CN113629241A - Preparation method of core-shell structure cathode material, cathode material and lithium ion battery - Google Patents
Preparation method of core-shell structure cathode material, cathode material and lithium ion battery Download PDFInfo
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- CN113629241A CN113629241A CN202110903146.7A CN202110903146A CN113629241A CN 113629241 A CN113629241 A CN 113629241A CN 202110903146 A CN202110903146 A CN 202110903146A CN 113629241 A CN113629241 A CN 113629241A
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- shell structure
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- 239000010406 cathode material Substances 0.000 title claims abstract description 40
- 239000011258 core-shell material Substances 0.000 title claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 79
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229920001817 Agar Polymers 0.000 claims abstract description 30
- 239000008272 agar Substances 0.000 claims abstract description 30
- 239000011257 shell material Substances 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000011572 manganese Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000000499 gel Substances 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 19
- 239000010405 anode material Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000007774 positive electrode material Substances 0.000 claims description 13
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- -1 halogen salt Chemical class 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 37
- 150000001768 cations Chemical class 0.000 description 17
- 239000011162 core material Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000012792 core layer Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 4
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 2
- 229910006596 α−NaFeO2 Inorganic materials 0.000 description 2
- 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
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910011624 LiNi0.7Co0.1Mn0.2O2 Inorganic materials 0.000 description 1
- 229910021311 NaFeO2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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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
- 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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Abstract
The invention provides a preparation method of a core-shell structure cathode material for a lithium ion battery, which comprises the following steps: weighing a precursor and a lithium source according to a stoichiometric ratio, uniformly mixing, and performing low-temperature pretreatment to obtain a core part material A; dissolving agar powder in water, uniformly stirring under the water bath heating condition to form a hot agar solution, dissolving a lithium source, a nickel source, a manganese source and a cobalt source in the hot agar solution, and uniformly stirring to form a transparent solution for an external shell material B; immersing the material A in the material B, aging for a certain time, cooling in a water bath to form gel, and removing moisture by freeze drying to obtain a material C; and sintering the material C to obtain the cathode material with the core-shell structure. The invention also provides the core-shell structure cathode material prepared by the preparation method and a lithium ion battery adopting the core-shell structure cathode material. The core-shell structure cathode material prepared by the invention not only has higher conductivity, but also can provide more effective charge transfer and obtain better electrochemical performance.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to the field of lithium ion battery anode materials, and specifically relates to a core-shell structure anode material for a lithium ion battery and a preparation method thereof.
Background
With the exhaustion of three major fossil fuels and the increasingly poor environmental pollution problem, the development of renewable energy and clean energy is imminent. Lithium Ion Battery (LIB) is currently the most promising secondary high-efficiency battery, and it is currently the fastest-developing chemical energy storage power source in the market. Compared with the traditional secondary battery, the lithium ion battery has the advantages of high energy density, high specific capacity, high working voltage, good rate performance, good cycle performance, low self-discharge rate, no memory effect, quick charge and discharge, environmental protection, long charge and discharge service life and the like, is considered to be an energy storage device for realizing the mutual conversion of chemical energy and electric energy, is widely researched and developed in recent years, is widely applied to the aspects of household appliances, portable electronic equipment, power automobiles and the like at present, and gradually relates to the field of electric automobile power.
