WO2024060547A1 - 一种废旧三元正极材料的再生方法 - Google Patents
一种废旧三元正极材料的再生方法 Download PDFInfo
- Publication number
- WO2024060547A1 WO2024060547A1 PCT/CN2023/082858 CN2023082858W WO2024060547A1 WO 2024060547 A1 WO2024060547 A1 WO 2024060547A1 CN 2023082858 W CN2023082858 W CN 2023082858W WO 2024060547 A1 WO2024060547 A1 WO 2024060547A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- positive electrode
- ternary cathode
- waste ternary
- temperature
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- 239000007774 positive electrode material Substances 0.000 title abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000463 material Substances 0.000 claims abstract description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 238000001354 calcination Methods 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- 239000007921 spray Substances 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000001301 oxygen Substances 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000011572 manganese Substances 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000005469 granulation Methods 0.000 claims abstract description 10
- 230000003179 granulation Effects 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims abstract description 3
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- 239000010406 cathode material Substances 0.000 claims description 78
- 239000000725 suspension Substances 0.000 claims description 28
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 230000001172 regenerating effect Effects 0.000 claims description 20
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 5
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 5
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 238000003756 stirring Methods 0.000 description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 32
- 239000007788 liquid Substances 0.000 description 29
- 239000002131 composite material Substances 0.000 description 17
- 239000000377 silicon dioxide Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 238000002386 leaching Methods 0.000 description 13
- 239000011343 solid material Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 239000013589 supplement Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000009469 supplementation Effects 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 101000827703 Homo sapiens Polyphosphoinositide phosphatase Proteins 0.000 description 1
- 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 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 102100023591 Polyphosphoinositide phosphatase Human genes 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- -1 aluminum ions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent 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
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ICKLSPKTPKWFAP-UHFFFAOYSA-N diazanium;bromide;chloride Chemical compound [NH4+].[NH4+].[Cl-].[Br-] ICKLSPKTPKWFAP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
-
- 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
Definitions
- the present invention relates to the technical field of recycling lithium ion cathode materials, and in particular to a method for regenerating waste ternary cathode materials.
- Lithium-ion batteries are secondary battery systems that use two different lithium-intercalating compounds that can reversibly insert and remove lithium ions as the positive and negative electrodes of the battery.
- lithium ions are extracted from the crystal lattice of the positive electrode material and inserted into the crystal lattice of the negative electrode material after passing through the electrolyte, making the negative electrode rich in lithium and the positive electrode poor in lithium; during discharge, lithium ions are extracted from the crystal lattice of the negative electrode material and pass through The electrolyte is then inserted into the crystal lattice of the positive electrode material, making the positive electrode rich in lithium and the negative electrode poor in lithium. In this way, the difference in potential between the positive and negative electrode materials relative to metallic lithium when inserting and extracting lithium ions is the operating voltage of the battery.
- Lithium-ion batteries can not only reduce the pressure of used batteries on the environment, but also prevent the waste of metal resources such as cobalt and nickel.
- the main industrial recycling methods for used ternary lithium-ion batteries are the fire method and the wet method:
- the fire method is to directly recycle battery materials through high-temperature treatment.
- the process is relatively simple, but the recovery rate is low and the high-temperature treatment time is long. Energy consumption is high, and organic matter such as electrolytes and binders will produce harmful gases at high temperatures, causing environmental pollution;
- the wet method is to disassemble the battery shell, crush and screen it, and then leaching the valuable metals in the electrode material, and then Precipitation separation or extraction separation is used to obtain the corresponding salts or oxides of each metal to realize the recycling of battery materials, but the process is complicated.
- the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art.
- the present invention proposes a method for regenerating waste ternary positive electrode materials, which makes the atomic arrangement of the material more compact by high-temperature annealing after lithium supplementation, reduces the atomic distance and refines the grains, thereby improving the crystallinity of the material; then, by fluoride doping in the material, the material cation mixing is reduced, the material structure is stabilized, and the cycle and rate performance are improved; and then, by coating the ternary positive electrode material, the ternary positive electrode material is isolated from the electrolyte, the side reactions are reduced and the collapse of the electrode material is slowed down.
- a method for regenerating waste ternary positive electrode materials comprises the following steps:
- the waste ternary cathode material described in step S1 is produced through the following steps: dismantling the waste ternary lithium battery, taking out the cathode sheet, and subjecting the cathode sheet to alkali leaching, solid-liquid separation, and drying. After calcination and grinding, the waste ternary cathode material is obtained.
- the acid described in step S1 is at least one of acetic acid, tartaric acid, malic acid or citric acid.
- the pH of the acid described in step S1 is 3-5.
- the lithium source described in step S2 is at least one of lithium hydroxide, lithium carbonate, lithium bicarbonate, lithium nitrate, lithium chloride or lithium bromide.
- the annealing temperature described in step S2 is 500-950°C, and the time is 1-3 hours.
- the annealing temperature described in step S2 is 700-900°C, and the time is 1-3 h.
- the nickel source described in step S3 is at least one of NiC 4 H 6 O 4 ⁇ 4H 2 O or Ni(NO 3 ) 2 ⁇ 6H 2 O;
- the cobalt source It is at least one of CoC 4 H 6 O 4 ⁇ 4H 2 O or Co(NO 3 ) 2 ⁇ 6H 2 O;
- the manganese source is MnC 4 H 6 O 4 ⁇ 4H 2 O or Mn(NO 3 ) At least one of 2 ⁇ 6H 2 O.
- the fluoride described in step S3 is at least one of ammonium fluoride, aluminum fluoride, sodium fluoride or potassium fluoride, and the molar ratio of the cathode material to the fluoride is 1: (0.001-0.05).
- the fluoride described in step S3 is aluminum fluoride, and the cathode material
- the molar ratio to aluminum fluoride is 1: (0.005-0.03).
- aluminum ions are used to partially replace the transition metal ion position and play a role in reducing cation mixing.
- the calcination temperature described in step S3 is 800-950°C and the time is 8-16 hours.
- the coating material in step S4 is porous graphene, and the porous graphene supports lithium salt, SiO 2 , AlF 3 , Al 2 O 3 , iron phosphate, ZrO 2 or V At least one of 2 O 5 .
- the preparation method of porous graphene loaded with coating particles described in step S4 is as follows: adding porous graphene to a solution containing cetyltrimethylammonium bromide and hydroxide. Sodium in deionized water, disperse evenly by ultrasonic; stir in a water bath, then add tetraethyl silicate dropwise, continue the reaction, centrifuge, filter and dry overnight; the above product reacts at high temperature in argon and cools naturally to room temperature Obtain composite materials.
- the coating material in step S4 is porous graphene, and the porous graphene supports SiO 2 .
- the NCM precursor in step S3 is coated by spraying.
- the multi-gradient calcination described in step S4 includes primary calcination and secondary calcination, the primary calcination heating rate is 1-6°C/min, the temperature is 400-500°C, and the time is 4 -6h; the secondary calcination heating rate is 1-6°C/min, the temperature is 800-950°C, and the time is 8-16h.
- annealing treatment is performed to make the atoms more closely arranged, reduce the atomic spacing, and refine the crystal grains, thus improving the crystallinity, crystal structure stability and electrochemical performance of the material.
- Fluoride doping is used. Fluorine can replace part of the oxygen in the crystal lattice to reduce the redox activity of oxygen and stabilize the structure, thereby improving the cycle and rate performance of the material.
- the present invention adopts gradient calcination, which can effectively slow down the crystal transformation speed of the ternary cathode material during calcination, reduce lattice defects, and improve the integrity and stability of the material.
- Coating the surface of the ternary cathode material can physically isolate the active material in the battery from the electrolyte, reduce the occurrence of side reactions, inhibit the dissolution of transition metal ions in the electrolyte, and at the same time, it has certain mechanical properties.
- the strong inactive coating also slows the collapse of the electrode material structure during long-term cycling.
- the present invention pre-prepares graphene loaded with a coating, the coating particles are relatively small in size and are uniformly dispersedly loaded on the graphene without agglomeration.
- the graphene loaded with the coating particles is coated on the positive electrode material by spraying. During subsequent aerobic sintering, the graphene is converted into carbon dioxide, and the loaded particles are uniformly coated on the ternary positive electrode material. Compared with the conventional solid-phase mixed coating method, the coating material is more evenly distributed.
- Figure 1 is an SEM image of the NCM precursor prepared in Example 1 of the present invention.
- Figure 2 is an SEM image of the coated ternary cathode material prepared in Example 1 of the present invention.
- Figure 3 is an XRD comparison chart of the calcined materials described in Example 1 and Comparative Example 1 of the present invention
- FIG. 4 is an EDS graph of element distribution after AlF 3 doping obtained in Example 1 of the present invention.
