CN114204151A - Method for repairing and modifying waste lithium ion battery positive electrode active material - Google Patents
Method for repairing and modifying waste lithium ion battery positive electrode active material Download PDFInfo
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- CN114204151A CN114204151A CN202111476718.4A CN202111476718A CN114204151A CN 114204151 A CN114204151 A CN 114204151A CN 202111476718 A CN202111476718 A CN 202111476718A CN 114204151 A CN114204151 A CN 114204151A
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- active material
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- lithium
- lithium ion
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- 239000002699 waste material Substances 0.000 title claims abstract description 74
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 58
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 41
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 66
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 30
- 239000003607 modifier Substances 0.000 claims abstract description 26
- 239000013589 supplement Substances 0.000 claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 230000008439 repair process Effects 0.000 claims abstract description 16
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000006182 cathode active material Substances 0.000 claims abstract description 11
- 238000004090 dissolution Methods 0.000 claims abstract description 11
- 239000006183 anode active material Substances 0.000 claims abstract description 9
- 238000000746 purification Methods 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 5
- 230000005012 migration Effects 0.000 claims abstract description 5
- 238000013508 migration Methods 0.000 claims abstract description 5
- 239000011241 protective layer Substances 0.000 claims abstract description 5
- 230000007797 corrosion Effects 0.000 claims abstract description 4
- 238000005260 corrosion Methods 0.000 claims abstract description 4
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- 230000001502 supplementing effect Effects 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- 239000012298 atmosphere Substances 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010405 anode material Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007785 strong electrolyte Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910001868 water Inorganic materials 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000003518 caustics Substances 0.000 abstract description 2
- 239000010793 electronic waste Substances 0.000 abstract description 2
- 239000011149 active material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000012612 commercial material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A method for repairing and modifying a waste lithium ion battery anode active material belongs to the field of resource treatment of electronic wastes. The organic solvent dissolution and the low-temperature aerobic heat treatment are combined to obtain a pure waste cathode active material, so that the high-efficiency enrichment and purification of the waste cathode active material are realized; uniformly mixing the waste positive active material with a lithium supplement additive and a coating modifier by combining lithium supplement and surface coating modification, supplementing the lithium element missing from the waste positive active material in a high-temperature solid-phase reaction mode, and forming a protective layer on the surface of the repair modified material; the corrosion effect of the electrolyte in the circulation process is reduced while the lithium ion and charge migration of the modified material is promoted, and the surface stability of the material is improved; through efficient enrichment and purification and high-temperature solid-phase reaction, the surface damaged structure and electrochemical performance of the waste positive electrode active material are recovered. The advantages are that: does not relate to corrosive agents such as strong acid, strong alkali and the like, shortens the technical process of recovery, and greatly reduces energy consumption and secondary pollution.
Description
Technical Field
The invention belongs to the field of resource treatment of electronic wastes, and particularly relates to a method for repairing and modifying a waste lithium ion battery positive electrode active material.
Background
The lithium ion battery has the advantages of long service life, no memory effect, high specific energy, strong environmental adaptability and the like, and is applied to the fields of new energy automobiles, large-scale wind power photoelectric energy storage, communication base station standby power supplies and the like. The lithium battery contains valuable metals such as nickel, cobalt, manganese, iron, copper, aluminum and the like, and the actual service life of the lithium battery is only two to three years, so that a large number of waste lithium ion batteries in the market cause severe pressure on environment and metal resource shortage, and the lithium battery needs to be subjected to efficient resource treatment.
The positive active material not only determines the overall electrochemical capacity of the battery, but also is the most economically valuable part of the battery composition. Due to the characteristics of the material and the working principle of the lithium ion battery, the structure of the positive active material can be changed after repeated cyclic charge and discharge, such as the phenomena of metal ion dissolution and structural change related to the surface structure, such as lithium ion loss, cation mixed discharge, surface side reaction and the like, and further the capacity attenuation of the battery is caused. The traditional recovery technology mainly comprises pyrometallurgy and hydrometallurgy, and is a resource recycling mode of decomposing and recombining valuable components and recovering the valuable components in the forms of metal ions, compounds and the like, and the mode has the defects of high energy consumption, long flow, easiness in causing secondary pollution and the like.
