CN116914123A - High-stability layered positive electrode material of battery for vehicle and preparation method thereof - Google Patents
High-stability layered positive electrode material of battery for vehicle and preparation method thereof Download PDFInfo
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- CN116914123A CN116914123A CN202311161730.5A CN202311161730A CN116914123A CN 116914123 A CN116914123 A CN 116914123A CN 202311161730 A CN202311161730 A CN 202311161730A CN 116914123 A CN116914123 A CN 116914123A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 239000007774 positive electrode material Substances 0.000 title abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 251
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 166
- 239000000463 material Substances 0.000 claims abstract description 154
- 239000011572 manganese Substances 0.000 claims abstract description 142
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 129
- 229910052751 metal Inorganic materials 0.000 claims abstract description 95
- 239000002184 metal Substances 0.000 claims abstract description 87
- 239000011734 sodium Substances 0.000 claims abstract description 73
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 51
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 51
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 46
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 49
- -1 gluconic acid ester Chemical class 0.000 claims description 31
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 18
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 18
- 239000000174 gluconic acid Substances 0.000 claims description 18
- 235000012208 gluconic acid Nutrition 0.000 claims description 18
- 239000002356 single layer Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000010406 cathode material Substances 0.000 claims description 15
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 13
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 13
- 229940071125 manganese acetate Drugs 0.000 claims description 13
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 13
- 229940078494 nickel acetate Drugs 0.000 claims description 13
- 239000001632 sodium acetate Substances 0.000 claims description 13
- 235000017281 sodium acetate Nutrition 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical group NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000011240 wet gel Substances 0.000 abstract description 35
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 abstract description 34
- 238000001354 calcination Methods 0.000 abstract description 23
- 229940050410 gluconate Drugs 0.000 abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001569 carbon dioxide Substances 0.000 abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- 239000010936 titanium Substances 0.000 description 35
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000011247 coating layer Substances 0.000 description 12
- 239000008098 formaldehyde solution Substances 0.000 description 11
- 238000000227 grinding Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- RIEABXYBQSLTFR-UHFFFAOYSA-N monobutyrin Chemical compound CCCC(=O)OCC(O)CO RIEABXYBQSLTFR-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 230000000630 rising effect Effects 0.000 description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000012792 core layer Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 3
- 238000009489 vacuum treatment Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/16—Preparation from compounds of sodium or potassium with amines and carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a high-stability layered positive electrode material of a vehicle battery and a preparation method thereof, which belong to the technical field of electrode materials, and in particular relates to a high-nickel layered ternary material prepared by mixing a sodium source, a nickel source, a manganese source and a metal M1 source, howeverAdding the material, a sodium source, a nickel source, a manganese source and a metal M2 source into a solvent, preparing a wet gel coated high-nickel layered ternary material under the action of a functional agent, and carrying out subsequent calcination and carbon dioxide introduction under vacuum to obtain a double-layer coated high-nickel layered ternary material, namely Na 2 CO 3 @NaNi 1‑x‑ y Mn x M2 y O 2 @NaNi 1‑a‑b Mn a M1 b O 2 The method comprises the steps of carrying out a first treatment on the surface of the The metal M1 source and the metal M2 source may each be selected from at least 1 of metal elements Li, zn, ti, V, co, cu, fe and Mg; the functional agent can be at least 1 of citric acid, gluconate and modified gluconate.
Description
Technical Field
The application belongs to the technical field of electrode materials, and particularly relates to a high-stability layered anode material of a battery for a vehicle and a preparation method of the high-stability layered anode material.
Background
Energy is always the material basis for supporting the prosperity of human society. Currently, the main energy sources utilized by humans are fossil energy sources such as coal, petroleum and natural gas. However, fossil energy reserves are limited and cannot meet the increasing demand. In order to alleviate the energy problems and environmental crisis associated with the excessive use of fossil energy, it is necessary to achieve efficient conversion, storage and utilization of renewable energy as early as possible. Recently, the battery market and researchers have been increasingly concerned about sodium ion batteries. Sodium and lithium abundance in the crust has been a key factor in considering the advantages of developing sodium ion batteries. As sodium ion battery technology matures, these advantages are also extended to low temperature performance, safety, transportation difficulties, battery design, and the like. Sodium ion batteries are therefore of great interest because of their naturally abundant and low cost sodium resources and similar operating mechanisms as lithium ion batteries are promising candidates for large-scale electrical energy storage.
Among the numerous positive electrode candidate materials, layered Na x TMO 2 (TM means nickel, cobalt, manganese, iron and the like) is recognized as one of the most promising positive electrodes because of the simple structure, stoichiometric adjustability and excellent electrochemical performance, and in general, positive electrode materials with higher nickel content have higher theoretical capacity, however, the materials are extremely easy to react with water and carbon dioxide in the air to generate metal hydroxide and metal carbonate, the byproducts easily cause serious water absorption on the surface of the materials, PVDF is insoluble in water and is agglomerated when meeting water, thus causing the problems of high viscosity and low fluidity of slurry, thus extremely easily causing gelation of slurry preparation, serious attenuation of positive electrode capacity and the like in the production and preparation process. Therefore, high nickel positive electrode materials have a severe storage environment requirement. At present, the problems are often solved by cladding and doping.
The currently reported coating materials comprise aluminum oxide, titanium dioxide, zirconium oxide, sodium metaaluminate, sodium niobate, sodium titanate, sodium borate, sodium zirconate and the like, and the ionic conductivity is low, so that the gram capacity and the multiplying power performance of the anode material can not be fully exerted. Among them, the oxide coating materials such as alumina of the application of CN115881920a require higher temperatures and thus consume higher costs, while some sodium ion conductors such as CN114597370a pass Na 2 MnPO 4 F-coated O3 type layered sodium ion battery anode material NaNi x M 1-x-y Mn y O 2 Adverse effects caused by side reaction caused by decomposition of high-voltage electrolyte are prevented, air stability of the material is improved, and the surface of the material and H are inhibited 2 O and CO 2 Improves the cycle stability and rate capability of the O3 layered sodium ion battery positive electrode material, however, the coated aluminum oxide and Na 2 MnPO 4 The F theoretical capacity is not ideal (aluminum oxide cannot store sodium), and excessive coating layers can lead to the reduction of the overall capacity of the battery, which is not beneficial to improving the energy density of the battery.