- a method for regenerating waste ternary cathode materials including the following steps:
- Step 1 After disassembling the used ternary lithium battery, take out the positive electrode sheet, put the positive electrode sheet into a sodium hydroxide solution with a mass fraction of 30% according to the solid-liquid ratio of 10g/L, control the temperature to 90°C, stir for 1.5h, and wait After the residual aluminum foil is completely dissolved, the solid and liquid are separated to obtain leachate and leach residue;
- Step 2 Wash the leaching residue with pure water and dry at 110°C for 10 hours;
- Step 3 calcining the dried leached residue at 500° C. in an oxygen atmosphere for 5 h, and grinding the dried leached residue to obtain a powder after cooling;
- Step 4 Add the powder obtained in Step 3 to acetic acid with a pH value of 4.0, stir at 50°C for 1 hour, and then separate the solid and liquid to obtain the solid material and the filtrate;
- Step 5 Wash the solid material obtained in Step 4 with pure water to obtain the activated cathode material
- Step 6 Add the activated cathode material to the 4mol/L lithium hydroxide solution at a solid-to-liquid ratio of 1g:20mL. Heating under pressure, airtight, nitrogen atmosphere, heating temperature is 280°C, heating time is 5h;
- Step 7 After the lithium supplement is completed, filter, dry in a vacuum oven at 80°C, then transfer to a tube furnace, heat to 900°C, and keep in flowing nitrogen for 2 hours;
- H 6 O 4 ⁇ 4H 2 O, CoC 4 H 6 O 4 ⁇ 4H 2 O, MnC 4 H 6 O 4 ⁇ 4H 2 O then add AlF 3 according to the molar ratio of positive electrode material to AlF 3 1:0.03, and then according to Add water at a mass-volume ratio of the mixture to water of 0.3g:1mL, and obtain a mixed suspension with uniform composition after ultrasonic for 10 minutes;
- Step 9 Add the suspension obtained in step 8 to the spray dryer, control the temperature of the spray dryer to 180°C, the feed rate to 450mL/h, the air inlet pressure to 0.5MPa, and the outlet temperature to 150°C to perform spray granulation.
- the precursor of spherical NCM523 was continuously prepared;
- Step 10 Put the NCM523 precursor prepared in step 9 into a muffle furnace and process industrial oxygen for calcination. The temperature is raised to 850°C and kept for 10 hours to obtain a calcined material;
- Step 11 prepare silica-loaded graphene: add porous graphene to deionized water containing cetyltrimethylammonium bromide and sodium hydroxide, and disperse evenly by ultrasonic. Stir in a water bath, then add tetraethyl silicate dropwise, continue the reaction, centrifuge, filter and dry overnight. The product is reacted at high temperature in argon gas, and then naturally cooled to room temperature to obtain a composite material;
- Step 12 adding water according to the mass volume ratio of the composite material prepared in step 11 to water at 1 g:100 mL, and ultrasonicating for 10 minutes to obtain a composite material suspension;
- Step 13 Spray the suspension prepared in step 12 on the calcined material described in step 10, and stir and mix at the same time.
- the stirring speed is 60 rpm and the stirring time is 20 min. This is done three times in total to obtain the mass of silica. 0.5% pre-coated NCM precursor;
- Step 14 Put the pre-coated NCM precursor prepared in Step 13 into a muffle furnace and process industrial oxygen for two-stage calcination. First, the temperature is raised to 500°C and kept for 5 hours. Then the temperature is raised to 900°C and kept for 12 hours to obtain regeneration.
- Figure 2 is an SEM image of the coated ternary cathode material prepared in Example 1 of the present invention. It can be seen from the figure that the coating effect of the ternary cathode material prepared in this example is good.
- FIG4 is an EDS diagram of element distribution after AlF 3 doping obtained in Example 1 of the present invention. It can be seen from the diagram that Ni, Co, Mn and F elements are evenly distributed, indicating that the material has good uniformity.
- a method for regenerating waste ternary cathode materials including the following steps:
- Step 1 After disassembling the used ternary lithium battery, take out the positive electrode sheet, put the positive electrode sheet into a sodium hydroxide solution with a mass fraction of 40% according to the solid-liquid ratio of 10g/L, control the temperature to 70°C, stir for 2 hours, and wait until the remaining After the aluminum foil is completely dissolved, the solid and liquid are separated to obtain leachate and leach residue;
- Step 2 Wash the leaching residue with pure water and dry at 100°C for 12 hours;
- Step 3 Calculate the dried leaching residue at 500°C in an oxygen atmosphere for 5 hours, cool and then grind to obtain powder;
- Step 4 Add the powder obtained in Step 3 to malic acid with a pH of 3.0, stir for 2 hours at 30°C, and then separate the solid and liquid to obtain the solid material and the filtrate;
- Step 5 Wash the solid material obtained in Step 4 with pure water to obtain the activated cathode material
- Step 6 Add the activated cathode material to the lithium carbonate solution of 3 mol/L at a solid-to-liquid ratio of 1g:20mL, and heat it under a nitrogen atmosphere at a heating temperature of 300°C and a heating time of 6 hours;
- Step 7 After the lithium supplement is completed, filter, dry in a vacuum oven at 80°C, then transfer to a tube furnace, heat to 800°C, and keep in flowing nitrogen for 1 hour;
- H 6 O 4 ⁇ 4H 2 O, CoC 4 H 6 O 4 ⁇ 4H 2 O, MnC 4 H 6 O 4 ⁇ 4H 2 O then add AlF 3 according to the molar ratio of positive electrode material to AlF 3 1:0.03, and then according to Add water at a mass-volume ratio of the mixture to water of 0.3g:1mL, and obtain a mixed suspension with uniform composition after ultrasonic for 10 minutes;
- Step 9 Add the suspension obtained in step 8 to the spray dryer, control the temperature of the spray dryer to 180°C, the feed rate to 450mL/h, the air inlet pressure to 0.5MPa, and the outlet temperature to 150°C to perform spray granulation.
- the precursor of spherical NCM622 was continuously prepared;
- Step 10 Put the NCM622 precursor prepared in step 9 into a muffle furnace and process industrial oxygen for calcination. The temperature is raised to 850°C and kept for 10 hours to obtain a calcined material;
- Step 11 prepare silica-loaded graphene: add porous graphene to a solution containing cetyltrimethyl bromide ammonium chloride and sodium hydroxide in deionized water and dispersed evenly by ultrasound. Stir in a water bath, then add tetraethyl silicate dropwise, continue the reaction, centrifuge, filter and dry overnight. The product is reacted at high temperature in argon gas, and then naturally cooled to room temperature to obtain a composite material;
- Step 12 Add water according to the mass-volume ratio of the composite material and water obtained in step 11: 1g:100mL, and obtain the composite material suspension after ultrasonic for 10 minutes;
- Step 13 Spray the suspension prepared in step 12 on the calcined material described in step 10, and stir and mix at the same time.
- the stirring speed is 60 rpm and the stirring time is 20 min. This is done three times in total to obtain the mass of silica. 0.5% pre-coated NCM precursor;
- Step 14 Put the pre-coated NCM precursor prepared in Step 13 into a muffle furnace and process industrial oxygen for two-stage calcination. First, the temperature is raised to 400°C and kept for 6 hours. Then the temperature is raised to 800°C and kept for 16 hours to obtain regeneration.
- a method for regenerating waste ternary cathode materials including the following steps:
- Step 1 After disassembling the used ternary lithium battery, take out the positive electrode sheet, put the positive electrode sheet into a sodium hydroxide solution with a mass fraction of 40% according to the solid-liquid ratio of 10g/L, control the temperature to 70°C, stir for 2 hours, and wait until the remaining After the aluminum foil is completely dissolved, the solid and liquid are separated to obtain leachate and leach residue;
- Step 2 washing the leached residue with pure water and drying at 110° C. for 10 h;
- Step 3 Calculate the dried leaching residue at 500°C in an oxygen atmosphere for 5 hours, cool and then grind to obtain powder;
- Step 4 Add the powder obtained in Step 3 to tartaric acid with a pH of 5.0, stir at 30°C for 2 hours, and then separate the solid and liquid to obtain the solid and filtrate;
- Step 5 Wash the solid material obtained in Step 4 with pure water to obtain the activated cathode material
- Step 6 Add the activated cathode material to the 5mol/L lithium hydroxide solution at a solid-to-liquid ratio of 1g:40mL, and heat it under a nitrogen atmosphere.
- the heating temperature is 280°C and the heating time is 5h;
- Step 7 After the lithium supplement is completed, filter, dry in a vacuum oven at 80°C, then transfer to a tube furnace, heat to 800°C, and keep in flowing nitrogen for 1 hour;
- Step 8 The ratio of the total molar amount of the three elements nickel, cobalt and manganese to the molar amount of lithium is 1:1.08 for the annealed cathode material.
- water according to the mass volume ratio of the mixture to water 0.3g:1mL, and obtain a mixed suspension with uniform composition after ultrasonic for 10 minutes;
- Step 9 Add the suspension obtained in step 8 to the spray dryer, control the temperature of the spray dryer to 180°C, the feed rate to 450mL/h, the air inlet pressure to 0.5MPa, and the outlet temperature to 150°C to perform spray granulation.
- the precursor of spherical NCM622 was continuously prepared;
- Step 10 Put the NCM622 precursor prepared in step 9 into a muffle furnace and process industrial oxygen for calcination. The temperature is raised to 850°C and kept for 10 hours to obtain a calcined material;
- Step 11 prepare silica-loaded graphene: add porous graphene to deionized water containing cetyltrimethylammonium bromide and sodium hydroxide, and disperse evenly by ultrasonic. Stir in a water bath, then add tetraethyl silicate dropwise, continue the reaction, centrifuge, filter and dry overnight. The product is reacted at high temperature in argon gas, and then naturally cooled to room temperature to obtain a composite material;
- Step 12 Add water according to the mass-volume ratio of the composite material and water obtained in step 11: 1g:100mL, and obtain the composite material suspension after ultrasonic for 10 minutes;
- Step 13 spraying the suspension prepared in step 12 on the calcined material in step 10 in a spraying manner, stirring and mixing at a stirring speed of 100 rpm and a stirring time of 20 min, and performing the process three times in total to obtain a pre-coated NCM precursor having a silica mass percentage of 0.5%;
- Step 14 Put the pre-coated NCM precursor prepared in Step 13 into a muffle furnace and process industrial oxygen for two-stage calcination. First, the temperature is raised to 500°C and kept for 6 hours. Then the temperature is raised to 850°C and kept for 16 hours to obtain regeneration.