Aiming at the structural change of the anode active material, the simple supplement of the deficient lithium element is not enough to improve the interface stability of the material. Therefore, the introduction of the coating modifier can form a protective layer on the surface of the particles, reduce the side reaction of the anode active material and the electrolyte, and further improve the cycle performance of the material. In order to ensure the uniformity of the reaction between the lithium supplement additive and the coating modifier and the surface of the waste anode active material, a thin and uniform coating layer is formed on the surface of the particles, and the uniform mixing of the materials is the key of the subsequent high-temperature solid-phase reaction.
Enrichment and purification pretreatment of the waste positive active material is a precondition for subsequent resource recovery, and if impurities in the material are not completely removed, continuous side reactions are easily caused, so that raw material consumption and product properties are changed. Although the traditional mechanical separation pretreatment method can realize the dissociation of the active material and the current collector to a certain extent, the problems that the active material and organic matter are mixed after the current collector is crushed, and the like exist. The binder can be aged and failed after circulation, the original properties of the material are changed, and the binder cannot be completely dissolved by simple solvent dissolution. When the pole piece is manufactured, the particle coating is compacted and densified, a large amount of organic matters in the gaps of the particles cannot be removed by direct heat treatment, and partial organic matters still remain on the surfaces of the particles.
Disclosure of Invention
The technical problem is as follows: the invention aims to overcome the defects in the prior art and provides the method for repairing and modifying the active material of the anode of the waste lithium ion battery, which is simple, shortens the recovery path and reduces the production cost.
The technical scheme is as follows: in order to realize the aim, the method for repairing and modifying the waste lithium ion battery positive active material obtains the pure waste positive active material by combining organic solvent dissolution and low-temperature aerobic heat treatment, and realizes high-efficiency enrichment and purification of the waste positive active material; uniformly mixing the waste positive active material with a lithium supplement additive and a coating modifier by combining lithium supplement and surface coating modification, supplementing the lithium element missing from the waste positive active material in a high-temperature solid-phase reaction mode, and forming a protective layer on the surface of the repair modified material; the corrosion effect of the electrolyte in the circulation process is reduced while the lithium ion and charge migration of the modified material is promoted, and the surface stability of the material is improved; through efficient enrichment and purification and high-temperature solid-phase reaction, the surface damaged structure and electrochemical performance of the waste positive electrode active material are recovered.
The method comprises the following specific steps:
step S1, discharging and disassembling: and disassembling the fully discharged and air-dried waste lithium ion battery monomer.
Step S2, preprocessing: most of organic binders in the positive plate are dissolved and removed by adopting an organic solvent, and the waste positive active material is obtained by filtering, drying and screening the organic binders and removing residual ineffective binders and conductive agents through low-temperature aerobic heat treatment.
Step S3, uniformly mixing: and (4) detecting the waste positive electrode active material obtained in the step (S2), determining the content of each metal element, and fully grinding and mixing the waste positive electrode active material with the lithium supplement additive and the coating modifier according to a certain proportion.
Step S4, repairing and modifying: and (5) carrying out high-temperature solid-phase reaction on the uniformly mixed materials in the step (S3) in an aerobic atmosphere, and grinding, dispersing, cleaning and drying the products after the reaction is finished to obtain the final repair modified positive active material.
Preferably, the waste cathode active material includes, but is not limited to, currently mainstream commercial cathode materials; the anode material is a nickel-cobalt-manganese ternary material, lithium cobaltate and a lithium iron phosphate material; the nickel-cobalt-manganese ternary material is 111 type, 811 type, 622 type or 523 type.
Preferably, in step S1, the discharge mode is chemical discharge, and the lithium ion battery is prepared into a 5-20 wt% solution by using a strong electrolyte of sodium chloride and potassium chloride and water, and the waste lithium ion battery monomer is soaked in the strong electrolyte solution for 24-48h for sufficient discharge, and the positive plate, the negative plate, the diaphragm and the shell are obtained after disassembly.