The nickel-rich ternary material is one of the anode materials meeting the requirement of the high-energy-density lithium ion battery at present. The nickel-rich ternary cathode material comprises nickel-rich nickel cobalt lithium manganate (LiNi)xCoyMnzO2) And lithium nickel cobalt aluminate (LiNi)xCoyAlzO2) The nickel content of the material is generally greater than 50%. Like other ternary materials, the nickel-rich ternary material has alpha-NaFeO2The crystal structure of (3), R3m space group. However, the layered nickel-rich positive electrode material has inherent defects and structural changes, and poor cycle performance, although the specific capacity increases with the increase of the nickel content. The main reasons are as follows: 1) unstable surface properties. Residual lithium on the surface of the nickel-rich ternary material is exposed in the air to easily form Li2CO3LiOH and other miscellaneous phases, and the alkalinity of the material particles is increased. This not only presents difficulties for the subsequent coating process, but the insulating impurity phase increases the interfacial resistance of the material. In addition, in the deep delithiated state, the particlesThe high valence transition metal ions on the particle surface have strong oxidizability, and are easy to react with electrolyte to cause capacity loss. Finally, repeated electrochemical reactions can induce degradation of the surface structure of the nickel-rich material, deteriorating electrochemical performance. 2) Structural defects and lithium nickel mixed-matrix. Limited by thermodynamic factors, it is difficult to prepare nickel-rich ternary materials which meet the composition of the stoichiometric ratio. Part of Ni2+Easily migrate to the lithium layer to occupy the lithium site, resulting in Li+/Ni2+And (4) cation mixing and discharging. The serious lithium-nickel deintercalation affects the deintercalation and electrochemical performance of lithium ions. Such structural defects increase the internal resistance of the material and reduce the electrochemical activity. 3) Intergranular cracks and microstrain. In electrochemical reactions, repeated phase transformations are usually accompanied by changes in lattice parameters and the generation of microstresses. Newly generated cracks are exposed in the electrolyte, and side reactions continuously occur to form additional insulating films and even cause pulverization of the electrode material, thereby increasing the impedance of the material and reducing the dynamic performance.
In order to improve the situation, researchers develop a ternary material with a core-shell structure, wherein the nickel content of the core structure at the spherical center is the highest, so that the ternary material has a high energy storage effect, and the nickel content of the shell structure at the outermost layer is lower, so that the content of divalent nickel ions outside the spherical shell is kept in a lower range, and lithium-nickel mixed discharge is effectively prevented. In addition, the in-situ technology is utilized to further study the changes of the surface composition, microstructure and electrochemical behavior of the material in the electrochemical process, and the reasonable selection and design of the coating experiment and the doping experiment are also very necessary.
In the prior art, the modification strategy of the nickel-rich ternary cathode material mainly comprises: surface and interface engineering, bulk phase doping, morphology control and other modification means. The coating mainly comprises a wet method and a dry method, and the main principle is that one or more elements are coated on the surface of the synthesized ternary material. In addition, the coating uniformity of the surface dry coating is not high, the coating stability is poor, the coating is easy to fall off, the structural lithium can fall off due to the surface wet coating, the specific surface area of the anode material is increased after washing, the change is irregular and can be circulated, and the intrinsic characteristics of the material are influenced. For example, CN106784837A discloses an oxidationThe preparation method of the aluminum-coated lithium ion battery anode material comprises the following steps: (1) adding water into the hydroxide precursor of the positive electrode material and stirring to obtain positive electrode material precursor slurry; (2) dissolving sodium metaaluminate in water to obtain an aluminum salt solution; (3) adding the precursor slurry of the anode material into an aluminum salt solution, stirring, and introducing CO2Obtaining an aluminum hydroxide coated anode material precursor; (4) filtering, washing and drying the slurry of the precursor of the positive electrode material coated by the aluminum hydroxide to obtain precursor powder of the positive electrode material coated by the aluminum hydroxide; (5) mixing the precursor powder of the positive electrode material coated by the aluminum hydroxide with lithium salt to obtain mixed powder; (6) and carrying out heat treatment on the mixed powder to obtain the aluminum oxide coated lithium ion battery anode material. The lithium ion battery anode material prepared by the method has an unstable structure.
The doping element exists in the phase structure of the anode material, can reduce the occurrence of parasitic reaction between the anode material and the electrolyte, and is helpful for improving the cycle performance of the anode material. However, since the coating is only carried out on the surface of the material, the crystal structure of the anode material is not substantially improved, and no coating element or only a small part of the coating element enters the crystal lattice, the improvement effect on inhibiting the cation mixed discharge of the anode material and improving the electronic conductivity of the material is limited.
