CN116143199B - Surface-coated layered oxide, preparation method thereof, positive plate, sodium ion battery and electric equipment - Google Patents
Surface-coated layered oxide, preparation method thereof, positive plate, sodium ion battery and electric equipment Download PDFInfo
- Publication number
- CN116143199B CN116143199B CN202310434242.0A CN202310434242A CN116143199B CN 116143199 B CN116143199 B CN 116143199B CN 202310434242 A CN202310434242 A CN 202310434242A CN 116143199 B CN116143199 B CN 116143199B
- Authority
- CN
- China
- Prior art keywords
- layered oxide
- tmo
- powder
- sodium
- coated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 22
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 124
- 239000011734 sodium Substances 0.000 claims abstract description 77
- 239000000843 powder Substances 0.000 claims abstract description 62
- 238000000498 ball milling Methods 0.000 claims abstract description 50
- 238000005245 sintering Methods 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims description 24
- 239000007790 solid phase Substances 0.000 claims description 21
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000001632 sodium acetate Substances 0.000 claims description 18
- 235000017281 sodium acetate Nutrition 0.000 claims description 18
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 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 description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000011247 coating layer Substances 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- 239000011858 nanopowder Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 238000005253 cladding Methods 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000007547 defect Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 42
- 230000000052 comparative effect Effects 0.000 description 41
- 238000000576 coating method Methods 0.000 description 18
- 238000001816 cooling Methods 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 238000000227 grinding Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000011812 mixed powder Substances 0.000 description 9
- 230000000630 rising effect Effects 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 239000011356 non-aqueous organic solvent Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- OQXNUCOGMMHHNA-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CC1COS(=O)(=O)O1 OQXNUCOGMMHHNA-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229910021201 NaFSI Inorganic materials 0.000 description 1
- 241001460678 Napo <wasp> Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- KBVUALKOHTZCGR-UHFFFAOYSA-M sodium;difluorophosphinate Chemical compound [Na+].[O-]P(F)(F)=O KBVUALKOHTZCGR-UHFFFAOYSA-M 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- FVCJARXRCUNQQS-UHFFFAOYSA-N trimethylsilyl dihydrogen phosphate Chemical compound C[Si](C)(C)OP(O)(O)=O FVCJARXRCUNQQS-UHFFFAOYSA-N 0.000 description 1
- IIVDETMOCZWPPU-UHFFFAOYSA-N trimethylsilyloxyboronic acid Chemical compound C[Si](C)(C)OB(O)O IIVDETMOCZWPPU-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a surface-coated layered oxide, which comprises the following steps: s1, preparing layered oxide Na y TMO 2 The powder is exposed to the air environment with the humidity more than or equal to 30 percent; s2, treating the layered oxide Na treated by the step S1 y TMO 2 Powder and TiO 2 Ball milling and mixing nanometer powder; s3, sintering the mixture obtained in the step S2 to obtain the surface-coated layered oxide. The invention also discloses the surface-coated layered oxide prepared by the method, a positive plate, a sodium ion battery and electric equipment. The surface-coated layered oxide provided by the invention can improve the defect of poor air stability of the layered oxide, and improves the cycle performance and the multiplying power performance of the layered oxide material.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a surface-coated layered oxide, a preparation method thereof, a positive plate, a sodium ion battery and electric equipment.
Background
Among various positive electrode materials of sodium ion batteries, O3-phase layered oxides have received attention because they can provide sufficient sodium in a full battery, have high electrochemical activity, have high theoretical specific capacities, and are easy to synthesize. However, the O3 phase layered oxide material has poor air stability and unstable structure, resulting in a certain influence on the cycle performance and rate performance of the material.
Therefore, how to improve the structural stability of the O3-phase layered oxide, and further improve the cycle performance and the rate performance of the battery becomes one of the key problems in the related art of sodium ion batteries.
Disclosure of Invention
The invention aims to solve the technical problem of providing a surface-coated layered oxide, which can improve the air stability of the layered oxide and improve the multiplying power performance and the cycle stability of the layered oxide material.