- a method for regenerating waste ternary cathode materials The only difference from Example 1 is that no annealing operation is performed. The other conditions remain unchanged and includes the following steps:
- Step 1 after disassembling the waste ternary lithium battery, take out the positive electrode sheet, put the positive electrode sheet into a sodium hydroxide solution with a mass fraction of 30% according to a solid-liquid ratio of 10g/L, control the temperature to 90°C, stir for 1.5h, and separate the solid and liquid after the residual aluminum foil is completely dissolved to obtain a leachate and a leach residue;
- Step 2 Wash the leaching residue with pure water and dry at 110°C for 10 hours;
- Step 3 calcining the dried leached residue at 500° C. in an oxygen atmosphere for 5 h, and grinding the dried leached residue to obtain a powder after cooling;
- Step 4 Add the powder obtained in Step 3 to acetic acid with a pH value of 4.0, stir at 50°C for 1 hour, and then separate the solid and liquid to obtain the solid material and the filtrate;
- Step 5 Wash the solid material obtained in Step 4 with pure water to obtain the activated cathode material
- Step 6 Add the activated cathode material to the 4mol/L lithium hydroxide solution at a solid-to-liquid ratio of 1g:20mL, and heat it under high pressure, airtightness, and nitrogen atmosphere.
- the heating temperature is 280°C and the heating time is 5h;
- H 6 O 4 ⁇ 4H 2 O, CoC 4 H 6 O 4 ⁇ 4H 2 O, MnC 4 H 6 O 4 ⁇ 4H 2 O then add AlF 3 according to the molar ratio of positive electrode material to AlF 3 1:0.03, and then according to Add water at a mass-volume ratio of the mixture to water of 0.3g:1mL, and obtain a mixed suspension with uniform composition after ultrasonic for 10 minutes;
- Step 8 Add the suspension obtained in Step 7 to the spray dryer, control the temperature of the spray dryer to 180°C, the feed rate to 450mL/h, the air inlet pressure to 0.5MPa, and the outlet temperature to 150°C to perform spray granulation.
- the precursor of spherical NCM523 was continuously prepared;
- Step 9 placing the NCM523 precursor prepared in step 8 into a muffle furnace, calcining it with industrial oxygen, raising the temperature to 850° C., and keeping the temperature for 10 hours to obtain a calcined material;
- Step 10 prepare silica-loaded graphene: add porous graphene to deionized water containing cetyltrimethylammonium bromide and sodium hydroxide, and disperse evenly by ultrasonic. Stir in a water bath, then add tetraethyl silicate dropwise, continue the reaction, centrifuge, filter and dry overnight. The product is reacted at high temperature in argon gas, and then naturally cooled to room temperature to obtain a composite material;
- Step 11 Add water according to the mass-volume ratio of the composite material and water obtained in step 10: 1g:100mL, and obtain the composite material suspension after ultrasonic for 10 minutes;
- Step 12 Spray the suspension prepared in Step 12 on the calcined material described in Step 9, while stirring and mixing.
- the stirring speed is 60 rpm and the stirring time is 20 min. This is done three times in total to obtain the mass of silica. 0.5% pre-coated NCM precursor;
- Step 13 Put the coated NCM precursor prepared in step 12 into a muffle furnace and process industrial oxygen for two steps.
- the temperature is first raised to 500°C and kept for 5 hours, then raised to 900°C and kept for 12 hours to obtain the regenerated ternary cathode material NCM523.
- Figure 3 is an XRD comparison chart of the coated ternary cathode material prepared in Example 1 and Comparative Example 1. It can be seen from the figure that the diffraction peak intensity of the ternary cathode material prepared in Example 1 is greater, that is, the annealing operation The purity and crystallinity of the ternary cathode material are improved, thereby improving the stability of the material.
- a method for regenerating waste ternary cathode materials The only difference from Example 1 is that no AlF 3 doping is added. The other conditions remain unchanged and includes the following steps:
- Step 1 After disassembling the used ternary lithium battery, take out the positive electrode sheet, put the positive electrode sheet into a sodium hydroxide solution with a mass fraction of 30% according to the solid-liquid ratio of 10g/L, control the temperature to 90°C, stir for 1.5h, and wait After the residual aluminum foil is completely dissolved, the solid and liquid are separated to obtain leachate and leach residue;
- Step 2 Wash the leaching residue with pure water and dry at 110°C for 10 hours;
- Step 3 Calculate the dried leaching residue at 500°C in an oxygen atmosphere for 5 hours, cool and then grind to obtain powder;
- Step 4 Add the powder obtained in Step 3 to acetic acid with a pH value of 4.0, stir at 50°C for 1 hour, and then separate the solid and liquid to obtain the solid material and the filtrate;
- Step 5 Wash the solid material obtained in Step 4 with pure water to obtain the activated cathode material
- Step 6 Add the activated cathode material to the 4mol/L lithium hydroxide solution at a solid-to-liquid ratio of 1g:20mL, and heat it under high pressure, airtightness, and nitrogen atmosphere.
- the heating temperature is 280°C and the heating time is 5h;
- Step 7 After the lithium supplement is completed, filter, dry in a vacuum oven at 80°C, then transfer to a tube furnace, heat to 900°C, and keep in flowing nitrogen for 2 hours;
- Step 9 Add the suspension obtained in step 8 to the spray dryer, control the temperature of the spray dryer to 180°C, the feed rate to 450mL/h, the air inlet pressure to 0.5MPa, and the outlet temperature to 150°C to perform spray granulation. , prepared continuously to the precursor of globular NCM523;
- Step 10 Put the NCM523 precursor prepared in step 9 into a muffle furnace and process industrial oxygen for calcination. The temperature is raised to 850°C and kept for 10 hours to obtain a calcined material;
- Step 11 prepare silica-loaded graphene: add porous graphene to deionized water containing cetyltrimethylammonium bromide and sodium hydroxide, and disperse evenly by ultrasonic. Stir in a water bath, then add tetraethyl silicate dropwise, continue the reaction, centrifuge, filter and dry overnight. The product is reacted at high temperature in argon gas, and then naturally cooled to room temperature to obtain a composite material;
- Step 12 adding water according to the mass volume ratio of the composite material prepared in step 11 to water at 1 g:100 mL, and ultrasonicating for 10 minutes to obtain a composite material suspension;
- Step 13 Spray the suspension prepared in step 12 on the calcined material described in step 10, and stir and mix at the same time.
- the stirring speed is 60 rpm and the stirring time is 20 min. This is done three times in total to obtain the mass of silica. 0.5% pre-coated NCM precursor;
- Step 14 Put the pre-coated NCM precursor prepared in Step 13 into a muffle furnace and process industrial oxygen for two-stage calcination. First, the temperature is raised to 500°C and kept for 5 hours. Then the temperature is raised to 900°C and kept for 12 hours to obtain regeneration.
- a method for regenerating waste ternary cathode materials The only difference from Example 1 is that no coating operation is performed. The other conditions remain unchanged and includes the following steps:
- Step 1 After disassembling the used ternary lithium battery, take out the positive electrode sheet, put the positive electrode sheet into a sodium hydroxide solution with a mass fraction of 30% according to the solid-liquid ratio of 10g/L, control the temperature to 90°C, stir for 1.5h, and wait After the residual aluminum foil is completely dissolved, the solid and liquid are separated to obtain leachate and leach residue;
- Step 2 Wash the leaching residue with pure water and dry at 110°C for 10 hours;
- Step 3 Calculate the dried leaching residue at 500°C in an oxygen atmosphere for 5 hours, cool and then grind to obtain powder;
- Step 4 Add the powder obtained in Step 3 to acetic acid with a pH value of 4.0, stir at 50°C for 1 hour, and then separate the solid and liquid to obtain the solid material and the filtrate;
- Step 5 Wash the solid material obtained in Step 4 with pure water to obtain the activated cathode material
- Step 6 Add the activated cathode material to the 4mol/L lithium hydroxide solution at a solid-to-liquid ratio of 1g:20mL, and heat it under high pressure, airtightness, and nitrogen atmosphere.
- the heating temperature is 280°C and the heating time is 5h;
- Step 7 After the lithium supplement is completed, filter, dry in a vacuum oven at 80°C, then transfer to a tube furnace, heat to 900°C, and keep in flowing nitrogen for 2 hours;
- H 6 O 4 ⁇ 4H 2 O, CoC 4 H 6 O 4 ⁇ 4H 2 O, MnC 4 H 6 O 4 ⁇ 4H 2 O then add AlF 3 according to the molar ratio of positive electrode material to AlF 3 1:0.03, and then according to Add water at a mass-volume ratio of the mixture to water of 0.3g:1mL, and obtain a mixed suspension with uniform composition after ultrasonic for 10 minutes;
- Step 9 Add the suspension obtained in step 8 to the spray dryer, control the temperature of the spray dryer to 180°C, the feed rate to 450mL/h, the air inlet pressure to 0.5MPa, and the outlet temperature to 150°C to perform spray granulation.