Preferably, in step S2, the anode sheet obtained by disassembly is dried to remove the surface electrolyte, cut into small pieces with the size of about 1 × 1cm, and immersed into the organic solvent according to the solid-to-liquid ratio of 50-150g/L, the dissolution temperature is 60-95 ℃, the dissolution time is 40-150min, and the stirring speed is 100-500 rpm.
Preferably, in step S2, the organic solvent is one of solvents that are compatible with N-methyl pyrrolidone, dimethylformamide, and dimethylacetamide and an organic binder.
Preferably, in step S2, the solution in which most of the binder is dissolved is filtered, dried, and sieved to obtain a positive electrode material black powder and an aluminum foil, respectively, and the black powder is subjected to low-temperature aerobic heat treatment to remove the residual ineffective binder and the residual conductive agent.
Preferably, in step S2, the low-temperature aerobic heat treatment mode is a muffle furnace or a tube furnace heating device, the aerobic atmosphere is air or oxygen, the heat treatment conditions are a temperature rise rate of 5-20 ℃/min, a temperature of 400-.
Preferably, in step S3, the lithium supplement additive is one or more of lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide, and lithium peroxide; the coating modifier is one or more of nano-scale titanium dioxide, nano-scale alumina, nano-scale magnesium oxide and nano-scale lithium aluminate.
Preferably, in step S3, the lithium supplement additive, the coating modifier and the waste positive electrode active material are mixed according to a molar ratio and a mass fraction ratio, respectively, where the molar ratio of the lithium element to the transition metal element is (1.05-1.50): 1, and the mass fraction of the coating modifier in the mixed material is 0.5-2.0 wt%; in the grinding and mixing process, the grinding mode is ball milling by a roller ball mill, the ball-material ratio is 1: 5-20, the rotating speed is 100-.
Preferably, in step S4, the high-temperature solid-phase reaction mode is heating in a muffle furnace or a tubular furnace, the heating rate is 5-10 ℃/min, the reaction temperature is 700-; the aerobic atmosphere is air or oxygen.
Preferably, in step S4, in the grinding and dispersing process, the grinding manner is ball milling by a roller ball mill, the ball-to-material ratio is 1: 5-20, the rotation speed is 100-. And cleaning the ground product with absolute ethyl alcohol and deionized water respectively, and drying in a vacuum oven to obtain the final repair modified positive active material.
Has the advantages that: by adopting the technical scheme, the invention can realize complete removal of organic matters by improving the pretreatment mode, and avoids the problems of continuous side reaction, raw material consumption, product property change and the like caused by residual impurities in the active material. The introduction of the coating modifier forms a coating layer on the surface of the material, promotes the migration of ions and charges on the interface of the active material, simultaneously lightens the erosion effect of the electrolyte in the circulation process and stabilizes the surface structure of the material. Compared with the prior art, the method obtains the pure waste lithium ion battery anode active material by an efficient pretreatment technology combining organic solvent dissolution and low-temperature aerobic heat treatment, then uniformly mixes the pure waste lithium ion battery anode active material with a lithium supplement additive and a coating modifier, and recovers the surface damaged structure and electrochemical performance of the waste anode active material in a high-temperature solid-phase reaction mode to prepare the anode active material with excellent performance. The method does not relate to corrosive agents such as strong acid, strong alkali and the like, greatly reduces energy consumption and secondary pollution brought by the traditional resource process, provides a short-flow, low-cost and easy-to-operate resource technology for industrial large-scale recovery of the waste lithium ion positive electrode active material, and has wide practicability in the technical field.
Drawings
Fig. 1 is a graph of the cycling performance and coulombic efficiency of the three materials at 1C.
Fig. 2 is a graph of rate performance for three materials.