Disclosure of Invention
The application aims to provide a high-stability layered positive electrode material which can be used for preparing batteries and is high in discharge capacity and good in stability after the batteries are prepared, and a preparation method thereof.
Na provided by the application 2 CO 3 @NaNi 1-x-y Mn x M2 y O 2 @NaNi 1-a-b Mn a M1 b O 2 Overcomes the defects of the background technology, has simple method and can be produced in large scale; the coating material has the advantages of acceptable theoretical capacity and stability; the surface formed metal carbonate layer further enhances the air stability of the material.
The technical scheme adopted by the application for achieving the purpose is as follows:
a highly stable layered cathode material comprising: the core layer is a high nickel layered ternary material NaNi 1-a-b Mn a M1 b O 2 Wherein a+b is less than or equal to 0.2, a is not 0, and b is not 0;
the middle layer is made of a low-nickel layered ternary material NaNi 1-x-y Mn x M2 y O 2 Wherein 0.6.ltoreq.x+y.ltoreq.0.9, x being other than 0, y being other than 0;
and an outer layer material. The application prepares the high nickel lamellar ternary material NaNi at first 1-a-b Mn a M1 b O 2 As a core layer, and then coating a low-nickel layered ternary material NaNi outside the core layer 1-x-y Mn x M2 y O 2 Preparation of low-nickel layered ternary material NaNi 1-x-y Mn x M2 y O 2 In the process of (2), by adding different functional agents to form wet gel, the low-nickel lamellar ternary material NaNi 1-x-y Mn x M2 y O 2 The metal source component of (2) can be fully coated on the nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 Outside, forming an intermediate layer outside the core layer after subsequent calcination, namely the low-nickel layered ternary material NaNi 1-x-y Mn x M2 y O 2 In this step, the step of forming wet gel is important, and the low-nickel layered ternary material NaNi 1-x-y Mn x M2 y O 2 Metal source of (2)The components are distributed in wet gel, and the structure and the groups in the wet gel enable the low-nickel lamellar ternary material NaNi to be formed 1-x-y Mn x M2 y O 2 The metal source components of the catalyst form different layers of distribution, and the distribution of the metal source components is used for determining the effect and the performance after being calcined to prepare the middle layer, so that the application discovers that the functional agent can be at least 1 of citric acid, gluconate and modified gluconate through exploring the functional agent. The functional agent is at least 1 of citric acid, gluconate and modified gluconate, and the positive electrode material prepared from the functional agent has high discharge capacity and good stability after being further prepared into a battery.
Preferably, M1 is at least 1 of a metal element Li, zn, ti, V, co, cu, fe and Mg; or, M2 is at least 1 of a metal element Li, zn, ti, V, co, cu, fe and Mg.
More preferably, M1 and M2 are the same metal element; or M1 and M2 are different metal elements; or M1 is Ti; or M2 is Ti; or, M2 is V.
Preferably, the low-nickel layered ternary material NaNi 1-x-y Mn x M2 y O 2 The content of the (C) is higher than that of the Ni-layered ternary material NaNi 1-a- b Mn a M1 b O 2 1-10% of the mass; or, the outer layer material is Na 2 CO 3 A layer; or the thickness of the outer layer material is 2-15 nanometers.
The application discloses a preparation method of a high-stability layered anode material, which is characterized by comprising the following steps: the metal source of the middle layer and the high nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 Mixing the materials in a solvent, adding a functional agent, and preparing a single-layer coated high-nickel layered ternary material, namely NaNi 1-x-y Mn x M2 y O 2 @NaNi 1-a-b Mn a M1 b O 2 Wherein a+b is less than or equal to 0.2, a is not 0, b is not 0,0.6 and x+y is less than or equal to 0.9, x is not 0, and y is not 0; then the single-layer coated high nickel layered ternary material is placed in a material containing CO 2 In a gas container, preparing a double-layer coated high-nickel layered ternary material, namely Na 2 CO 3 @NaNi 1-x-y Mn x M2 y O 2 @NaNi 1-a- b Mn a M1 b O 2 。
Preferably, the metal source includes a sodium source, a nickel source, a manganese source, and a metal M2 source; or, the solvent includes at least 1 of acetone and ethanol; alternatively, the functional agent comprises citric acid.
More preferably, the sodium source is sodium acetate or sodium nitrate; or, the nickel source is nickel acetate or nickel nitrate; or the manganese source is manganese acetate or manganese nitrate; or, the functional agent also comprises gluconic acid ester or modified gluconic acid ester, wherein the modified gluconic acid ester has 1, 3-propylene diamine group. After the citric acid is used, the gluconic acid ester or the modified gluconic acid ester is further used together with the citric acid, and the use of the citric acid and the modified gluconic acid ester together is found to be superior to the use of the citric acid and the gluconic acid ester, so that the modified group of the modified gluconic acid ester in the functional agent has an excellent effect when the modified group of the modified gluconic acid ester and the citric acid together act together, the discharge capacity of a finally prepared battery is improved, and the stability of a positive electrode material prepared by using the modified gluconic acid ester is good.
Preferably, M1 is Ti; or M2 is Ti; or, M2 is V.
Preferably, a=0.1; or, b=0.1; or, x=0.4; or, y=0.4.
Preferably, the high nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 In the preparation of (2), mixing a sodium source, a nickel source, a manganese source and a metal M1 source, grinding, tabletting, calcining at 900-1100 ℃ for 10-20h, cooling and grinding again to obtain the high-nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 。
Preferably, the high nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 In the preparation of (2), the sodium source is sodium acetate or sodium nitrate; the nickel source is nickel acetate or nickel nitrate; the manganese source is manganese acetate or manganese nitrate.