- the precursor of spherical NCM523 was continuously prepared;
- Step 10 Put the spherical NCM precursor prepared in step 9 into a muffle furnace and process industrial oxygen for two-stage calcination. First, the temperature is raised to 500°C and kept for 5 hours. Then the temperature is raised to 900°C and kept for 12 hours to obtain the regenerated three-stage NCM precursor. Yuan cathode material NCM523.
- a method for regenerating waste ternary cathode materials The only difference from Example 1 is that the pre-coating does not include graphene. The other conditions remain unchanged and includes the following steps:
- Step 1 After disassembling the used ternary lithium battery, take out the positive electrode sheet, put the positive electrode sheet into a sodium hydroxide solution with a mass fraction of 30% according to the solid-liquid ratio of 10g/L, control the temperature to 90°C, stir for 1.5h, and wait After the residual aluminum foil is completely dissolved, the solid and liquid are separated to obtain leachate and leach residue;
- Step 2 Wash the leaching residue with pure water and dry at 110°C for 10 hours;
- Step 3 Calculate the dried leaching residue at 500°C in an oxygen atmosphere for 5 hours, cool and then grind to obtain powder;
- Step 4 Add the powder obtained in Step 3 to acetic acid with a pH value of 4.0, stir at 50°C for 1 hour, and then separate the solid and liquid to obtain the solid material and the filtrate;
- Step 5 Wash the solid material obtained in Step 4 with pure water to obtain the activated cathode material
- Step 6 Add the activated cathode material to the 4mol/L lithium hydroxide solution at a solid-to-liquid ratio of 1g:20mL. Heating under pressure, airtight, nitrogen atmosphere, heating temperature is 280°C, heating time is 5h;
- Step 7 After the lithium supplement is completed, filter, dry in a vacuum oven at 80°C, then transfer to a tube furnace, heat to 900°C, and keep in flowing nitrogen for 2 hours;
- H 6 O 4 ⁇ 4H 2 O, CoC 4 H 6 O 4 ⁇ 4H 2 O, MnC 4 H 6 O 4 ⁇ 4H 2 O then add AlF 3 according to the molar ratio of positive electrode material to AlF 3 1:0.03, and then according to Add water at a mass-volume ratio of the mixture to water of 0.3g:1mL, and obtain a mixed suspension with uniform composition after ultrasonic for 10 minutes;
- Step 9 Add the suspension obtained in step 8 to the spray dryer, control the temperature of the spray dryer to 180°C, the feed rate to 450mL/h, the air inlet pressure to 0.5MPa, and the outlet temperature to 150°C to perform spray granulation.
- the precursor of spherical NCM523 was continuously prepared;
- Step 10 Put the NCM523 precursor prepared in step 9 into a muffle furnace and process industrial oxygen for calcination. The temperature is raised to 850°C and kept for 10 hours to obtain a calcined material;
- Step 11 Add tetraethyl silicate dropwise to the deionized water containing cetyltrimethylammonium bromide and sodium hydroxide, stir in a water bath, continue the reaction, centrifuge, filter and dry overnight. The product is reacted at high temperature in argon gas, and then naturally cooled to room temperature to obtain silica;
- Step 12 adding water according to the mass volume ratio of the silica and water obtained in step 11 at 1 g:100 mL, and ultrasonicating for 10 minutes to obtain a silica suspension;
- Step 13 Spray the suspension prepared in step 12 on the calcined material described in step 10, and stir and mix at the same time.
- the stirring speed is 60 rpm and the stirring time is 20 min. This is done three times in total to obtain the mass of silica. 0.5% pre-coated NCM precursor;
- Step 14 Put the pre-coated NCM precursor prepared in Step 13 into a muffle furnace and process industrial oxygen for two-stage calcination. First, the temperature is raised to 500°C and kept for 5 hours. Then the temperature is raised to 900°C and kept for 12 hours to obtain regeneration.
- the present invention uses button batteries to test the first Coulombic efficiency, discharge capacity and 200 cycle capacity retention rate of the ternary cathode materials prepared in Examples 1-3 and Comparative Examples 1-4 at 25°C. Test conditions are: 2.8-4.25V, using 0.1C charge and discharge, using LAND charge and discharge meter.
- the first Coulombic efficiency of the ternary cathode material prepared by the present invention is more than 90%, the discharge capacity reaches more than 173mAh ⁇ g -1 , and the 200-cycle capacity retention rate reaches more than 90%, indicating that the regeneration of the present invention Ternary cathode materials have better electrochemical properties.
- Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the ternary cathode material prepared in Comparative Example 1 has not been annealed, and its purity, crystallinity and stability are not as good as those of Example 1, so the discharge capacity is lower.
- Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the ternary cathode material prepared in Comparative Example 2 was not doped with AlF 3 and could not reduce the cation mixing of the recovered ternary cathode material. Therefore, the first Coulombic efficiency and cycle performance were lower. Low.
- Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that the ternary cathode material prepared in Comparative Example 3 is not coated, and side reactions between the active material and the electrolyte will affect the battery capacity and electrode structure.
- Example 1 -3 all use graphene loaded with coatings, which are coated on the cathode material by spraying. During subsequent aerobic sintering, the graphene is converted into carbon dioxide, and the loaded particles will be evenly coated on the ternary cathode. In terms of materials, compared with conventional solid-phase mixed coating methods, the coating material is more evenly distributed, resulting in better cycle performance.
- Comparative Example 4 The difference between Comparative Example 4 and Example 1 is that the silica used for coating is not loaded on graphene. It can be seen from Table 1 that the cycle performance is lower, indicating that the coating effect of silica is better than that loaded on graphene. The resulting composite material is less effective.
Landscapes
- 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)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种废旧三元正极材料的再生方法,该方法包括以下步骤:(1)将废旧三元正极材料与酸混合进行活化;(2)将活化后的正极材料与锂源溶液混合,在加压加热条件下进行补锂,补锂后的正极材料在惰性气氛中退火;(3)将退火后的正极材料、镍源、钴源、锰源、氟化物和水混合,得到混合物后进行喷雾造粒,得到NCM前驱体,所述NCM前驱体在有氧氛围下煅烧,得到煅烧料;(4)采用负载有包覆物微粒的多孔石墨烯对所述煅烧料进行液相预包覆,所得预包覆物在有氧氛围下煅烧,得到包覆的三元正极材料。本发明通过退火、掺杂、梯度煅烧和包覆的手段有效提高了再生三元正极材料的纯度、结构的稳定性和电化学性能。
Description
本发明涉及锂离子正极材料回收技术领域,具体涉及一种废旧三元正极材料的再生方法。
锂离子电池是以两种不同的能够可逆地插入及脱出锂离子的嵌锂化合物分别作为电池的正极和负极的二次电池体系。充电时,锂离子从正极材料的晶格中脱出,经过电解质后插入到负极材料的晶格中,使得负极富锂,正极贫锂;放电时锂离子从负极材料的晶格中脱出,经过电解质后插入到正极材料的晶格中,使得正极富锂,负极贫锂。这样正负极材料在插入及脱出锂离子时相对于金属锂的电位的差值,就是电池的工作电压。
目前大量的锂离子电池被废弃,废弃的锂离子电池中含有大量不可再生且经济价值高的金属资源,如钴、锂、镍、铜、铝等,假如能有效地回收处理废弃或不合格的锂离子电池,不仅能减轻废旧电池对环境的压力,还可以防止造成钴、镍等金属资源的浪费。
工业上废旧三元锂离子电池的主要回收再生的方法为火法和湿法:火法是直接通过高温处理的方式回收电池材料,其工艺过程比较简单,但回收率低且高温处理时间长,能耗高,电解液、粘结剂等有机物高温下还会产生有害气体造成环境污染;湿法是通过拆解电池外壳,破碎、筛分后对电极材料中的有价金属进行浸出,再进行沉淀分离或萃取分离获得各金属相应的盐或氧化物来实现电池材料的回收利用,但工艺较复杂。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此,本发明提出一种废旧三元正极材料的再生方法,该方法通过补锂后进行高温退火,使得材料的原子间排列更为紧密,缩小了原子间距从而使晶粒细化,进而提高材料的结晶度;然后通过在材料中进行氟化物掺杂,降低材料阳离子混排,稳定材料的结构,提升循环和倍率性能;再通过对三元正极材料进行包覆,将三元正极材料与电解液隔离,减少副反应并减缓电极材料的坍塌。
本发明的上述技术目的是通过以下技术方案得以实现的:
一种废旧三元正极材料的再生方法,包括以下步骤:
S1:将废旧三元正极材料与酸混合进行活化;
S2:将活化后的正极材料与锂源溶液混合,在加压加热条件下进行补锂,补锂后的正极材料在惰性气氛中退火;
S3:将退火后的正极材料、镍源、钴源、锰源、氟化物和水混合,得到混合物后进行喷雾造粒,得到NCM前驱体,所述NCM前驱体在有氧氛围下煅烧,得到煅烧料;
S4:采用负载有包覆物微粒的多孔石墨烯对所述煅烧料进行液相预包覆,所得预包覆物在有氧氛围下煅烧,得到包覆的三元正极材料。
在本发明的一些实施方式中,步骤S1所述废旧三元正极材料经过以下步骤制得:拆解废旧三元锂电池,取出正极片,对所述正极片进行碱浸、固液分离、干燥、煅烧、研磨处理后,得到废旧三元正极材料。
在本发明的一些实施方式中,步骤S1中所述的酸为乙酸、酒石酸、苹果酸或柠檬酸中的至少一种。
在本发明的一些优选的实施方式中,步骤S1所述的酸的pH为3-5。
在本发明的一些实施方式中,步骤S2中所述的锂源为氢氧化锂、碳酸锂、碳酸氢锂、硝酸锂、氯化锂或溴化锂中的至少一种。
在本发明的一些实施方式中,步骤S2中所述的退火温度为500-950℃,时间为1-3h。
在本发明的一些优选的实施方式中,步骤S2中所述的退火温度为700-900℃,时间为1-3h。
在本发明的一些实施方式中,步骤S3中所述的镍源为NiC4H6O4·4H2O或Ni(NO3)2·6H2O中的至少一种;所述的钴源为CoC4H6O4·4H2O或Co(NO3)2·6H2O中的至少一种;所述的锰源为MnC4H6O4·4H2O或Mn(NO3)2·6H2O中的至少一种。
在本发明的一些实施方式中,步骤S3中所述的氟化物为氟化铵、氟化铝、氟化钠或氟化钾中的至少一种,正极材料与氟化物的摩尔比为1:(0.001-0.05)。
在本发明的一些优选的实施方式中,步骤S3中所述的氟化物为氟化铝,正极材料
与氟化铝的摩尔比为1:(0.005-0.03),作为优选的氟化铝,铝离子用于部分取代过渡金属离子位置,起到降低阳离子混排的作用。
在本发明的一些实施方式中,步骤S3中所述的煅烧温度为800-950℃,时间8-16h。
在本发明的一些实施方式中,步骤S4中所述的包覆材料为多孔石墨烯,所述多孔石墨烯负载锂盐、SiO2、AlF3、Al2O3、磷酸铁、ZrO2或V2O5中的至少一种。
在本发明的一些实施方式中,步骤S4中所述的负载有包覆物微粒的多孔石墨烯的制备方法如下:将多孔石墨烯加入到含有十六烷基三甲基溴化铵和氢氧化钠的去离子水中,超声分散均匀;在水浴中搅拌,再逐滴加入硅酸四乙酯,继续反应,经过离心,过滤后过夜烘干;上述产物在氩气中高温反应,自然冷却至室温得到复合材料。
在本发明的一些优选的实施方式中,步骤S4中所述的包覆材料为多孔石墨烯,所述多孔石墨烯负载SiO2。
在本发明的一些实施方式中,对步骤S3所述的NCM前驱体采用喷雾的方式进行包覆。
在本发明的一些实施方式中,步骤S4中所述的多梯度煅烧包括一次煅烧和二次煅烧,所述一次煅烧升温速率为1-6℃/min,温度为400-500℃,时间为4-6h;所述二次煅烧升温速率为1-6℃/min,温度为800-950℃,时间为8-16h。
根据本发明的一种优选的实施方式,至少具有以下有益效果:
1、水热补锂后进行退火处理,使得原子间排列更加紧密,缩小原子间距从而使晶粒细化,从而提高材料的结晶度、晶体结构的稳定性和电化学性能。
2、采用氟化物掺杂,氟可替代晶格中部分氧,以降低氧的氧化还原活性,起到稳定结构的作用,从而提升材料的循环和倍率性能。
3、作为优选的,本发明采用梯度煅烧,可以有效减缓三元正极材料在煅烧时的晶型转变速度,减少晶格缺陷,提升材料的完整性和稳定性。
4、采用在三元正极材料表面进行包覆,可以使电池中的活性物质与电解液之间进行物理隔离,减少副反应的发生,抑制过渡金属离子在电解液的溶解,同时,具有一定机械强度的非活性包覆层还可在长期循环过程中减缓电极材料结构的坍塌。
5、本发明预先制备负载有包覆物的石墨烯,包覆物颗粒粒度较小,均匀分散地负载在石墨烯上,不会团聚,通过喷雾的方式将负载有包覆物颗粒的石墨烯包覆于正极材料上,后续进行有氧烧结时,石墨烯转化为二氧化碳,而负载的颗粒则会均匀包覆在三元正极材料上,与常规的固相混合包覆方式相比,包覆材料分布更加均匀。
下面结合附图和实施例对本发明做进一步的说明,其中:
图1为本发明实施例1制得的NCM前驱体的SEM图;
图2为本发明实施例1制得的包覆后的三元正极材料的SEM图;
图3为本发明实施例1与对比例1所述煅烧料的XRD对比图;
图4为本发明实施例1制得的AlF3掺杂后的元素分布EDS图。