Detailed Description
In order to more intuitively illustrate the electrochemical performance of the surface-repaired positive electrode active material in the examples, which is compared with waste materials and commercial materials, the present invention is further explained below with reference to the accompanying drawings and specific examples:
according to the method for repairing and modifying the waste lithium ion battery positive active material, the pure waste positive active material is obtained by combining organic solvent dissolution and low-temperature aerobic heat treatment, so that the efficient enrichment and purification of the waste positive active material are realized; uniformly mixing the waste positive active material with a lithium supplement additive and a coating modifier by combining lithium supplement and surface coating modification, supplementing the lithium element missing from the waste positive active material in a high-temperature solid-phase reaction mode, and forming a protective layer on the surface of the repair modified material; the corrosion effect of the electrolyte in the circulation process is reduced while the lithium ion and charge migration of the modified material is promoted, and the surface stability of the material is improved; through efficient enrichment and purification and high-temperature solid-phase reaction, the surface damaged structure and electrochemical performance of the waste positive electrode active material are recovered. The method comprises the following specific steps:
step S1, discharging and disassembling: and disassembling the fully discharged and air-dried waste lithium ion battery monomer.
Step S2, preprocessing: most of organic binders in the positive plate are dissolved and removed by adopting an organic solvent, and the waste positive active material is obtained by filtering, drying and screening the organic binders and removing residual ineffective binders and conductive agents through low-temperature aerobic heat treatment.
Step S3, uniformly mixing: and (4) detecting the waste positive electrode active material obtained in the step (S2), determining the content of each metal element, and fully grinding and mixing the waste positive electrode active material with the lithium supplement additive and the coating modifier according to a certain proportion.
Step S4, repairing and modifying: and (5) carrying out high-temperature solid-phase reaction on the uniformly mixed materials in the step (S3) in an aerobic atmosphere, and grinding, dispersing, cleaning and drying the products after the reaction is finished to obtain the final repair modified positive active material.
Preferably, the waste cathode active material includes, but is not limited to, currently mainstream commercial cathode materials; the anode material is a nickel-cobalt-manganese ternary material, lithium cobaltate and a lithium iron phosphate material; the nickel-cobalt-manganese ternary material is 111 type, 811 type, 622 type or 523 type.
Preferably, in step S1, the discharge mode is chemical discharge, and the lithium ion battery is prepared into a 5-20 wt% solution by using a strong electrolyte of sodium chloride and potassium chloride and water, and the waste lithium ion battery monomer is soaked in the strong electrolyte solution for 24-48h for sufficient discharge, and the positive plate, the negative plate, the diaphragm and the shell are obtained after disassembly.
Preferably, in step S2, the anode sheet obtained by disassembly is dried to remove the surface electrolyte, cut into small pieces with the size of about 1 × 1cm, and immersed into the organic solvent according to the solid-to-liquid ratio of 50-150g/L, the dissolution temperature is 60-95 ℃, the dissolution time is 40-150min, and the stirring speed is 100-500 rpm.
Preferably, in step S2, the organic solvent is one of solvents that are compatible with N-methyl pyrrolidone, dimethylformamide, and dimethylacetamide and an organic binder.
Preferably, in step S2, the solution in which most of the binder is dissolved is filtered, dried, and sieved to obtain a positive electrode material black powder and an aluminum foil, respectively, and the black powder is subjected to low-temperature aerobic heat treatment to remove the residual ineffective binder and the residual conductive agent.
Preferably, in step S2, the low-temperature aerobic heat treatment mode is a muffle furnace or a tube furnace heating device, the aerobic atmosphere is air or oxygen, the heat treatment conditions are a temperature rise rate of 5-20 ℃/min, a temperature of 400-.
Preferably, in step S3, the lithium supplement additive is one or more of lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide, and lithium peroxide; the coating modifier is one or more of nano-scale titanium dioxide, nano-scale alumina, nano-scale magnesium oxide and nano-scale lithium aluminate.
Preferably, in step S3, the lithium supplement additive, the coating modifier and the waste positive electrode active material are mixed according to a certain ratio, the molar ratio of lithium element to transition metal element is (1.05-1.50): 1, and the mass fraction of the coating modifier in the mixed material is 0.5-2.0 wt%; in the grinding and mixing process, the grinding mode is ball milling by a roller ball mill, the ball-material ratio is 1: 5-20, the rotating speed is 100-.
Preferably, in step S4, the high-temperature solid-phase reaction mode is heating in a muffle furnace or a tubular furnace, the heating rate is 5-10 ℃/min, the reaction temperature is 700-; the aerobic atmosphere is air or oxygen.