In the process of inserting and extracting lithium ions in the material, the particles with fine and uniform particle size can shorten the migration path of the lithium ions in a solid phase, and fully utilize active substances near the center of the particles, thereby improving the electrochemical performance of the material; meanwhile, the specific surface area is increased due to the fine material particles and uniform appearance, and the electrolyte can be in contact with the active substances more fully during electrode reaction. Therefore, the preparation method is perfected, and the synthesized particles with fine particle size and uniform distribution are important ways for improving the electrochemical performance of the composite material. In general, metal ion doping is a method for effectively improving the long-term cycling stability of the layered nickel-rich material, but cannot reduce the direct contact between the material and air or electrolyte and reduce the generation of lithium residues on the surface of the material. Although the step of washing the surface residues can be added in the preparation process, the nickel-rich material is very sensitive to moisture and is easy to carry out lithium removal reaction, and the surface crystal structure is damaged, so that the electrochemical performance of the material is reduced. Therefore, the surface coating is needed to be further adopted for modification to modify the layered nickel-rich cathode material, so that the de-intercalation of lithium ions is facilitated, and the excessive lithium residues on the surface of the material are reduced. The doping modification has good lithium ion conductivity, is beneficial to the de-intercalation of lithium ions, and can greatly improve the rate capability of the layered nickel-rich cathode material, thereby improving the power density and the energy density of the cathode material of the lithium ion battery. The surface coating modification can reduce the alkali content on the surface of the material, reduce the occurrence of side reactions and improve the cycle performance and the safety performance of the layered nickel-rich cathode material.
Therefore, how to solve the above-mentioned deficiencies of the prior art is a problem to be solved by the present invention.
Disclosure of Invention
The invention aims to solve the technical problems of how to improve the electrochemical performance of the anode material, reduce side reactions and improve the cycle performance and safety performance of the anode material.
The invention solves the technical problems through the following technical means: a preparation method of a core-shell structure cathode material comprises a core part, a transition layer and an outer shell part, so that a multi-stage structure is formed, the core part is a ternary material, the outer shell part is a porous modified ternary material, the outer shell part is densely attached to the core part, and the transition layer is a gradient modified interface, wherein the preparation method of the core-shell structure cathode material comprises the following steps:
s1, weighing the precursor and the lithium source according to the stoichiometric ratio, uniformly mixing, and performing low-temperature pretreatment to obtain a core part material A;
s2, dissolving agar powder in water, uniformly stirring under a water bath heating condition to form a hot agar solution, dissolving a lithium source, a nickel source, a manganese source and a cobalt source in the hot agar solution, and uniformly stirring to form a transparent solution for the external shell material B;
s3, immersing the core part material A into the outer shell material B, aging for a certain time, cooling in a water bath to form gel, and removing moisture in the gel by freeze drying to obtain a material C;
and S4, sintering the material C to obtain the cathode material with the core-shell structure.
The core-shell structure cathode material prepared by the invention is a nickel cobalt lithium manganate material with a porous shell structure, the gaps among the porous nanostructures of the external shell part are favorable for the electrolyte to permeate into the electrode, the porous structure of the external shell part is favorable for increasing the specific surface area, increasing the contact between the electrolyte and the electrode material and obtaining more active points, and the shape, the pore diameter and the size distribution of the shape are favorable for promoting the high-speed diffusion of ions and obtaining high electrochemical performance. Not only has higher conductivity, but also provides more effective charge transfer and obtains better electrochemical performance.
Preferably, the lithium source in steps S1 and S2 is at least one of lithium hydroxide, lithium carbonate, lithium chloride, lithium nitrate, lithium acetate, lithium sulfate, lithium phosphate and lithium hydrogen phosphate, and the molar ratio of the 1 lithium element in step S to the total amount of metal elements in the precursor is (1-1.2): 1, in the step S2, the molar ratio of the lithium element to the total amount of the nickel-cobalt-manganese metal element is (0.90-1): 1.
preferably, the low-temperature pretreatment condition in step S1 is that the volume concentration of the oxygen atmosphere is 30-99%, the temperature is 300-500 ℃, and the time is 2-6 hours.
Preferably, in step S2, the nickel source, the cobalt source, and the manganese source are at least one of soluble sulfate, carbonate, halogen salt, or nitrate.
Preferably, the sol in the step S2 is treated under the conditions of 70-90 ℃ in a water bath and normal temperature and pressure.
Preferably, in step S2, an additive may be introduced, the additive is one or more of nano oxides, hydroxides or soluble salts of Sr, Al, W, Ti, Mg, Zr, Ba, Y, La, V, Ta, Y, and the molar ratio of the addition amount to the metal element content of the shell layer cathode material is a, where 0 < a < 0.35.