Preferably, the high nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 In the preparation of (2), the metal M1 source is metal element Li, zn, ti, V, co, cu, fe and Mg1 less.
Preferably, the high nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 In the preparation of (a), a sodium source, a nickel source, a manganese source and a metal M1 source are mixed in a ratio of 1:1-a-b: a: b is used in a molar ratio of a+b.ltoreq.0.2, a being other than 0 and b being other than 0.
Preferably, the preparation of the high-stability layered cathode material comprises the preparation of a wet gel coated high-nickel layered ternary material, the preparation of a single-layer coated high-nickel layered ternary material and the preparation of a double-layer coated high-nickel layered ternary material.
More preferably, in the preparation of the wet gel coated high nickel layered ternary material, a sodium source, a nickel source, a manganese source, a metal M2 source and a high nickel layered ternary material NaNi 1-a-b Mn a M1 b O 2 Adding the mixture into a solvent, adding a functional agent, stirring and mixing for 5-10h at 20-40 ℃, and then carrying out heat treatment on the mixed solution for 1-5h at 60-80 ℃ to obtain the wet gel coated high nickel lamellar ternary material.
Still more preferably, in the preparation of the wet gel coated high nickel layered ternary material, the sodium source is sodium acetate or sodium nitrate; the nickel source is nickel acetate or nickel nitrate; the manganese source is manganese acetate or manganese nitrate; solvents include acetone or ethanol; the functional agent is citric acid, and the usage amount of the citric acid is 10-30wt% of the solvent. The metal M2 source is at least 1 of metal elements Li, zn, ti, V, co, cu, fe and Mg.
Preferably, the functional agent further comprises gluconate, and the use amount of the gluconate is 1-5wt% of the citric acid.
More preferably, in the preparation of the gluconate, the gluconate is added into a methanol solution, hydrochloric acid is added into the mixture for stirring and mixing, pyridine-2-formaldehyde solution is added into the mixture for reaction at the temperature of 0-20 ℃ for 24-72 hours, deionized water is added into the mixture after the reaction is finished, stirring treatment is carried out for 1-3 hours, the filtrate is removed by filtration, and the product is neutralized to be neutral by pyridine, washed and dried to obtain the gluconate.
More preferably, in the preparation of the gluconate, the methanol solution is formed by mixing deionized water and methanol, the methanol content in the methanol solution is 40-60wt%, the gluconic acid usage amount is 40-60wt% of the methanol solution, the pyridine-2-formaldehyde solution is formed by mixing pyridine-2-formaldehyde with methanol, the pyridine-2-formaldehyde content in the pyridine-2-formaldehyde solution is 20-40wt%, and the pyridine-2-formaldehyde usage amount is 70-90wt% of the gluconic acid based on the pyridine-2-formaldehyde.
Preferably, the functional agent further comprises a modified gluconate ester, wherein the use amount of the modified gluconate ester is 1-5wt% of the citric acid.
More preferably, in the preparation of the modified gluconate, the gluconate is added into methanol, DMAP and 1, 3-propylene diamine are then added for reaction for 24-72 hours at the temperature of 10-30 ℃, suction filtration is carried out after the reaction is finished, and the product is washed by deionized water and dried to obtain the modified gluconate.
More preferably, in the preparation of the modified gluconate, the gluconate is used in an amount of 4-16wt% of methanol, the DMAP is used in an amount of 0.1-0.3wt% of the gluconate, and the 1, 3-propanediamine is used in an amount of 40-80wt% of the gluconate.
Preferably, the functional agent further comprises glycerol monobutyrate, and the glycerol monobutyrate is used in an amount of 0.5-2wt% of citric acid. In the preparation of the high-stability layered cathode material, the functional agent can also be glycerol monobutyrate, and the research shows that the glycerol monobutyrate, citric acid and modified gluconic acid ester have better co-use effect.
More preferably, in the preparation of the single-layer coated high-nickel layered ternary material, the wet gel coated high-nickel layered ternary material is dried for 6 to 12 hours at the temperature of between 110 and 130 ℃, ground into powder, pre-calcined for 3 to 6 hours at the temperature of between 500 and 650 ℃ in air, and then calcined for 10 to 15 hours at the temperature of between 850 and 1000 ℃ to obtain the single-layer coated high-nickel layered ternary material, namely NaNi 1-x-y Mn x M2 y O 2 @NaNi 1-a-b Mn a M1 b O 2 . The temperature rising rate in the pre-calcination is 5-10 ℃/min, and the temperature rising rate in the calcination is 5-10 ℃/min.
More preferably, in the preparation of the double-layer coated high-nickel layered ternary material, the single-layer coated high-nickel layered ternary material is placed in a high-pressure reaction vessel, and after vacuumizing, 7 MPa to 10 MPa of CO is added 2 Treating the gas at 40-60 ℃ for 18-24h,obtaining a double-layer coated high-nickel layered ternary material, namely Na 2 CO 3 @NaNi 1-x-y Mn x M2 y O 2 @NaNi 1-a-b Mn a M1 b O 2 . Wherein, the content of the intermediate layer accounts for 1-10% of the mass of the high nickel lamellar ternary material; the thickness of the outer layer is 2-15 nanometers, a is not 0, b is not 0, x+y is not 0.9 and x is not 0, and y is not 0.
The application discloses application of the high-stability layered cathode material in preparing a battery for a vehicle.
The application utilizes a laminar positive electrode material interlayer with better stability to coat a positive electrode material with high capacity, poor air stability and poor cycle performance, then utilizes supercritical carbon dioxide to react with residual alkali on the surface of the obtained coating material, and then generates a uniform and compact sodium carbonate outer layer on the surface of the coating layer. The middle layer with better stability can improve the overall stability of the material, the circulation performance and the multiplying power performance are enhanced, the sodium carbonate outer layer can effectively prevent the material from being contacted with moisture in the air, and the water absorption of the material or the side reaction of the electrode surface is reduced, so that the air stability of the material is improved.