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述,以充分地理解本发明的目的、特征和效果。显然,所描述的实施例只是本发明的一部分实施例,而不是全部实施例,基于本发明的实施例,本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例,均属于本发明保护的范围。
实施例1
一种废旧三元正极材料的再生方法,包括以下步骤:
步骤1,废旧三元锂电池拆解后,取出正极片,按照固液比10g/L将正极片放入质量分数30%的氢氧化钠溶液中,控制温度为90℃,搅拌1.5h,待残余铝箔完全溶解后固液分离,得到浸出液和浸出渣;
步骤2,对浸出渣采用纯水洗涤,在110℃下干燥10h;
步骤3,将干燥后的浸出渣在500℃下,氧气氛围中煅烧5h,冷却后研磨得到粉末;
步骤4,将步骤3所得粉末加入到pH值为4.0的乙酸中,50℃下搅拌1h,随后固液分离得到固料与滤液;
步骤5,对步骤4所得固料采用纯水洗涤,得到活化后的正极材料;
步骤6,将活化正极材料按固液比1g:20mL加入到4mol/L的氢氧化锂溶液中,高
压、密闭、氮气氛围下加热,加热温度为280℃,加热时间为5h;
步骤7,补锂结束后过滤,在真空烘箱80℃下干燥,然后转移到管式炉中,加热至900℃,在流动的氮气中保温2h;
步骤8,将退火后的正极材料按照镍钴锰三元素总摩尔量与锂的摩尔量之比为1:1.08,同时按照Ni:Co:Mn=5:2:3,往滤渣中加入NiC4H6O4·4H2O、CoC4H6O4·4H2O、MnC4H6O4·4H2O,然后按照正极材料与AlF3的摩尔比1:0.03添加AlF3,再按照混合物与水的质量体积比0.3g:1mL的比例加水,超声10min后得到成分均一的混合悬浮液;
步骤9,将步骤8所得的悬浮液加到喷雾干燥器中,控制喷雾干燥器的温度为180℃,进料速度为450mL/h,进气压力0.5MPa,出口温度150℃,进行喷雾造粒,连续制备得到球状NCM523的前驱体;
步骤10,将步骤9制备出的NCM523前驱体放入马弗炉中,加工业氧气进行煅烧,温度升至850℃,保温10h,得到煅烧料;
步骤11,制备负载二氧化硅的石墨烯:将多孔石墨烯加入到含有十六烷基三甲基溴化铵和氢氧化钠的去离子水中,超声分散均匀。在水浴中搅拌,再逐滴加入硅酸四乙酯,继续反应,经过离心,过滤后过夜烘干。所述产物在氩气中高温反应,自然冷却至室温得到复合材料;
步骤12,按照步骤11所制得复合材料与水的质量体积比1g:100mL的比例加水,超声10min后得到复合材料悬浮液;
步骤13,将步骤12所制得的悬浮液以喷雾的方式喷淋在步骤10所述的煅烧料上,同时搅拌混合,搅拌速度为60rpm,搅拌时间20min,一共进行三次,得到二氧化硅质量百分数为0.5%的预包覆NCM前驱体;
步骤14,将步骤13制备出的预包覆NCM前驱体放入马弗炉中,加工业氧气进行两段煅烧,首先升温至500℃,保温5h,再升温至900℃,保温12h,得到再生的三元正极材料NCM523。
图2为本发明实施例1制得的包覆后的三元正极材料的SEM图,由图可见,本实施例制备的三元正极材料包覆效果较好。
图4为本发明实施例1制得的AlF3掺杂后的元素分布EDS图,由图可见,Ni、Co、Mn、F元素均匀分布,说明材料的均一性好。
实施例2
一种废旧三元正极材料的再生方法,包括以下步骤:
步骤1,废旧三元锂电池拆解后,取出正极片,按照固液比10g/L将正极片放入质量分数40%的氢氧化钠溶液中,控制温度为70℃,搅拌2h,待残余铝箔完全溶解后固液分离,得到浸出液和浸出渣;
步骤2,对浸出渣采用纯水洗涤,在100℃下干燥12h;
步骤3,将干燥后的浸出渣在500℃下,氧气氛围中煅烧5h,冷却后研磨得到粉末;
步骤4,将步骤3所得粉末加入到pH为3.0的苹果酸中,30℃下搅拌2h,随后固液分离得到固料与滤液;
步骤5,对步骤4所得固料采用纯水洗涤,得到活化后的正极材料;
步骤6,将活化正极材料按固液比1g:20mL加入到3mol/L的碳酸锂溶液中,氮气氛围下加热,加热温度为300℃,加热时间为6h;
步骤7,补锂结束后过滤,在真空烘箱80℃下干燥,然后转移到管式炉中,加热至800℃,在流动的氮气中保温1h;
步骤8,将退火后的正极材料按照镍钴锰三元素总摩尔量与锂的摩尔量之比为1:1.08,同时按照Ni:Co:Mn=6:2:2,往滤渣中加入NiC4H6O4·4H2O、CoC4H6O4·4H2O、MnC4H6O4·4H2O,然后按照正极材料与AlF3的摩尔比1:0.03添加AlF3,再按照混合物与水的质量体积比0.3g:1mL的比例加水,超声10min后得到成分均一的混合悬浮液;
步骤9,将步骤8所得的悬浮液加到喷雾干燥器中,控制喷雾干燥器的温度为180℃,进料速度为450mL/h,进气压力0.5MPa,出口温度150℃,进行喷雾造粒,连续制备得到球状NCM622的前驱体;
步骤10,将步骤9制备出的NCM622前驱体放入马弗炉中,加工业氧气进行煅烧,温度升至850℃,保温10h,得到煅烧料;
步骤11,制备负载二氧化硅的石墨烯:将多孔石墨烯加入到含有十六烷基三甲基溴
化铵和氢氧化钠的去离子水中,超声分散均匀。在水浴中搅拌,再逐滴加入硅酸四乙酯,继续反应,经过离心,过滤后过夜烘干。所述产物在氩气中高温反应,自然冷却至室温得到复合材料;
步骤12,按照步骤11所制得复合材料与水的质量体积比1g:100mL的比例加水,超声10min后得到复合材料悬浮液;
步骤13,将步骤12所制得的悬浮液以喷雾的方式喷淋在步骤10所述的煅烧料上,同时搅拌混合,搅拌速度为60rpm,搅拌时间20min,一共进行三次,得到二氧化硅质量百分数为0.5%的预包覆NCM前驱体;
步骤14,将步骤13制备出的预包覆NCM前驱体放入马弗炉中,加工业氧气进行两段煅烧,首先升温至400℃,保温6h,再升温至800℃,保温16h,得到再生的三元正极材料NCM622。
实施例3
一种废旧三元正极材料的再生方法,包括如下步骤:
步骤1,废旧三元锂电池拆解后,取出正极片,按照固液比10g/L将正极片放入质量分数40%的氢氧化钠溶液中,控制温度为70℃,搅拌2h,待残余铝箔完全溶解后固液分离,得到浸出液和浸出渣;
步骤2,对浸出渣采用纯水洗涤,在110℃下干燥10h;
步骤3,将干燥后的浸出渣在500℃下,氧气氛围中煅烧5h,冷却后研磨得到粉末;
步骤4,将步骤3所得粉末加入到pH为5.0的酒石酸中,30℃下搅拌2h,随后固液分离得到固料与滤液;
步骤5,对步骤4所得固料采用纯水洗涤,得到活化后的正极材料;
步骤6,将活化正极材料按固液比1g:40mL加入到5mol/L的氢氧化锂溶液中,氮气氛围下加热,加热温度为280℃,加热时间为5h;
步骤7,补锂结束后过滤,在真空烘箱80℃下干燥,然后转移到管式炉中,加热至800℃,在流动的氮气中保温1h;
步骤8,将退火后的正极材料按照镍钴锰三元素总摩尔量与锂的摩尔量之比为1:1.08,
同时按照Ni:Co:Mn=6:2:2,往滤渣中加入NiC4H6O4·4H2O、CoC4H6O4·4H2O、MnC4H6O4·4H2O,然后按照正极材料与AlF3的摩尔比1:0.03添加AlF3,再按照混合物与水的质量体积比0.3g:1mL的比例加水,超声10min后得到成分均一的混合悬浮液;
步骤9,将步骤8所得的悬浮液加到喷雾干燥器中,控制喷雾干燥器的温度为180℃,进料速度为450mL/h,进气压力0.5MPa,出口温度150℃,进行喷雾造粒,连续制备得到球状NCM622的前驱体;
步骤10,将步骤9制备出的NCM622前驱体放入马弗炉中,加工业氧气进行煅烧,温度升至850℃,保温10h,得到煅烧料;
步骤11,制备负载二氧化硅的石墨烯:将多孔石墨烯加入到含有十六烷基三甲基溴化铵和氢氧化钠的去离子水中,超声分散均匀。在水浴中搅拌,再逐滴加入硅酸四乙酯,继续反应,经过离心,过滤后过夜烘干。所述产物在氩气中高温反应,自然冷却至室温得到复合材料;
步骤12,按照步骤11所制得复合材料与水的质量体积比1g:100mL的比例加水,超声10min后得到复合材料悬浮液;
步骤13,将步骤12所制得的悬浮液以喷雾的方式喷淋在步骤10所述的煅烧料上,同时搅拌混合,搅拌速度为100rpm,搅拌时间20min,一共进行三次,得到二氧化硅质量百分数为0.5%的预包覆NCM前驱体;
步骤14,将步骤13制备出的预包覆NCM前驱体放入马弗炉中,加工业氧气进行两段煅烧,首先升温至500℃,保温6h,再升温至850℃,保温16h,得到再生的三元正极材料NCM622。
对比例1
一种废旧三元正极材料的再生方法,与实施例1的区别仅在于没有进行退火操作,其余条件不变,包括如下步骤:
步骤1,废旧三元锂电池拆解后,取出正极片,按照固液比10g/L将正极片放入质量分数30%的氢氧化钠溶液中,控制温度为90℃,搅拌1.5h,待残余铝箔完全溶解后固液分离,得到浸出液和浸出渣;
步骤2,对浸出渣采用纯水洗涤,在110℃下干燥10h;
步骤3,将干燥后的浸出渣在500℃下,氧气氛围中煅烧5h,冷却后研磨得到粉末;
步骤4,将步骤3所得粉末加入到pH值为4.0的乙酸中,50℃下搅拌1h,随后固液分离得到固料与滤液;
步骤5,对步骤4所得固料采用纯水洗涤,得到活化后的正极材料;
步骤6,将活化正极材料按固液比1g:20mL加入到4mol/L的氢氧化锂溶液中,高压、密闭、氮气氛围下加热,加热温度为280℃,加热时间为5h;
步骤7,将退火后的正极材料按照镍钴锰三元素总摩尔量与锂的摩尔量之比为1:1.08,同时按照Ni:Co:Mn=5:2:3,往滤渣中加入NiC4H6O4·4H2O、CoC4H6O4·4H2O、MnC4H6O4·4H2O,然后按照正极材料与AlF3的摩尔比1:0.03添加AlF3,再按照混合物与水的质量体积比0.3g:1mL的比例加水,超声10min后得到成分均一的混合悬浮液;
步骤8,将步骤7所得的悬浮液加到喷雾干燥器中,控制喷雾干燥器的温度为180℃,进料速度为450mL/h,进气压力0.5MPa,出口温度150℃,进行喷雾造粒,连续制备得到球状NCM523的前驱体;
步骤9,将步骤8制备出的NCM523前驱体放入马弗炉中,加工业氧气进行煅烧,温度升至850℃,保温10h,得到煅烧料;
步骤10,制备负载二氧化硅的石墨烯:将多孔石墨烯加入到含有十六烷基三甲基溴化铵和氢氧化钠的去离子水中,超声分散均匀。在水浴中搅拌,再逐滴加入硅酸四乙酯,继续反应,经过离心,过滤后过夜烘干。所述产物在氩气中高温反应,自然冷却至室温得到复合材料;
步骤11,按照步骤10所制得复合材料与水的质量体积比1g:100mL的比例加水,超声10min后得到复合材料悬浮液;
步骤12,将步骤12所制得的悬浮液以喷雾的方式喷淋在步骤9所述的煅烧料上,同时搅拌混合,搅拌速度为60rpm,搅拌时间20min,一共进行三次,得到二氧化硅质量百分数为0.5%的预包覆NCM前驱体;
步骤13,将步骤12制备出的包覆NCM前驱体放入马弗炉中,加工业氧气进行两
段煅烧,首先升温至500℃,保温5h,再升温至900℃,保温12h,得到再生的三元正极材料NCM523。