Preferably, the aging time in step S3 is 0.5-3 hours, and the step can be repeated according to the experimental requirement of the shell thickness.
Preferably, in the step S3, the water bath cooling temperature is 5-20 ℃, and the freeze drying condition is-40 ℃ to 0 ℃ for 5-48 hours.
Preferably, the sintering condition in step S4 is that the volume concentration of the oxygen atmosphere is 30-99%, the temperature is 500-900 ℃, and the time is 8-24 hours.
The invention also provides a core-shell structure cathode material prepared by the preparation method of the core-shell structure cathode material according to any one of the schemes.
The invention also provides a lithium ion battery adopting the core-shell structure cathode material.
The invention has the advantages that:
(1) according to the nickel cobalt lithium manganate material with the porous shell structure, the gaps among the porous nanostructures of the shell are favorable for the electrolyte to permeate into the electrode, the porous structure of the surface shell is favorable for increasing the specific surface area, increasing the contact between the electrolyte and the electrode material and obtaining more active points, and the shape, the pore diameter and the size distribution of the nickel cobalt lithium manganate material are favorable for promoting the high-speed diffusion of ions and obtaining high electrochemical performance. Not only has higher conductivity, but also provides more effective charge transfer and obtains better electrochemical performance.
(2) The core-shell structure can effectively adapt to volume expansion in the charge and discharge process and prevent the material from being broken, thereby improving the cycle stability and the rate capability of the material.
(3) The core has higher nickel content, and the shell is made of a material with lower nickel content. The ternary material prepared by the method has higher capacity, the surface residual alkali content is controlled, the nickel-rich material is reduced, the residual alkali washing procedure is reduced, and the problems of water absorption and the like caused by nickel-rich ternary in the preparation process of the battery cell pole piece are avoided.
(4) The agar powder can be decomposed in the sintering process to form amorphous carbon, and the in-situ modified material can increase the conductivity.
(5) The synthesis method adopted by the invention does not need complex equipment, the used raw materials are cheap, the process is simple and easy to operate, and large-scale industrial production can be realized.
Drawings
Fig. 1 is an X-ray diffraction pattern of the porous lithium ion battery cathode material with a layered structure prepared in example 1, and from an XRD spectrogram of fig. 1, it can be seen that the material belongs to an α -NaFeO2 layered structure, has no other impurity peak, has a sharp diffraction peak, and has a good crystal structure of the cathode material.
FIG. 2 is the SEM topography of example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
S1, weighing precursor Ni according to the stoichiometric ratio of 1:1.10.7Co0.1Mn0.2(OH)2Lithium source LiOH. H2O, after being uniformly mixed, the volume concentration of the oxygen atmosphere is 30%, and the core material A is obtained after pretreatment for 3 hours at the low temperature of 400 ℃;
s2, dissolving agar powder in water at normal temperature and pressure, stirring uniformly under 70 ℃ water bath heating condition to form hot agar solution, and adding 2.0mol L of agar solution-1Nickel sulfate, cobalt sulfate and manganese sulfate (cation molar ratio Ni: Co: Mn: 50:20:30) and LiOH. H2O is dissolved in the hot agar solution, wherein the stoichiometric ratio of metal cations to lithium elements is 1: 0.9, uniformly stirring to form a transparent solution, adding nano alumina into the solution, wherein the molar ratio of the addition amount of the alumina to the total amount of the nickel-cobalt-manganese metal cations is 0.35, and the uniform solution is used for a shell material B;
s3, immersing the core material A into the core layer solution B, aging for 2 hours, cooling in a water bath at 5 ℃ to form gel, freezing at-5 ℃ for 15 hours, and drying to remove water to obtain a material C;
s4, sintering the material C for 24 hours at 500 ℃ under the condition that the volume concentration of an oxygen atmosphere is 50% to obtain a positive electrode material with a core-shell structure;
the specific surface area of the material prepared by the method is 0.95 square meters per gram, and the electrochemical performance of the material is tested.