Preferably, in step S4, in the grinding and dispersing process, the grinding manner is ball milling by a roller ball mill, the ball-to-material ratio is 1: 5-20, the rotation speed is 100-. And cleaning the ground product with absolute ethyl alcohol and deionized water respectively, and drying in a vacuum oven to obtain the final repair modified positive active material.
Example 1:
and (3) placing the waste ternary 523 type lithium ion battery monomer in a 5 wt% sodium chloride solution to be soaked for 48 hours for full discharge, and disassembling to respectively obtain a positive plate, a negative plate, a diaphragm and a shell.
And drying the anode plate obtained by disassembly to remove the surface electrolyte, cutting the anode plate into small pieces with the size of about 1 multiplied by 1cm, and dissolving the anode plate for 120min by adopting N-methyl pyrrolidone as a dissolving agent under the conditions that the solid-liquid ratio is 50g/L, the temperature is 60 ℃, and the stirring speed is 300 rpm.
Filtering, drying and screening the solution in which most of the binder is dissolved to obtain black powder and aluminum foil of the anode material respectively, then placing the black powder in a muffle furnace to carry out low-temperature aerobic heat treatment, raising the temperature to 500 ℃ at the speed of 20 ℃/min, and roasting for 120min in the air atmosphere.
Detecting the content of each metal element in the obtained pure waste positive active material, and respectively using lithium carbonate and nano-scale titanium dioxide as a lithium supplement additive and a coating modifier, wherein the molar ratio of the lithium element to the transition metal element is 1.10: 1, the mass fraction of the coating modifier in the mixed material is 1.0 wt%. Ball-milling the mixed material in a roller ball mill, wherein the ball-material ratio is 1: 5, grinding for 30min at the rotating speed of 200 r/min.
Placing the uniformly mixed materials in a tube furnace, heating to 800 ℃ at the speed of 10 ℃/min, reacting for 10 hours in an oxygen atmosphere, naturally cooling, and then adding the mixture into a reactor with the ball-to-material ratio of 1: 5. grinding for 30min under the condition that the rotating speed is 200 r/min. And respectively cleaning with absolute ethyl alcohol and deionized water, and drying in a vacuum oven to obtain the final repair modified cathode active material.
Example 2:
and (3) soaking the waste lithium cobaltate battery monomer in 10 wt% sodium chloride solution for 48h for full discharge, and disassembling to respectively obtain a positive plate, a negative plate, a diaphragm and a shell.
And drying the anode plate obtained by disassembly to remove the surface electrolyte, cutting the anode plate into small pieces with the size of about 1 multiplied by 1cm, and dissolving the anode plate for 90min by adopting N-methyl pyrrolidone as a dissolving agent under the conditions that the solid-liquid ratio is 80g/L, the temperature is 90 ℃, and the stirring speed is 300 rpm.
Filtering, drying and screening the solution in which most of the binder is dissolved to obtain black powder and aluminum foil of the anode material respectively, then placing the black powder in a muffle furnace to carry out low-temperature aerobic heat treatment, raising the temperature to 450 ℃ at the speed of 20 ℃/min, and roasting for 60min in the air atmosphere.
Detecting the content of each metal element in the obtained pure waste cathode active material, and respectively taking lithium nitrate and nano-grade alumina as a lithium supplement additive and a coating modifier, wherein the molar ratio of the lithium element to the transition metal element is 1.05: 1, the mass fraction of the coating modifier in the mixed material is 0.8 wt%. Ball-milling the mixed material in a roller ball mill, wherein the ball-material ratio is 1: 10, grinding for 20min at the rotating speed of 300 r/min.
Placing the uniformly mixed materials in a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, reacting for 12h in an oxygen atmosphere, naturally cooling, and then adding the mixture of the materials in a ball-material ratio of 1: 10. grinding for 20min under the condition that the rotating speed is 300 r/min. And respectively cleaning with absolute ethyl alcohol and deionized water, and drying in a vacuum oven to obtain the final repair modified cathode active material.
Example 3:
and (3) placing the waste ternary 523 type lithium ion battery monomer in a 10 wt% sodium chloride solution to be soaked for 36h for full discharge, and disassembling to respectively obtain a positive plate, a negative plate, a diaphragm and a shell.