The application prepares the high nickel lamellar ternary material NaNi by mixing a sodium source, a nickel source, a manganese source and a metal M1 source 1-a-b Mn a M1 b O 2 Then adding the material, a sodium source, a nickel source, a manganese source and a metal M2 source into a solvent, under the action of a functional agent, preparing a wet gel coated high-nickel layered ternary material, and carrying out subsequent calcination and carbon dioxide introduction under vacuum treatment to obtain a double-layer coated high-nickel layered ternary material, namely Na 2 CO 3 @NaNi 1-x-y Mn x M2 y O 2 @NaNi 1-a-b Mn a M1 b O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein a+b is less than or equal to 0.2, and x+y is less than or equal to 0.6 and less than or equal to 0.9; the metal M1 source and the metal M2 source can be at least 1 selected from metal elements Li, zn, ti, V, co, cu, fe and Mg, and the metal M1 source and the metal M2 source can be consistent or inconsistent; the functional agent can be at least 1 of citric acid, gluconate and modified gluconate; therefore, has the following beneficial effects: from high to highAfter the stable layered cathode material is prepared into a battery, the discharge capacity is high, and the stability of the high-stability layered cathode material is good, so that the stability of the prepared battery is good. Therefore, the application is a high-stability layered positive electrode material which can be used for preparing batteries, has high discharge capacity after the batteries are prepared, and has good stability for the vehicle batteries, and a preparation method thereof.
Drawings
FIG. 1 is a schematic diagram of a positive electrode material structure;
FIG. 2 is a graph of discharge capacity;
fig. 3 is a graph of performance retention.
Reference numerals: 1 is a core layer, 2 is an intermediate layer, and 3 is an outer layer.
Detailed Description
The technical scheme of the application is further described in detail below with reference to the specific embodiments and the attached drawings:
na prepared in the following examples in the present application 2 CO 3 @NaNi 1-x-y Mn x M2 y O 2 @NaNi 1-a-b Mn a M1 b O 2 The structure of (a) is shown in fig. 1, wherein 1 is a core layer, 2 is an intermediate layer, and 3 is an outer layer, in the embodiment of the present application, a=0.1, b=0.1, x=0.4, y=0.4, and M1 is Ti, M2 is Ti or V, and the beneficial effects of the present application can be achieved only by the specific parameters and specific elements, and in the scope of the present application, a, b, x, y can be arbitrarily selected, and M1 and M2 can be arbitrarily selected.
Example 1: preparation method of high-stability layered positive electrode material of vehicle battery
High nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 Is prepared from the following steps: mixing a sodium source, a nickel source, a manganese source and a metal M1 source, grinding, tabletting, calcining at 1000 ℃ for 15 hours, cooling and grinding again to obtain the high-nickel lamellar ternary material NaNi 1-a- b Mn a M1 b O 2 . The sodium source is sodium acetate, the nickel source is nickel acetate, the manganese source is manganese acetate, and the metal M1 source is metal element Ti; sodium source, nickel source, manganese source and metal M1 source are combined in a ratio of 1:1-a-b: a: bMolar ratio is used, where a=0.1, b=0.1.
Preparing a wet gel coated high-nickel layered ternary material: sodium source, nickel source, manganese source, metal M2 source and high nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 Adding the mixture into a solvent, adding a functional agent, stirring and mixing for 8 hours at 30 ℃, and then carrying out heat treatment on the mixed solution for 3 hours at 70 ℃ to obtain the wet gel coated high-nickel layered ternary material. The sodium source is sodium acetate, the nickel source is nickel acetate, the manganese source is manganese acetate, the solvent comprises acetone, the functional agent is citric acid, and the use amount of the citric acid is 20wt% of the solvent. The metal M2 source is a metal element Ti. Sodium source, nickel source, manganese source and metal M2 source 1:1-x-y: x: y is used in a molar ratio where x=0.4 and y=0.4.
Preparing a single-layer coated high-nickel layered ternary material: drying the wet gel coated high-nickel layered ternary material for 10 hours at 120 ℃, grinding to powder, pre-calcining for 5 hours at 600 ℃ in air, and calcining for 12 hours at 900 ℃ to obtain the single-layer coated high-nickel layered ternary material. The temperature rising rate in the pre-calcination is 10 ℃/min, and the temperature rising rate in the calcination is 10 ℃/min.
Preparing a double-layer coated high-nickel layered ternary material: placing the single-layer coated high-nickel layered ternary material into a high-pressure reaction container, vacuumizing, and adding CO of 8 MPa 2 Treating the gas at 50 ℃ for 21h to obtain a double-layer coated high-nickel layered ternary material, namely Na 2 CO 3 @NaNi 1-x-y Mn x M2 y O 2 @NaNi 1-a-b Mn a M1 b O 2 . Wherein, the content of the coating layer 1 accounts for 5% of the mass of the high-nickel layered ternary material; the thickness of the coating layer 2 was 10nm. Wherein a=0.1, b=0.1, where x=0.4, y=0.4. M1 is Ti, and M2 is Ti.
Example 2: preparation method of high-stability layered positive electrode material of vehicle battery
Compared with the embodiment 1, the difference is that the content of the coating layer 1 in the prepared double-layer coated high-nickel layered ternary material is 8% of the mass of the high-nickel layered ternary material.
Example 3: preparation method of high-stability layered positive electrode material of vehicle battery
This example differs from example 1 in that in the preparation of the wet gel coated high nickel layered ternary material, the metal M2 source is V.