FIG. 1 is the X-ray diffraction pattern of the lithium ion battery positive electrode material with porous layered structure prepared in examples 1-4, and from the XRD pattern of FIG. 1, it can be seen that the material belongs to alpha-NaFeO2The layered structure has no other miscellaneous peak, the diffraction peak is sharp, and the crystal structure of the anode material is better. FIG. 2 is the SEM topography of example 1.
Example 2
S1, according to 1: 1.0 stoichiometric ratio of Ni precursor0.8Co0.1Mn0.1(OH)2Li, lithium source2CO3After uniform mixing, the volume concentration of the oxygen atmosphere is 50%, and the core material A is obtained after pretreatment for 6 hours at low temperature of 300 ℃;
s2, dissolving agar powder in water at normal temperature and pressure, stirring uniformly under the condition of water bath heating at 90 ℃ to form hot agar solution, and adding 2.0mol L of agar solution-1Nickel acetate, cobalt acetate and manganese acetate (molar ratio of cations Ni: Co: Mn 60:20:20) and Li2CO3Dissolving in the hot agar solution, wherein the stoichiometric ratio of metal cation to lithium element is 1: 0.97, uniformly stirring to form a transparent solution, adding nano tungsten oxide into the solution, wherein the molar ratio of the addition amount of the tungsten oxide to the total amount of the nickel-cobalt-manganese metal cations is 0.08, and the uniform solution is used for a shell material B;
s3, immersing the core material A into the core layer solution B, aging for 0.5 hour, cooling in a water bath at 20 ℃ to form gel, and freeze-drying at-50 ℃ for 5 hours to remove water to obtain a material C;
s4, sintering the material C at 700 ℃ for 15 hours under the condition that the volume concentration of an oxygen atmosphere is 99% to obtain a positive electrode material with a core-shell structure;
the specific surface area of the material prepared by the method is 0.98 square meter per gram, and the electrochemical performance test is carried out on the material
Example 3
S1, according to 1: 1.2 stoichiometric ratio weighing precursor Ni0.7Co0.10Mn0.2(OH)2LiNO as a lithium source3After uniform mixing, the volume concentration of the oxygen atmosphere is 99%, and the core material A is obtained after pretreatment for 2 hours at the low temperature of 500 ℃;
s2, dissolving agar powder in water at normal temperature and pressure, stirring uniformly under the condition of water bath heating at 80 ℃ to form hot agar solution, and adding 2.0mol L of agar solution-1Nickel nitrate, cobalt nitrate and manganese nitrate (with a molar ratio of cations of Ni: Co: Mn: 60:20:20) and LiNO3Dissolving in the hot agar solution, wherein the stoichiometric ratio of metal cation to lithium element is 1:1, uniformly stirring to form a transparent solution, adding aluminum hydroxide into the solution, wherein the molar ratio of the addition amount of the aluminum hydroxide to the total amount of nickel-cobalt-manganese metal cations is 0.05, and the uniform solution is used for a shell material B;
s3, immersing the core material A into the core layer solution B, aging for 2 hours, cooling in a water bath at 15 ℃ to form gel, and freeze-drying at-1 ℃ for 48 hours to remove water to obtain a material C;
s4, sintering the material C for 8 hours at 900 ℃ under the condition that the volume concentration of an oxygen atmosphere is 30% to obtain the cathode material with the core-shell structure;
the specific surface area of the material prepared by the method is 0.85 square meters per gram, and the electrochemical performance of the material is tested.
Example 4
S1, weighing precursor Ni according to the stoichiometric ratio of 1:1.10.6Co0.2Mn0.2(OH)2Lithium source LiOH. H2O, after being uniformly mixed, the volume concentration of the oxygen atmosphere is 30%, and the core material A is obtained after pretreatment for 3 hours at the low temperature of 400 ℃;
s2, dissolving agar powder in water at normal temperature and pressure, stirring uniformly under the condition of water bath heating at 90 ℃ to form hot agar solution, and adding 2.0mol L of agar solution-1Nickel sulfate, cobalt sulfate and manganese sulfate (cation molar ratio Ni: Co: Mn: 50:20:30) and LiOH. H2O is dissolved in the hot agar solution, wherein the stoichiometric ratio of metal cations to lithium elements is 1: 0.95, stirring uniformly to form a transparent solution, adding nano alumina and alumina into the solutionThe molar ratio of the addition amount to the total amount of the nickel-cobalt-manganese metal cations is 0.35, and the uniform solution is used for a shell material B;
s3, immersing the core material A into the core layer solution B, aging for 3 hours, cooling in a water bath at 5 ℃ to form gel, freezing for 15 hours at-10 ℃, and drying to remove water to obtain a material C;
s4, sintering the material C for 15 hours at 600 ℃ under the condition that the volume concentration of an oxygen atmosphere is 50% to obtain a positive electrode material with a core-shell structure;
the specific surface area of the material prepared by the method is 0.90 square meters per gram, and the electrochemical performance of the material is tested.