And drying the anode plate obtained by disassembly to remove the surface electrolyte, cutting the anode plate into small pieces with the size of about 1 multiplied by 1cm, and dissolving the anode plate for 60min by adopting N-methyl pyrrolidone as a dissolving agent under the conditions that the solid-liquid ratio is 80g/L, the temperature is 80 ℃, and the stirring speed is 400 rpm.
Filtering, drying and screening the solution in which most of the binder is dissolved to obtain black powder and aluminum foil of the anode material respectively, then placing the black powder in a muffle furnace to carry out low-temperature aerobic heat treatment, raising the temperature to 600 ℃ at the speed of 20 ℃/min, and roasting for 60min in the air atmosphere.
Detecting the content of each metal element in the obtained pure waste cathode active material, and respectively taking lithium nitrate and nano-grade alumina as a lithium supplement additive and a coating modifier, wherein the molar ratio of the lithium element to the transition metal element is 1.05: 1, the mass fraction of the coating modifier in the mixed material is 1.0 wt%. Ball-milling the mixed material in a roller ball mill, wherein the ball-material ratio is 1: 15, grinding for 30min at the rotating speed of 250 r/min.
Placing the uniformly mixed materials in a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, reacting for 8 hours in an oxygen atmosphere, naturally cooling, and then adding the mixture of the materials in a ball-material ratio of 1: 15. grinding for 30min under the condition that the rotating speed is 250 r/min. And respectively cleaning with absolute ethyl alcohol and deionized water, and drying in a vacuum oven to obtain the final repair modified cathode active material.
The waste ternary 523 material, the repair modified ternary 523 material and the commercial ternary 523 material in the embodiment 1 are mixed with a conductive agent Super-P and a binder polyvinylidene fluoride in a ratio of 8: 1: 1, adopting a metal lithium sheet as a negative electrode, adopting a polyethylene and polypropylene composite membrane as a diaphragm, dissolving 1mol/L lithium hexafluorophosphate in ethylene carbonate as electrolyte, and assembling into a CR2032 type button half-cell for carrying out electrochemical performance test.
The cycle performance curve and the rate performance curve of the three materials are shown in fig. 1 and fig. 2, and under the 1C rate, compared with the waste material, the discharge specific capacity of the repair modified material is obviously improved, and the first cycle discharge specific capacity is 149.5 mAh.g-1And shows excellent electrochemical performance close to that of commercial materials. The rate performance test result shows that the repair modified material has good cycle stability.
Claims (10)
1. A method for repairing and modifying a waste lithium ion battery anode active material is characterized by comprising the following steps: the organic solvent dissolution and the low-temperature aerobic heat treatment are combined to obtain a pure waste cathode active material, so that the high-efficiency enrichment and purification of the waste cathode active material are realized; uniformly mixing the waste positive active material with a lithium supplement additive and a coating modifier by combining lithium supplement and surface coating modification, supplementing the lithium element missing from the waste positive active material in a high-temperature solid-phase reaction mode, and forming a protective layer on the surface of the repair modified material; the corrosion effect of the electrolyte in the circulation process is reduced while the lithium ion and charge migration of the modified material is promoted, and the surface stability of the material is improved; through efficient enrichment and purification and high-temperature solid-phase reaction, the surface damaged structure and electrochemical performance of the waste positive electrode active material are recovered.
2. The method for repairing and modifying the waste lithium ion battery positive electrode active material according to claim 1, characterized by comprising the following specific steps:
step S1, discharging and disassembling: disassembling the fully discharged and air-dried waste lithium ion battery monomer;
step S2, preprocessing: dissolving and removing most of organic binders in the positive plate by adopting an organic solvent, filtering, drying and screening, and then removing residual ineffective binders and conductive agents by low-temperature aerobic heat treatment to obtain a pure waste positive active material;
step S3, uniformly mixing: detecting the waste positive active material obtained in the step S2, determining the content of each metal element, and fully grinding and mixing the waste positive active material with a lithium supplement additive and a coating modifier according to a certain proportion;
step S4, repairing and modifying: and (5) carrying out high-temperature solid-phase reaction on the uniformly mixed materials in the step (S3) in an aerobic atmosphere, and grinding, dispersing, cleaning and drying the products after the reaction is finished to obtain the final repair modified positive active material.