Example 4: preparation method of high-stability layered positive electrode material of vehicle battery
Preparation of gluconate: adding gluconic acid into a methanol solution, adding hydrochloric acid, stirring and mixing, adding pyridine-2-formaldehyde solution, reacting at 10 ℃ for 48 hours, adding deionized water after the reaction is finished, stirring and treating for 2 hours, filtering to remove filtrate, neutralizing the product with pyridine to be neutral, washing, and drying to obtain gluconic acid ester. The methanol solution is formed by mixing deionized water and methanol, the using amount of the methanol solution is 100g, wherein the content of ethanol is 50g; the usage amount of the gluconic acid is 50g, the pyridine-2-formaldehyde solution is formed by mixing pyridine-2-formaldehyde and methanol, the content of the pyridine-2-formaldehyde in the pyridine-2-formaldehyde solution is 30wt%, and the usage amount of the pyridine-2-formaldehyde solution is 40g based on the measurement of the pyridine-2-formaldehyde.
High nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 Is prepared from the following steps: mixing a sodium source, a nickel source, a manganese source and a metal M1 source, grinding, tabletting, calcining at 1000 ℃ for 15 hours, cooling and grinding again to obtain the high-nickel lamellar ternary material NaNi 1-a- b Mn a M1 b O 2 . The sodium source is sodium acetate, the nickel source is nickel acetate, the manganese source is manganese acetate, and the metal M1 source is metal element Ti; sodium source, nickel source, manganese source and metal M1 source are combined in a ratio of 1:1-a-b: a: b is used in a molar ratio of a=0.1 and b=0.1.
Preparing a wet gel coated high-nickel layered ternary material: sodium source, nickel source, manganese source, metal M2 source and high nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 Adding the mixture into a solvent, adding a functional agent, stirring and mixing for 8 hours at 30 ℃, and then carrying out heat treatment on the mixed solution for 3 hours at 70 ℃ to obtain the wet gel coated high-nickel layered ternary material. The sodium source is sodium acetate, the nickel source is nickel acetate, the manganese source is manganese acetate, and the solvent comprises propyleneThe ketone and the functional agent are citric acid and gluconic acid ester, the use amount of the citric acid is 20wt% of the solvent, and the use amount of the gluconic acid ester is 3wt% of the citric acid. The metal M2 source is a metal element Ti. Sodium source, nickel source, manganese source and metal M2 source 1:1-x-y: x: y is used in a molar ratio where x=0.4 and y=0.4.
Preparing a single-layer coated high-nickel layered ternary material: drying the wet gel coated high-nickel layered ternary material for 10 hours at 120 ℃, grinding to powder, pre-calcining for 5 hours at 600 ℃ in air, and calcining for 12 hours at 900 ℃ to obtain the single-layer coated high-nickel layered ternary material. The temperature rising rate in the pre-calcination is 10 ℃/min, and the temperature rising rate in the calcination is 10 ℃/min.
Preparing a double-layer coated high-nickel layered ternary material: placing the single-layer coated high-nickel layered ternary material into a high-pressure reaction container, vacuumizing, and adding CO of 8 MPa 2 Treating the gas at 50 ℃ for 21h to obtain a double-layer coated high-nickel layered ternary material, namely Na 2 CO 3 @NaNi 1-x-y Mn x M2 y O 2 @NaNi 1-a-b Mn a M1 b O 2 . Wherein, the content of the coating layer 1 accounts for 5% of the mass of the high-nickel layered ternary material; the thickness of the coating layer 2 was 10nm. Wherein a=0.1, b=0.1, where x=0.4, y=0.4. M1 is Ti, and M2 is Ti.
Example 5: preparation method of high-stability layered positive electrode material of vehicle battery
Compared with the embodiment 4, the difference is that the content of the coating layer 1 in the prepared double-layer coated high-nickel layered ternary material is 8% of the mass of the high-nickel layered ternary material.
Example 6: preparation method of high-stability layered positive electrode material of vehicle battery
This example differs from example 4 in that in the preparation of the wet gel coated high nickel layered ternary material, the metal M2 source is V.
Example 7: preparation method of high-stability layered positive electrode material of vehicle battery
Preparation of gluconate: adding gluconic acid into a methanol solution, adding hydrochloric acid, stirring and mixing, adding pyridine-2-formaldehyde solution, reacting at 10 ℃ for 48 hours, adding deionized water after the reaction is finished, stirring and treating for 2 hours, filtering to remove filtrate, neutralizing the product with pyridine to be neutral, washing, and drying to obtain gluconic acid ester. The methanol solution is formed by mixing deionized water and methanol, the using amount of the methanol solution is 100g, wherein the content of ethanol is 50g; the usage amount of the gluconic acid is 50g, the pyridine-2-formaldehyde solution is formed by mixing pyridine-2-formaldehyde and methanol, the content of the pyridine-2-formaldehyde in the pyridine-2-formaldehyde solution is 30wt%, and the usage amount of the pyridine-2-formaldehyde solution is 40g based on the measurement of the pyridine-2-formaldehyde.
Preparation of modified gluconate: adding the gluconate into methanol, then adding DMAP and 1, 3-propylene diamine, reacting for 48 hours at 20 ℃, filtering after the reaction is finished, washing a product by deionized water, and drying to obtain the modified gluconate. The amount of methanol used was 100g, the amount of gluconate used was 10g, the amount of DMAP used was 0.02g, and the amount of 1, 3-propanediamine used was 6g.
High nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 Is prepared from the following steps: mixing a sodium source, a nickel source, a manganese source and a metal M1 source, grinding, tabletting, calcining at 1000 ℃ for 15 hours, cooling and grinding again to obtain the high-nickel lamellar ternary material NaNi 1-a- b Mn a M1 b O 2 . The sodium source is sodium acetate, the nickel source is nickel acetate, the manganese source is manganese acetate, and the metal M1 source is metal element Ti; sodium source, nickel source, manganese source and metal M1 source are combined in a ratio of 1:1-a-b: a: b is used in a molar ratio of a=0.1 and b=0.1.