图3为实施例1与对比例1制得的包覆后的三元正极材料的XRD对比图,由图可见实施例1所制得三元正极材料的衍射峰强度较大,即退火的操作使三元正极材料的纯度和结晶度得到提升,从而提高了材料的稳定性。
对比例2
一种废旧三元正极材料的再生方法,与实施例1的区别仅在于没有加入AlF3掺杂,其余条件不变,包括如下步骤:
步骤1,废旧三元锂电池拆解后,取出正极片,按照固液比10g/L将正极片放入质量分数30%的氢氧化钠溶液中,控制温度为90℃,搅拌1.5h,待残余铝箔完全溶解后固液分离,得到浸出液和浸出渣;
步骤2,对浸出渣采用纯水洗涤,在110℃下干燥10h;
步骤3,将干燥后的浸出渣在500℃下,氧气氛围中煅烧5h,冷却后研磨得到粉末;
步骤4,将步骤3所得粉末加入到pH值为4.0的乙酸中,50℃下搅拌1h,随后固液分离得到固料与滤液;
步骤5,对步骤4所得固料采用纯水洗涤,得到活化后的正极材料;
步骤6,将活化正极材料按固液比1g:20mL加入到4mol/L的氢氧化锂溶液中,高压、密闭、氮气氛围下加热,加热温度为280℃,加热时间为5h;
步骤7,补锂结束后过滤,在真空烘箱80℃下干燥,然后转移到管式炉中,加热至900℃,在流动的氮气中保温2h;
步骤8,将退火后的正极材料按照镍钴锰三元素总摩尔量与锂的摩尔量之比为1:1.08,同时按照Ni:Co:Mn=5:2:3,往滤渣中加入NiC4H6O4·4H2O、CoC4H6O4·4H2O、MnC4H6O4·4H2O,然后按照混合物与水的质量体积比0.3g:1mL的比例加水,超声10min后得到成分均一的混合悬浮液;
步骤9,将步骤8所得的悬浮液加到喷雾干燥器中,控制喷雾干燥器的温度为180℃,进料速度为450mL/h,进气压力0.5MPa,出口温度150℃,进行喷雾造粒,连续制备得
到球状NCM523的前驱体;
步骤10,将步骤9制备出的NCM523前驱体放入马弗炉中,加工业氧气进行煅烧,温度升至850℃,保温10h,得到煅烧料;
步骤11,制备负载二氧化硅的石墨烯:将多孔石墨烯加入到含有十六烷基三甲基溴化铵和氢氧化钠的去离子水中,超声分散均匀。在水浴中搅拌,再逐滴加入硅酸四乙酯,继续反应,经过离心,过滤后过夜烘干。所述产物在氩气中高温反应,自然冷却至室温得到复合材料;
步骤12,按照步骤11所制得复合材料与水的质量体积比1g:100mL的比例加水,超声10min后得到复合材料悬浮液;
步骤13,将步骤12所制得的悬浮液以喷雾的方式喷淋在步骤10所述的煅烧料上,同时搅拌混合,搅拌速度为60rpm,搅拌时间20min,一共进行三次,得到二氧化硅质量百分数为0.5%的预包覆NCM前驱体;
步骤14,将步骤13制备出的预包覆NCM前驱体放入马弗炉中,加工业氧气进行两段煅烧,首先升温至500℃,保温5h,再升温至900℃,保温12h,得到再生的三元正极材料NCM523。
对比例3
一种废旧三元正极材料的再生方法,与实施例1的区别仅在于没有进行包覆操作,其余条件不变,包括如下步骤:
步骤1,废旧三元锂电池拆解后,取出正极片,按照固液比10g/L将正极片放入质量分数30%的氢氧化钠溶液中,控制温度为90℃,搅拌1.5h,待残余铝箔完全溶解后固液分离,得到浸出液和浸出渣;
步骤2,对浸出渣采用纯水洗涤,在110℃下干燥10h;
步骤3,将干燥后的浸出渣在500℃下,氧气氛围中煅烧5h,冷却后研磨得到粉末;
步骤4,将步骤3所得粉末加入到pH值为4.0的乙酸中,50℃下搅拌1h,随后固液分离得到固料与滤液;
步骤5,对步骤4所得固料采用纯水洗涤,得到活化后的正极材料;
步骤6,将活化正极材料按固液比1g:20mL加入到4mol/L的氢氧化锂溶液中,高压、密闭、氮气氛围下加热,加热温度为280℃,加热时间为5h;
步骤7,补锂结束后过滤,在真空烘箱80℃下干燥,然后转移到管式炉中,加热至900℃,在流动的氮气中保温2h;
步骤8,将退火后的正极材料按照镍钴锰三元素总摩尔量与锂的摩尔量之比为1:1.08,同时按照Ni:Co:Mn=5:2:3,往滤渣中加入NiC4H6O4·4H2O、CoC4H6O4·4H2O、MnC4H6O4·4H2O,然后按照正极材料与AlF3的摩尔比1:0.03添加AlF3,再按照混合物与水的质量体积比0.3g:1mL的比例加水,超声10min后得到成分均一的混合悬浮液;
步骤9,将步骤8所得的悬浮液加到喷雾干燥器中,控制喷雾干燥器的温度为180℃,进料速度为450mL/h,进气压力0.5MPa,出口温度150℃,进行喷雾造粒,连续制备得到球状NCM523的前驱体;
步骤10,将步骤9制备出的球状NCM前驱体放入马弗炉中,加工业氧气进行两段煅烧,首先升温至500℃,保温5h,再升温至900℃,保温12h,得到再生的三元正极材料NCM523。
对比例4
一种废旧三元正极材料的再生方法,与实施例1的区别仅在于预包覆物不包括石墨烯,其余条件不变,包括如下步骤:
步骤1,废旧三元锂电池拆解后,取出正极片,按照固液比10g/L将正极片放入质量分数30%的氢氧化钠溶液中,控制温度为90℃,搅拌1.5h,待残余铝箔完全溶解后固液分离,得到浸出液和浸出渣;
步骤2,对浸出渣采用纯水洗涤,在110℃下干燥10h;
步骤3,将干燥后的浸出渣在500℃下,氧气氛围中煅烧5h,冷却后研磨得到粉末;
步骤4,将步骤3所得粉末加入到pH值为4.0的乙酸中,50℃下搅拌1h,随后固液分离得到固料与滤液;
步骤5,对步骤4所得固料采用纯水洗涤,得到活化后的正极材料;
步骤6,将活化正极材料按固液比1g:20mL加入到4mol/L的氢氧化锂溶液中,高
压、密闭、氮气氛围下加热,加热温度为280℃,加热时间为5h;
步骤7,补锂结束后过滤,在真空烘箱80℃下干燥,然后转移到管式炉中,加热至900℃,在流动的氮气中保温2h;
步骤8,将退火后的正极材料按照镍钴锰三元素总摩尔量与锂的摩尔量之比为1:1.08,同时按照Ni:Co:Mn=5:2:3,往滤渣中加入NiC4H6O4·4H2O、CoC4H6O4·4H2O、MnC4H6O4·4H2O,然后按照正极材料与AlF3的摩尔比1:0.03添加AlF3,再按照混合物与水的质量体积比0.3g:1mL的比例加水,超声10min后得到成分均一的混合悬浮液;
步骤9,将步骤8所得的悬浮液加到喷雾干燥器中,控制喷雾干燥器的温度为180℃,进料速度为450mL/h,进气压力0.5MPa,出口温度150℃,进行喷雾造粒,连续制备得到球状NCM523的前驱体;
步骤10,将步骤9制备出的NCM523前驱体放入马弗炉中,加工业氧气进行煅烧,温度升至850℃,保温10h,得到煅烧料;
步骤11,往含有十六烷基三甲基溴化铵和氢氧化钠的去离子水中逐滴加入硅酸四乙酯,在水浴中搅拌,继续反应,经过离心,过滤后过夜烘干。所述产物在氩气中高温反应,自然冷却至室温得到二氧化硅;
步骤12,按照步骤11所制得二氧化硅与水的质量体积比1g:100mL的比例加水,超声10min后得到二氧化硅悬浮液;
步骤13,将步骤12所制得的悬浮液以喷雾的方式喷淋在步骤10所述的煅烧料上,同时搅拌混合,搅拌速度为60rpm,搅拌时间20min,一共进行三次,得到二氧化硅质量百分数为0.5%的预包覆NCM前驱体;
步骤14,将步骤13制备出的预包覆NCM前驱体放入马弗炉中,加工业氧气进行两段煅烧,首先升温至500℃,保温5h,再升温至900℃,保温12h,得到再生的三元正极材料NCM523。
试验例
本发明采用扣式电池在25℃下测试实施例1-3和对比例1-4所制备的三元正极材料的首次库伦效率、放电容量以及200周循环容量保持率。测试条件为:2.8-4.25V,采用
0.1C充放电,采用LAND充放电仪。
表1本发明实施例与对比例的电化学性能测试数据:
由表1可知,本发明制得的三元正极材料的首次库伦效率在90%以上,放电容量达到173mAh·g-1以上,200周循环容量保持率达到了90%以上,说明本发明再生的三元正极材料有较好的电化学性能。
对比例1与实施例1的区别在于对比例1所制得的三元正极材料没有经过退火操作,其纯度、结晶度和稳定性均不如实施例1,因而放电容量较低。
对比例2与实施例1的区别在于对比例2所制得的三元正极材料没有加入AlF3进行掺杂,无法降低回收的三元正极材料的阳离子混排,因而首次库伦效率及循环性能较低。
对比例3与实施例1的区别在于对比例3所制得的三元正极材料没有进行包覆,其中的活性物质与电解液会发生副反应从而影响电池的容量和电极结构,而实施例1-3均采用了负载有包覆物的石墨烯,通过喷雾的方式包覆在正极材料上,后续进行有氧烧结时,石墨烯转化为二氧化碳,负载的颗粒则会均匀包覆在三元正极材料上,与常规的固相混合包覆方式相比,包覆材料分布更加均匀,从而得到较好的循环性能。
对比例4与实施例1的区别在于用于包覆的二氧化硅没有负载在石墨烯上,由表1可以看出循环性能较低,表明二氧化硅的包覆效果比负载在石墨烯上时所形成的复合材料效果差。
上面结合附图对本发明实施例作了详细说明,但是本发明不限于上述实施例,在所属技术领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作
出各种变化。此外,在不冲突的情况下,本发明的实施例及实施例中的特征可以相互组合。
Claims (10)
- 一种废旧三元正极材料的再生方法,其特征在于,包括以下步骤:S1:将废旧三元正极材料与酸混合进行活化;S2:将活化后的正极材料与锂源溶液混合,在加压加热条件下进行补锂,补锂后的正极材料在惰性气氛中退火;S3:将退火后的正极材料、镍源、钴源、锰源、氟化物和水混合,得到混合物后进行喷雾造粒,得到NCM前驱体,所述NCM前驱体在有氧氛围下煅烧,得到煅烧料;S4:采用负载有包覆物微粒的多孔石墨烯对所述煅烧料进行液相预包覆,所得预包覆物在有氧氛围下煅烧,得到包覆的三元正极材料。
- 根据权利要求1所述的一种废旧三元正极材料的再生方法,其特征在于,步骤S1中所述的酸为乙酸、酒石酸、苹果酸或柠檬酸中的至少一种。
- 根据权利要求1所述的一种废旧三元正极材料的再生方法,其特征在于,步骤S2中所述的锂源溶液为含有氢氧化锂、碳酸锂、碳酸氢锂、硝酸锂、氯化锂或溴化锂中至少一种的溶液。
- 根据权利要求1所述的一种废旧三元正极材料的再生方法,其特征在于,步骤S2中所述的退火温度为500-950℃,时间为1-3h。
- 根据权利要求1所述的一种废旧三元正极材料的再生方法,其特征在于,步骤S3中所述的镍源为NiC4H6O4·4H2O或Ni(NO3)2·6H2O中的至少一种;所述的钴源为CoC4H6O4·4H2O或Co(NO3)2·6H2O中的至少一种;所述的锰源为MnC4H6O4·4H2O或Mn(NO3)2·6H2O中的至少一种。
- 根据权利要求1所述的一种废旧三元正极材料的再生方法,其特征在于,步骤S3中所述的氟化物为氟化铵、氟化铝、氟化钠或氟化钾中的至少一种,退火后的正极材料与氟化物的摩尔比为1:(0.001-0.05)。
- 根据权利要求1所述的一种废旧三元正极材料的再生方法,其特征在于,步骤S3中所述的煅烧温度为800-950℃,时间8-16h。
- 根据权利要求1所述的一种废旧三元正极材料的再生方法,其特征在于,步骤 S4中所述的包覆物微粒为锂盐、SiO2、AlF3、Al2O3、磷酸铁、ZrO2或V2O5中的至少一种。