3. The method for repairing and modifying the positive active material of the waste lithium ion battery according to claim 2, wherein the method comprises the following steps: in step S1, the discharge mode is chemical discharge, strong electrolyte such as sodium chloride and potassium chloride and water are used for preparing 5-20 wt% solution, the waste lithium ion battery monomer is placed in the strong electrolyte solution for soaking for 24-48h for full discharge, and the positive plate, the negative plate, the diaphragm and the shell are obtained after disassembly.
4. The method for repairing and modifying the positive active material of the waste lithium ion battery according to claim 2, wherein the method comprises the following steps: in step S2, drying the anode plate obtained by disassembly to remove the surface electrolyte, cutting into small pieces with the size of about 1 × 1cm, immersing the small pieces into an organic solvent according to the solid-to-liquid ratio of 50-150g/L, wherein the dissolving temperature is 60-95 ℃, the dissolving time is 40-150min, and the stirring speed is 100-500 rpm; the organic solvent is one of solvents which are similar to and compatible with the organic binder, such as N-methyl pyrrolidone, dimethylformamide, dimethylacetamide and the like.
5. The method for repairing and modifying the positive active material of the waste lithium ion battery according to claim 2, wherein the method comprises the following steps: in step S2, filtering, drying and screening the solution in which most of the binder is dissolved to respectively obtain black powder and aluminum foil of the anode material, and then carrying out low-temperature aerobic heat treatment on the black powder to remove the residual ineffective binder and the residual conductive agent; the low-temperature aerobic heat treatment mode is heating equipment such as a muffle furnace, a tubular furnace and the like, the aerobic atmosphere is air or oxygen, the heat treatment condition is that the temperature rise rate is 5-20 ℃/min, the temperature is 400-.
6. The method for repairing and modifying the positive active material of the waste lithium ion battery according to claim 2, wherein the method comprises the following steps: in step S3, the lithium supplement additive is one or more of lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide, and lithium peroxide; the coating modifier is one or more of nano-scale titanium dioxide, nano-scale alumina, nano-scale magnesium oxide and nano-scale lithium aluminate.
7. The method for repairing and modifying the positive active material of the waste lithium ion battery according to claim 2, wherein the method comprises the following steps: in step S3, the lithium supplement additive, the coating modifier and the waste positive electrode active material are mixed according to a molar ratio and a mass fraction ratio, respectively, wherein the molar ratio of lithium element to transition metal element is (1.05-1.50): 1, and the mass fraction of the coating modifier in the mixed material is 0.5-2.0 wt%; in the grinding and mixing process, the grinding mode is ball milling by a roller ball mill, the ball-material ratio is 1: 5-20, the rotating speed is 100-.
8. The method for repairing and modifying the positive active material of the waste lithium ion battery according to claim 2, wherein the method comprises the following steps: in step S4, the high temperature solid phase reaction mode is heating in a muffle furnace or a tube furnace, the heating rate is 5-10 ℃/min, the reaction temperature is 700-900 ℃, the reaction time is 8-12h, and the oxygen atmosphere is air or oxygen.
9. The method for repairing and modifying the positive active material of the waste lithium ion battery according to claim 2, wherein the method comprises the following steps: in the step S4, in the grinding and dispersing process, the grinding mode is ball milling by a roller ball mill, the ball-material ratio is 1: 5-20, the rotating speed is 100-. And cleaning the ground product with absolute ethyl alcohol and deionized water respectively, and drying in a vacuum oven to obtain the final repair modified positive active material.
10. The method for repairing and modifying the waste lithium ion battery positive electrode active material according to claim 1 or 2, wherein the waste positive electrode active material comprises but is not limited to a currently mainstream commercial positive electrode material; the anode material is a nickel-cobalt-manganese ternary material, lithium cobaltate and a lithium iron phosphate material; the nickel-cobalt-manganese ternary material is 111 type, 811 type, 622 type or 523 type.
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