Preparing a wet gel coated high-nickel layered ternary material: sodium source, nickel source, manganese source, metal M2 source and high nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 Adding the mixture into a solvent, adding a functional agent, stirring and mixing for 8 hours at 30 ℃, and then carrying out heat treatment on the mixed solution for 3 hours at 70 ℃ to obtain the wet gel coated high-nickel layered ternary material. The sodium source is sodium acetate, the nickel source is nickel acetate, the manganese source is manganese acetate, the solvent comprises acetone, and the functional agent is citric acid and modified gluconateThe amount of citric acid used was 20wt% of the solvent, and the amount of modified gluconate was 3wt% of the citric acid. The metal M2 source is a metal element Ti. Sodium source, nickel source, manganese source and metal M2 source 1:1-x-y: x: y is used in a molar ratio where x=0.4 and y=0.4.
Preparing a single-layer coated high-nickel layered ternary material: drying the wet gel coated high-nickel layered ternary material for 10 hours at 120 ℃, grinding to powder, pre-calcining for 5 hours at 600 ℃ in air, and calcining for 12 hours at 900 ℃ to obtain the single-layer coated high-nickel layered ternary material. The temperature rising rate in the pre-calcination is 10 ℃/min, and the temperature rising rate in the calcination is 10 ℃/min.
Preparing a double-layer coated high-nickel layered ternary material: placing the single-layer coated high-nickel layered ternary material into a high-pressure reaction container, vacuumizing, and adding CO of 8 MPa 2 Treating the gas at 50 ℃ for 21h to obtain a double-layer coated high-nickel layered ternary material, namely Na 2 CO 3 @NaNi 1-x-y Mn x M2 y O 2 @NaNi 1-a-b Mn a M1 b O 2 . Wherein, the content of the coating layer 1 accounts for 5% of the mass of the high-nickel layered ternary material; the thickness of the coating layer 2 was 10nm. Wherein a=0.1, b=0.1, where x=0.4, y=0.4. M1 is Ti, and M2 is Ti.
Example 8: preparation method of high-stability layered positive electrode material of vehicle battery
Compared with the embodiment 7, the difference is that the content of the coating layer 1 in the prepared double-layer coated high-nickel layered ternary material is 8% of the mass of the high-nickel layered ternary material.
Example 9: preparation method of high-stability layered positive electrode material of vehicle battery
This example differs from example 7 in that in the preparation of the wet gel coated high nickel layered ternary material, the metal M2 source is V.
Example 10: preparation method of high-stability layered positive electrode material of vehicle battery
This example differs from example 7 in the preparation of a wet gel coated high nickel layered ternary material.
Preparing a wet gel coated high-nickel layered ternary material: sodium source, nickel source, manganese source, metal M2 source and high nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 Adding the mixture into a solvent, adding a functional agent, stirring and mixing for 8 hours at 30 ℃, and then carrying out heat treatment on the mixed solution for 3 hours at 70 ℃ to obtain the wet gel coated high-nickel layered ternary material. The sodium source is sodium acetate, the nickel source is nickel acetate, the manganese source is manganese acetate, the solvent comprises acetone, the functional agent is citric acid, glycerol monobutyrate and modified gluconate, the usage amount of the citric acid is 20wt% of the solvent, the usage amount of the glycerol monobutyrate is 1.2wt% of the citric acid, and the usage amount of the modified gluconate is 3wt% of the citric acid. The metal M2 source is a metal element Ti. Sodium source, nickel source, manganese source and metal M2 source 1:1-x-y: x: y is used in a molar ratio where x=0.4 and y=0.4.
Example 11: preparation method of high-stability layered positive electrode material of vehicle battery
Compared with the embodiment 10, the difference is that the content of the coating layer 1 in the prepared double-layer coated high-nickel layered ternary material is 8% of the mass of the high-nickel layered ternary material.
Example 12: preparation method of high-stability layered positive electrode material of vehicle battery
This example differs from example 10 in that in the preparation of the wet gel coated high nickel layered ternary material, the metal M2 source is V.
Comparative example 1: preparation method of high-stability layered positive electrode material of vehicle battery
This comparative example differs from example 7 in the preparation of a wet gel coated high nickel layered ternary material.
Preparing a wet gel coated high-nickel layered ternary material: sodium source, nickel source, manganese source, metal M2 source and high nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 Adding the mixture into a solvent, adding a functional agent, stirring and mixing for 8 hours at 30 ℃, and then carrying out heat treatment on the mixed solution for 3 hours at 70 ℃ to obtain the wet gel coated high-nickel layered ternary material. The sodium source is sodium acetate and nickel sourceThe nickel acetate and manganese source are manganese acetate, the solvent comprises acetone, the functional agent is citric acid and modified gluconic acid ester, the amount of citric acid used was 20wt% of the solvent, and the amount of modified gluconate was 0.5wt% of citric acid. The metal M2 source is a metal element Ti. Sodium source, nickel source, manganese source and metal M2 source 1:1-x-y: x: y is used in a molar ratio where x=0.4 and y=0.4.
Comparative example 2: preparation method of high-stability layered positive electrode material of vehicle battery
This comparative example differs from example 7 in the preparation of a wet gel coated high nickel layered ternary material.
Preparing a wet gel coated high-nickel layered ternary material: sodium source, nickel source, manganese source, metal M2 source and high nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 Adding the mixture into a solvent, adding a functional agent, stirring and mixing for 8 hours at 30 ℃, and then carrying out heat treatment on the mixed solution for 3 hours at 70 ℃ to obtain the wet gel coated high-nickel layered ternary material. The sodium source is sodium acetate, the nickel source is nickel acetate, the manganese source is manganese acetate, the solvent comprises acetone, the functional agent is citric acid and modified gluconate, the usage amount of the citric acid is 20wt% of the solvent, and the usage amount of the modified gluconate is 6wt% of the citric acid. The metal M2 source is a metal element Ti. Sodium source, nickel source, manganese source and metal M2 source 1:1-x-y: x: y is used in a molar ratio where x=0.4 and y=0.4.