- 根据权利要求1所述的一种废旧三元正极材料的再生方法,其特征在于,步骤S3中,所述预包覆的过程为:将所述负载有包覆物微粒的多孔石墨烯与水混合制成悬浮液,所述悬浮液以喷雾的方式喷淋在所述煅烧料上,同时对煅烧料进行搅拌,即得所述预包覆物。
- 根据权利要求1所述的一种废旧三元正极材料的再生方法,其特征在于,步骤S4中所述的煅烧采用多梯度煅烧,包括一次煅烧和二次煅烧,所述一次煅烧升温速率为1-6℃/min,温度为400-500℃,时间为4-6h;所述二次煅烧升温速率为1-6℃/min,温度为800-950℃,时间为8-16h。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211149641.4 | 2022-09-21 | ||
CN202211149641.4A CN115498298A (zh) | 2022-09-21 | 2022-09-21 | 一种废旧三元正极材料的再生方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2024060547A1 true WO2024060547A1 (zh) | 2024-03-28 |
Family
ID=84470933
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2023/082858 WO2024060547A1 (zh) | 2022-09-21 | 2023-03-21 | 一种废旧三元正极材料的再生方法 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN115498298A (zh) |
WO (1) | WO2024060547A1 (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115498298A (zh) * | 2022-09-21 | 2022-12-20 | 广东邦普循环科技有限公司 | 一种废旧三元正极材料的再生方法 |
US20240304882A1 (en) * | 2023-03-07 | 2024-09-12 | 24M Technologies, Inc. | Direct regeneration of spent lithium electrodes via heat treatment |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017096525A1 (zh) * | 2015-12-08 | 2017-06-15 | 北京当升材料科技股份有限公司 | 锂离子电池正极材料、其制备方法、锂离子电池正极以及锂离子电池 |
CN108615869A (zh) * | 2018-05-18 | 2018-10-02 | 浙江美都海创锂电科技有限公司 | 氧化物包覆氮化石墨烯负载镍钴锰正极材料的制备及应用 |
CN111009645A (zh) * | 2019-11-27 | 2020-04-14 | 宜宾锂宝新材料有限公司 | 一种石墨烯基/AlPO4复合包覆改性高镍三元正极材料的方法 |
CN111129487A (zh) * | 2020-01-03 | 2020-05-08 | 昆明理工大学 | 一种废旧三元正极材料的水热补锂-喷雾重塑再生方法 |
CN113120971A (zh) * | 2021-03-17 | 2021-07-16 | 广东邦普循环科技有限公司 | 一种废旧三元正极材料的再生方法和应用 |
CN113636605A (zh) * | 2021-07-07 | 2021-11-12 | 华中科技大学 | 完全失效三元正极材料低成本空气条件下的物理修复方法 |
CN113745493A (zh) * | 2021-08-31 | 2021-12-03 | 深圳市华胜超级材料系统工程有限公司 | 一种石墨烯改性高镍系正极材料的制备方法 |
CN114853061A (zh) * | 2022-04-29 | 2022-08-05 | 芜湖天弋能源科技有限公司 | 一种多孔片状钠离子电池负极材料制备方法 |
CN115498298A (zh) * | 2022-09-21 | 2022-12-20 | 广东邦普循环科技有限公司 | 一种废旧三元正极材料的再生方法 |
-
2022
- 2022-09-21 CN CN202211149641.4A patent/CN115498298A/zh active Pending
-
2023
- 2023-03-21 WO PCT/CN2023/082858 patent/WO2024060547A1/zh unknown
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017096525A1 (zh) * | 2015-12-08 | 2017-06-15 | 北京当升材料科技股份有限公司 | 锂离子电池正极材料、其制备方法、锂离子电池正极以及锂离子电池 |
CN108615869A (zh) * | 2018-05-18 | 2018-10-02 | 浙江美都海创锂电科技有限公司 | 氧化物包覆氮化石墨烯负载镍钴锰正极材料的制备及应用 |
CN111009645A (zh) * | 2019-11-27 | 2020-04-14 | 宜宾锂宝新材料有限公司 | 一种石墨烯基/AlPO4复合包覆改性高镍三元正极材料的方法 |
CN111129487A (zh) * | 2020-01-03 | 2020-05-08 | 昆明理工大学 | 一种废旧三元正极材料的水热补锂-喷雾重塑再生方法 |
CN113120971A (zh) * | 2021-03-17 | 2021-07-16 | 广东邦普循环科技有限公司 | 一种废旧三元正极材料的再生方法和应用 |
CN113636605A (zh) * | 2021-07-07 | 2021-11-12 | 华中科技大学 | 完全失效三元正极材料低成本空气条件下的物理修复方法 |
CN113745493A (zh) * | 2021-08-31 | 2021-12-03 | 深圳市华胜超级材料系统工程有限公司 | 一种石墨烯改性高镍系正极材料的制备方法 |
CN114853061A (zh) * | 2022-04-29 | 2022-08-05 | 芜湖天弋能源科技有限公司 | 一种多孔片状钠离子电池负极材料制备方法 |
CN115498298A (zh) * | 2022-09-21 | 2022-12-20 | 广东邦普循环科技有限公司 | 一种废旧三元正极材料的再生方法 |
Also Published As
Publication number | Publication date |
---|---|
CN115498298A (zh) | 2022-12-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zhou et al. | Pyrometallurgical technology in the recycling of a spent lithium ion battery: evolution and the challenge | |
Zhao et al. | Regeneration and reutilization of cathode materials from spent lithium-ion batteries | |
CN106495161B (zh) | 一种基于金属介入金属热还原制备纳米硅的方法 | |
WO2024060547A1 (zh) | 一种废旧三元正极材料的再生方法 | |
JP7220360B2 (ja) | 正極材料の回収方法、得られた正極材料およびその用途 | |
WO2020098087A1 (zh) | 一种锂离子电池氧化亚硅复合负极材料及制法 | |
CN112952049A (zh) | 一种修复高镍正极材料表面结构的方法、由其得到的高镍正极材料以及锂离子电池 | |
CN113120971B (zh) | 一种废旧三元正极材料的再生方法和应用 | |
Fei et al. | Selective lithium extraction of cathode materials from spent lithium-ion batteries via low-valent salt assisted roasting | |
CN113200574A (zh) | 一种从混合废旧锂电再生富锂锰基正极的方法 | |
CN113072052B (zh) | 一种废磷酸铁锂补锂修复方法和应用 | |
Shen et al. | Recycling cathodes from spent lithium-ion batteries based on the selective extraction of lithium | |
CN113314710A (zh) | 一种从废旧锂离子电池中回收与再生正极材料的方法 | |
WO2023179048A1 (zh) | 一种氟铝共掺杂的钴酸锂正极材料及其制备方法 | |
WO2023207247A1 (zh) | 一种多孔隙球形钴氧化物颗粒及其制备方法 | |
Chen et al. | Hydrometallurgical processes for valuable metals recycling from spent lithium-ion batteries | |
CN115504524A (zh) | 一种单晶高镍材料及其制备方法和应用 | |
CN111403842A (zh) | 废旧锂电池正极材料的回收方法和球形氧化镍材料及应用 | |
CN106477623A (zh) | 一种制备绒球状钛酸锂的方法 | |
CN113871589A (zh) | 一种熔盐辅助钛酸锂包覆的富锂锰基正极材料及其制备方法 | |
WO2024082544A1 (zh) | 废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法 | |
CN117276731A (zh) | 一种深共晶溶剂回收再生废旧锂离子电池正极材料的方法 | |
CN115924879B (zh) | 一种从报废磷酸铁锂材料中回收磷酸铁锂的方法 | |
WO2023060992A1 (zh) | 正极边角料回收合成高安全性正极材料的方法和应用 | |
CN116102080A (zh) | 一种利用废旧钠离子电池再生制备正极材料的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 23866847 Country of ref document: EP Kind code of ref document: A1 |