Comparative example 1
Example 1 omits the freeze-drying process of step S3, and instead, it is dried at room temperature.
S1, weighing precursor Ni according to the stoichiometric ratio of 1:1.10.7Co0.1Mn0.2(OH)2Lithium source LiOH. H2O, after being uniformly mixed, the volume concentration of the oxygen atmosphere is 30%, and the core material A is obtained after pretreatment for 3 hours at the low temperature of 400 ℃;
s2, dissolving agar powder in water at normal temperature and pressure, stirring uniformly under 70 ℃ water bath heating condition to form hot agar solution, and adding 2.0mol L of agar solution-1Nickel sulfate, cobalt sulfate and manganese sulfate (cation molar ratio Ni: Co: Mn: 50:20:30) and LiOH. H2O is dissolved in the hot agar solution, wherein the stoichiometric ratio of metal cations to lithium elements is 1: 0.9, uniformly stirring to form a transparent solution, adding nano alumina into the solution, wherein the molar ratio of the addition amount of the alumina to the total amount of the nickel-cobalt-manganese metal cations is 0.35, and the uniform solution is used for a shell material B;
s3, immersing the core material A into the core layer solution B, aging for 2 hours, cooling in a water bath at 5 ℃ to form gel, and drying at normal temperature to remove water to obtain a material C;
s4, sintering the material C for 24 hours at 500 ℃ under the condition that the volume concentration of an oxygen atmosphere is 50% to obtain a positive electrode material with a core-shell structure;
the specific surface area of the material prepared by the method is 0.5 square meters per gram, and the electrochemical performance of the material is tested.
Comparative example 2
Commercial LiNi0.7Co0.1Mn0.2O2The specific surface area of the material is 0.5 square meters per gram, and the electrochemical performance of the material is tested.
The electrochemical performance test process of the cathode material prepared in each example is as follows:
electrochemical performance test conditions: weighing a certain mass of the positive electrode material, SP and PVDF according to a mass ratio of 90:05:05, adding NMP, and uniformly mixing to prepare slurry. And uniformly coating the slurry on a rectangular aluminum foil, then transferring the rectangular aluminum foil to an oven, drying the rectangular aluminum foil at 105 ℃ for 12 hours, cutting the rectangular aluminum foil into round small pieces by using a slicing machine, and compacting the round small pieces to obtain the positive plate. And (3) assembling the obtained positive plate, a metal lithium plate of a negative electrode, 1mol/LLIPF6/EC-DMC electrolyte and a Clegard2300 diaphragm into a 2016 button cell in an argon atmosphere glove box, and performing electrochemical performance test on a Wuhan blue charging and discharging tester at the test voltage of 2.8V-4.3V and the multiplying power test current of 0.2C, 0.33C, 0.5C, 1C and 2C. The cycle performance is 50 weeks of 1C multiplying cycle under the condition of 25 ℃.
The test comparisons for examples 1-4 and the comparative example above are given in the following table:
as can be seen from the above table, examples 1-4 are superior to comparative examples 1-2 in cell 0.2C rate charge-discharge, first charge-discharge efficiency, cell 0.33C rate discharge, cell 0.5C rate discharge, cell 1C rate discharge, and cell 2C rate discharge capacity, as compared to comparative examples 1-2. Meanwhile, the cycle performance capacity retention rate of the examples 1-4 is better than that of the comparative examples 1-2.