Test example:
the modified gluconate prepared in example 7 was subjected to the present application 1 HNMR characterization, the results of which are shown below: 1 HNMR（DMSO-d6，400MHz，TMS，25℃）:δ8.45（d，1H，Ar-H），7.87（d，1H，CONH），7.91（dd，1H，Ar-H），7.67（d，1H，Ar-H），7.45（dd，1H，Ar-H），5.69（s，1H，OCHO），4.26（d，2H，OH），3.98（s，1H，OH），3.79（d，2H，CH 2 ），3.61-3.63（m，1H，CH），3.57（dd，1H，CH），3.39（dd，2H，CH），3.34（t，2H，NH 2 ），3.15-3.21（m，2H，CH 2 ），2.52（t，2H，CH 2 ），1.49-1.55（m，2H，CH 2 ）。
preparation of electrode plates: the double-layer coated high-nickel layered ternary material prepared in each example and comparative example of the application, acetylene black and PVDF are mixed according to the mass ratio of 7:2:1 in a solvent, wherein the solvent is NMP, the PVDF is 3wt% of NMP, the slurry is coated on clean aluminum foil, the aluminum foil is dried for 1h in a vacuum drying oven at 100 ℃, then the aluminum foil is kept for 12h at 70 ℃, and the aluminum foil is sliced to prepare electrode slices with the diameter of 12 mm.
Preparation of button cell: the electrode plate is used as a battery positive electrode plate, sodium metal is used as a negative electrode, glass fiber is used as a diaphragm, 1M sodium perchlorate solution is used as electrolyte, the solvent of the sodium perchlorate solution is a mixed solution of EC, DMC and FEC, and in the solvent preparation of the sodium perchlorate solution, the volume ratio of EC to DMC is 1:1, and then mixing with FEC, wherein the FEC accounts for 5wt% of the solvent, and packaging after assembling the CR2032 button cell to obtain the button cell.
The application performs discharge capacity test on the prepared button cell, the charge-discharge multiplying power is 0.5C, the test result is shown in figure 2, wherein S1 is example 1, S2 is example 2, S3 is example 3, S4 is example 4, S5 is example 5, S6 is example 6, S7 is example 7, S8 is example 8, S9 is example 9, S10 is example 10, S11 is example 11, S12 is example 12, D1 is comparative example 1, D2 is comparative example 2, and the application prepares the high nickel layered ternary material NaNi by mixing a sodium source, a nickel source, a manganese source and a metal M1 source 1-a-b Mn a M1 b O 2 Then adding the material, a sodium source, a nickel source, a manganese source and a metal M2 source into a solvent, under the action of a functional agent, preparing a wet gel coated high-nickel layered ternary material, and carrying out subsequent calcination and carbon dioxide introduction under vacuum treatment to obtain a double-layer coated high-nickel layered ternary material, namely Na 2 CO 3 @NaNi 1-x-y Mn x M2 y O 2 @NaNi 1-a-b Mn a M1 b O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein a=0.1, b=0.1, where x=0.4, y=0.4; the metal M1 source and the metal M2 source can be selected from at least 1 of metal elements Li, zn, ti, V, co, cu, fe and Mg, and the metal M1 source and the metal M2 source can be consistent and alsoMay be inconsistent; the functional agent is citric acid, and is prepared from citric acid, sodium source, nickel source, manganese source, metal M2 source, and NaNi 1-a-b Mn a M1 b O 2 Formation of NaNi 1-x-y Mn x M2 y O 2 @NaNi 1-a-b Mn 0.1 M1 b O 2 And finally preparing Na 2 CO 3 @NaNi 0.2 Mn 0.4 Ti 0.4 O 2 @NaNi 0.8 Mn 0.1 Ti 0.1 O 2 The use of the material and the functional agent of the second layer can adjust the NaNi 0.2 Mn 0.4 Ti 0.4 O 2 With NaNi 0.8 Mn 0.1 Ti 0.1 O 2 And finally improving the discharge capacity of the prepared button cell; the application can also prepare Na 2 CO 3 @NaNi 0.2 Mn 0.4 V 0.4 O 2 @NaNi 0.8 Mn 0.1 Ti 0.1 O 2 The discharge capacity of the prepared button cell is improved; through research, the application is used for preparing Na 2 CO 3 @NaNi 0.2 Mn 0.4 V 0.4 O 2 @NaNi 0.8 Mn 0.1 Ti 0.1 O 2 In the material of (2), the gluconic acid ester or the modified gluconic acid ester can be used together with the citric acid as a functional agent, and the use effect of the modified gluconic acid ester is better than that of the gluconic acid ester; further, glycerol monobutyrate may be added to the functional agent, and when citric acid, modified gluconic acid ester and glycerol monobutyrate are used together as the functional agent, na is obtained 2 CO 3 @NaNi 0.2 Mn 0.4 V 0.4 O 2 @NaNi 0.8 Mn 0.1 Ti 0.1 O 2 After the button cell is made of the material, the discharge capacity of the obtained button cell is higher.
