a nickel-cobalt-manganese ternary cathode material regenerated from a precursor treated in example two and a charge-discharge curve of a nickel-cobalt-manganese ternary cathode material regenerated from a precursor treated at the same temperature without corrosion inhibitor, wherein the reversible capacity of the precursor obtained by the conventional method after lithium supplementing regeneration is 162.3mAh/g, and the reversible capacity of the precursor obtained by the method after lithium supplementing regeneration is 172.7mAh/g, so that the performance is improved.
FIG. 5 shows a charge-discharge curve of a lithium iron phosphate positive electrode material regenerated from a precursor treated in example one and a charge-discharge curve of a lithium iron phosphate positive electrode material regenerated from a precursor treated at the same temperature without corrosion inhibitor, wherein the reversible capacity of the precursor obtained by the conventional method after lithium supplementing regeneration is 112mAh/g, and the reversible capacity of the precursor obtained by the method after lithium supplementing regeneration is 150mAh/g, so that the method is remarkably improved.
FIG. 6 shows a charge-discharge curve of a lithium nickel manganese oxide cathode material regenerated with the precursor treated in example six and a charge-discharge curve of a lithium nickel manganese oxide cathode material regenerated with the precursor treated at the same temperature without corrosion inhibitor, wherein the reversible capacity of the precursor obtained by the conventional method after lithium supplementing regeneration is 110.3mAh/g, and the reversible capacity of the precursor obtained by the method after lithium supplementing regeneration is 126.5mAh/g, so that the method is remarkably improved.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. A pretreatment method for improving the performance of a regenerated positive electrode material in the regeneration process of a battery material is characterized by comprising the following steps:
(1) Disassembling the waste batteries to obtain positive pole pieces; then, separating an aluminum foil in the positive electrode plate from a material layer on the positive electrode plate to obtain a positive electrode material; wherein the waste battery is a waste lithium ion battery or a waste sodium ion battery;
(2) Mixing the positive electrode material obtained in the step (1) with a solid corrosion inhibitor to obtain a mixture, and calcining at the temperature of 450-700 ℃ to obtain a positive electrode active material with the conductive agent and the binder removed, thereby completing pretreatment;
wherein, when the waste battery is a waste lithium ion battery, the solid corrosion inhibitor is a solid lithium-containing compound, and the solid lithium-containing compound itself and/or decomposition products under calcination are alkaline;
when the waste battery is a waste sodium ion battery, the solid corrosion inhibitor is a solid sodium-containing compound, which is alkaline in itself and/or the decomposition products upon calcination.
2. The pretreatment method according to claim 1, wherein in the step (2), when the solid corrosion inhibitor is a solid lithium-containing compound, the molar ratio of the lithium content of the solid corrosion inhibitor to the active material contained in the battery positive electrode material corresponding to the waste battery is 0.5 to 10%;
when the solid corrosion inhibitor is a solid sodium-containing compound, the molar ratio of the sodium content of the solid corrosion inhibitor to the active material contained in the battery positive electrode material corresponding to the waste battery is 0.5-10%.
3. The pretreatment method according to claim 1, wherein in the step (1), the binder in the positive electrode sheet is at least one of polyvinylidene fluoride (PVDF) and Polytetrafluoroethylene (PTFE).
4. The pretreatment method of claim 1, wherein in the step (1), the waste battery is a waste lithium ion battery, and the positive electrode material comprises lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium cobalt oxide, lithium nickel manganese oxide, and lithium manganese oxide;
or the waste battery is a waste sodium ion battery, and correspondingly, the positive electrode material comprises sodium vanadium phosphate, sodium nickel manganese oxide and sodium nickel iron manganese oxide.
5. The pretreatment method of claim 1, wherein in the step (2), the calcination atmosphere in which the calcination is performed is one or more of air, oxygen, argon, and hydrogen;
preferably, when the positive electrode material is nickel cobalt lithium manganate, nickel cobalt lithium aluminate, lithium cobaltate, nickel lithium manganate, nickel sodium manganate or nickel iron sodium manganate, the calcining atmosphere in which the calcining is performed is one or more of air or oxygen;
when the positive electrode material is lithium iron phosphate or sodium vanadium phosphate, the calcining atmosphere in which the calcination is performed is one or more of argon or hydrogen.
6. The pretreatment method of claim 1, wherein in the step (2), the calcination time is not more than 3 hours.
7. The pretreatment method according to claim 1, wherein in the step (2), the solid lithium-containing compound is selected from one or more of lithium hydroxide and a hydrate thereof, lithium carbonate, lithium oxide, lithium oxalate, lithium acetate and a hydrate thereof;
the solid sodium-containing compound is selected from one or more of sodium hydroxide, sodium carbonate, sodium oxide, sodium oxalate, sodium acetate and hydrates thereof.
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