Compared with the comparative example 1, the difference between the surface areas of the two materials is larger, namely the lithium ion battery cathode material obtained by freeze drying is better than the lithium ion battery cathode material obtained by compounding A and B independently.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a core-shell structure cathode material is used for a lithium ion battery, and is characterized in that: the method comprises the following steps:
s1, weighing the precursor and the lithium source according to the stoichiometric ratio, uniformly mixing, and performing low-temperature pretreatment to obtain a core part material A;
s2, dissolving agar powder in water, uniformly stirring under a water bath heating condition to form a hot agar solution, dissolving a lithium source, a nickel source, a manganese source and a cobalt source in the hot agar solution, and uniformly stirring to form a transparent solution for the external shell material B;
s3, immersing the core part material A into the outer shell material B, aging for a certain time, cooling in a water bath to form gel, and removing moisture in the gel by freeze drying to obtain a material C;
and S4, sintering the material C to obtain the cathode material with the core-shell structure.
2. The preparation method of the core-shell structure cathode material according to claim 1, characterized in that: in the steps S1 and S2, the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium chloride, lithium nitrate, lithium acetate, lithium sulfate, lithium phosphate and lithium hydrogen phosphate, and the molar ratio of the 1 lithium element in the step S to the total amount of the metal elements in the precursor is (1-1.2): 1, in the step S2, the molar ratio of the lithium element to the total amount of the nickel-cobalt-manganese metal element is (0.90-1): 1.
3. the preparation method of the core-shell structure cathode material according to claim 1, characterized in that: in step S1, the low-temperature pretreatment conditions are that the volume concentration of the oxygen atmosphere is 30-99%, the temperature is 300-500 ℃, and the time is 2-6 hours.
4. The preparation method of the core-shell structure cathode material according to claim 1, characterized in that: in step S2, the nickel source, the cobalt source, and the manganese source are at least one of soluble sulfate, carbonate, halogen salt, or nitrate.
5. The preparation method of the core-shell structure cathode material according to claim 1, characterized in that: the sol in the step S2 is treated under the conditions of 70-90 ℃ in water bath and normal temperature and pressure.
6. The preparation method of the core-shell structure cathode material according to claim 1, characterized in that: and step S2, an additive is introduced, the additive is one or more of nano oxides, hydroxides or soluble salts of Sr, Al, W, Ti, Mg, Zr, Ba, Y, La, V, Ta and Y, the molar ratio of the addition amount to the metal element content of the shell layer anode material is a, and a is more than 0 and less than 0.35.
7. The preparation method of the core-shell structure cathode material according to claim 1, characterized in that: in the step S3, the aging time is 0.5-3 hours, the water bath cooling temperature is 5-20 ℃, and the freeze drying condition is-40 ℃ to 0 ℃ for 5-48 hours.
8. The preparation method of the core-shell structure cathode material according to claim 1, characterized in that: in the step S4, the sintering conditions are that the volume concentration of the oxygen atmosphere is 30-99%, the temperature is 500-900 ℃, and the time is 8-24 hours.
9. The core-shell structure cathode material prepared by the preparation method of the core-shell structure cathode material according to any one of claims 1 to 8, characterized in that: the core-shell structure anode material comprises a core part, a transition layer and an outer shell part, so that a multi-stage structure is formed, the core part is a ternary material, the outer shell part is a porous modified ternary material, the outer shell part is densely attached to the core part, and the transition layer is a gradient modified interface.
10. A lithium ion battery using the core-shell structure positive electrode material of claim 9.
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| CN109273701A (en) * | 2018-11-23 | 2019-01-25 | 中南大学 | High nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material and preparation method thereof |
| CN110085845A (en) * | 2019-05-13 | 2019-08-02 | 中南大学 | A kind of nickel-base anode material and preparation method thereof with core-shell structure |
| CN110311127A (en) * | 2019-07-17 | 2019-10-08 | 江苏翔鹰新能源科技有限公司 | A kind of preparation method of the high Ni-monocrystal tertiary cathode material of core-shell structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114388779A (en) * | 2022-01-12 | 2022-04-22 | 万华化学(四川)有限公司 | Composite ternary cathode material, preparation method thereof and lithium ion battery |
| CN114388779B (en) * | 2022-01-12 | 2024-02-02 | 万华化学(四川)有限公司 | Composite ternary positive electrode material, preparation method thereof and lithium ion battery |
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