The application verifies the stability of the prepared double-layer coated high-nickel layered ternary material, namely, the double-layer coated high-nickel layered ternary material is placed for 30 days at room temperature after being successfully prepared, and then the double-layer coated high-nickel layered ternary material is prepared into an electrode plate and a button cell is prepared from the electrode plate, and the preparation is carried outThe discharge capacity test, charge and discharge rate 0.5C, calculated the performance retention, test results as shown in FIG. 3, wherein S1 is example 1, S2 is example 2, S3 is example 3, S4 is example 4, S5 is example 5, S6 is example 6, S7 is example 7, S8 is example 8, S9 is example 9, S10 is example 10, S11 is example 11, S12 is example 12, D1 is comparative example 1, D2 is comparative example 2, the application prepares high nickel layered ternary material NaNi by mixing sodium source, nickel source, manganese source and metal M1 source 1-a-b Mn a M1 b O 2 Then adding the material, a sodium source, a nickel source, a manganese source and a metal M2 source into a solvent, under the action of a functional agent, preparing a wet gel coated high-nickel layered ternary material, and carrying out subsequent calcination and carbon dioxide introduction under vacuum treatment to obtain a double-layer coated high-nickel layered ternary material, namely Na 2 CO 3 @NaNi 1-x-y Mn x M2 y O 2 @NaNi 1-a- b Mn a M1 b O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein a=0.1, b=0.1, where x=0.4, y=0.4; the metal M1 source and the metal M2 source can be at least 1 selected from metal elements Li, zn, ti, V, co, cu, fe and Mg, and the metal M1 source and the metal M2 source can be consistent or inconsistent; the functional agent is citric acid, and is prepared from citric acid, sodium source, nickel source, manganese source, metal M2 source, and NaNi 1-a-b Mn a M1 b O 2 Formation of NaNi 1-x-y Mn x M2 y O 2 @NaNi 1-a-b Mn 0.1 M1 b O 2 And finally preparing Na 2 CO 3 @NaNi 0.2 Mn 0.4 Ti 0.4 O 2 @NaNi 0.8 Mn 0.1 Ti 0.1 O 2 The use of the material and the functional agent of the second layer can adjust the NaNi 0.2 Mn 0.4 Ti 0.4 O 2 With NaNi 0.8 Mn 0.1 Ti 0.1 O 2 And finally improving the discharge capacity of the prepared button cell; the application can also prepare Na 2 CO 3 @NaNi 0.2 Mn 0.4 V 0.4 O 2 @NaNi 0.8 Mn 0.1 Ti 0.1 O 2 The discharge capacity of the prepared button cell is improved; through research, the application is used for preparing Na 2 CO 3 @NaNi 0.2 Mn 0.4 V 0.4 O 2 @NaNi 0.8 Mn 0.1 Ti 0.1 O 2 In the material of (2), the gluconic acid ester or the modified gluconic acid ester can be used together with the citric acid as a functional agent, and the use effect of the modified gluconic acid ester is better than that of the gluconic acid ester; further, glycerol monobutyrate may be added to the functional agent, and when citric acid, modified gluconic acid ester and glycerol monobutyrate are used together as the functional agent, na is obtained 2 CO 3 @NaNi 0.2 Mn 0.4 V 0.4 O 2 @NaNi 0.8 Mn 0.1 Ti 0.1 O 2 After the button cell is made of the material, the discharge capacity of the obtained button cell is higher.
The above embodiments are merely for illustrating the present application and not for limiting the same, and various changes and modifications may be made by one of ordinary skill in the art without departing from the spirit and scope of the application. Therefore, all equivalent technical solutions are also within the scope of the present application, which is defined by the claims.
Claims (10)
1. A highly stable layered cathode material comprising: is a high nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 Wherein a+b is less than or equal to 0.2, a is not 0, and b is not 0;
the middle layer is made of a low-nickel layered ternary material NaNi 1-x-y Mn x M2 y O 2 Wherein 0.6.ltoreq.x+y.ltoreq.0.9, x being other than 0, y being other than 0;
and an outer layer material.
2. The highly stable layered cathode material according to claim 1, characterized in that: m1 is at least 1 of metal elements Li, zn, ti, V, co, cu, fe and Mg; or, M2 is at least 1 of metal element Li, zn, ti, V, co, cu, fe and Mg.
3. The highly stable layered cathode material according to claim 2, characterized in that: m1 and M2 are the same metal element; or, M1 and M2 are different metal elements; or, M1 is Ti; or, M2 is Ti; or, M2 is V.
4. The highly stable layered cathode material according to claim 1, characterized in that: the low-nickel layered ternary material NaNi 1-x-y Mn x M2 y O 2 The content of the (C) is higher than that of the Ni-layered ternary material NaNi 1-a-b Mn a M1 b O 2 1-10% of the mass; or, the outer layer material is Na 2 CO 3 A layer; or the thickness of the outer layer material is 2-15 nanometers.
5. A preparation method of a high-stability layered anode material is characterized by comprising the following steps: the metal source of the middle layer and the high nickel lamellar ternary material NaNi 1-a-b Mn a M1 b O 2 Mixing the materials in a solvent, adding a functional agent, and preparing a single-layer coated high-nickel layered ternary material, namely NaNi 1-x-y Mn x M2 y O 2 @NaNi 1-a-b Mn a M1 b O 2 Wherein a+b is less than or equal to 0.2, a is not 0, b is not 0,0.6 and x+y is less than or equal to 0.9, x is not 0, and y is not 0; then the single-layer coated high nickel layered ternary material is placed in a material containing CO 2 In a gas container, preparing a double-layer coated high-nickel layered ternary material, namely Na 2 CO 3 @NaNi 1-x-y Mn x M2 y O 2 @NaNi 1-a-b Mn a M1 b O 2 。
6. The method for preparing a highly stable layered cathode material according to claim 5, characterized in that: the metal source comprises a sodium source, a nickel source, a manganese source and a metal M2 source; or, the solvent includes at least 1 of acetone and ethanol; alternatively, the functional agent comprises citric acid.
7. The method for preparing a highly stable layered cathode material according to claim 6, characterized in that: the sodium source is sodium acetate or sodium nitrate; or, the nickel source is nickel acetate or nickel nitrate; or, the manganese source is manganese acetate or manganese nitrate; or, the functional agent also comprises gluconic acid ester or modified gluconic acid ester, wherein the modified gluconic acid ester has 1, 3-propylene diamine group.
8. The method for preparing a highly stable layered cathode material according to claim 5, characterized in that: m1 is Ti; or, M2 is Ti; or, M2 is V.
9. The method for preparing a highly stable layered cathode material according to claim 5, characterized in that: a=0.1; or, the b=0.1; or, the x=0.4; or, the y=0.4.
10. Use of the highly stable layered cathode material according to claim 1 for the preparation of a battery for a vehicle.
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