In order to solve the technical problems, the invention provides the following technical scheme:
the first aspect of the present invention provides a method for preparing a surface-coated layered oxide, comprising the steps of:
s1, layered oxide Na y TMO 2 The powder is exposed to the air environment with the humidity more than or equal to 30 percent;
s2, the layered oxide Na treated in the step S1 y TMO 2 Powder and TiO 2 Ball milling and mixing nanometer powder;
s3, sintering the mixture obtained in the step S2 to obtain the surface-coated layered oxide;
in the step S1, y is more than 0.8 and less than or equal to 1, and TM is one or more selected from Ti, V, cr, mn, fe, co, ni, cu, zn, li, B, mg, al, K, ca, zr, nb, sn.
Further, in step S1: the Na is y TMO 2 Is NaNi i Fe j Mn k M m O 2 M is one of Li, B, mg, al, K, ca, co, V, cr, cu, zn, zr, nb and SnOr a plurality of; wherein: 0<i≤0.4,0<j≤0.5,0<k≤0.6,0<m is less than or equal to 0.2, and i+j+k+m=1;
and/or the layered oxide Na y TMO 2 The powder is exposed to the air environment with the humidity of more than or equal to 30 percent for 24-36 hours.
Further, in step S1, the layered oxide NaNi i Fe j Mn k M m O 2 The preparation method of (2) comprises the following steps:
a. precursor Ni i Fe j Mn k M m (OH) 2 Ball-milling and mixing with a sodium source;
b. pre-sintering the mixture obtained in the step a, and then performing solid-phase sintering to obtain the layered oxide NaNi i Fe j Mn k M m O 2 ;
Wherein: in the step a, the sodium source is selected from one or more of sodium carbonate, sodium hydroxide, sodium acetate, sodium oxalate and sodium nitrate;
and/or in the step b, the temperature of the presintering is 200-550 ℃, and the presintering time is 1-8 hours; the temperature of the solid phase sintering is 750-1100 ℃, and the time of the solid phase sintering is 4-20 h.
Further, in step S2: the TiO 2 The addition amount of the nano powder is the layered oxide Na y TMO 2 0.4-0.8 wt% of the weight of the material;
and/or the rotation speed of the ball milling is 300-600 r/min, and the ball milling time is 2-7 h.
Further, in step S3: the sintering treatment temperature is 600-800 ℃, and the sintering treatment time is 0.5-3.5 h.
In a second aspect, the present invention provides a surface-coated layered oxide comprising layered oxide Na y TMO 2 Located in the layered oxide Na y TMO 2 Na of surface 4 Ti 5 O 12 A cladding layer, wherein: y is more than 0.8 and less than or equal to 1, and TM is one or more selected from Ti, V, cr, mn, fe, co, ni, cu, zn, li, B, mg, al, K, ca, zr, nb, sn.
Further, the Na y TMO 2 Is NaNi i Fe j Mn k M m O 2 M is one or more of Li, B, mg, al, K, ca, co, V, cr, cu, zn, zr, nb and Sn; wherein: 0<i≤0.4,0<j≤0.5,0<k≤0.6,0<m is less than or equal to 0.2, and i+j+k+m=1;
and/or the layered oxide Na y TMO 2 The particle diameter D50 of the particles is 7-12 mu m;
and/or, the Na 4 Ti 5 O 12 The thickness of the coating layer is 5-20 nm.
In a third aspect, the present invention provides a positive electrode sheet comprising the surface-coated layered oxide prepared by the aforementioned preparation method, or comprising the aforementioned surface-coated layered oxide.
According to a fourth aspect of the invention, there is provided a sodium ion battery comprising the positive electrode sheet described above.
In a fifth aspect, the invention provides an electric device, which comprises the sodium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
1. in the surface-coated layered oxide of the present invention, layered oxide Na y TMO 2 Has Na on the surface 4 Ti 5 O 12 A dense coating layer which on the one hand hinders the material from being mixed with H in the air 2 O、CO 2 O and O 2 The reaction occurs, so that the air stability of the material is greatly improved; on the other hand, the structural change of the layered oxide material caused by sodium ion deintercalation in the circulation process is inhibited, and the structural stability of the material in the circulation process is improved.
2. In the surface-coated layered oxide of the present invention, na 4 Ti 5 O 12 The existence of the compact coating layer prevents the material from being in direct contact with the electrolyte to a certain extent, ensures the stability of the material interface and improves the cycle performance of the layered oxide material.
3. The surface-coated layered oxide of the present invention, ti during sintering 4+ The sodium ions can diffuse into the bulk phase of the material at high temperature to form bulk phase doping, so that the interlayer spacing of the material is enlarged, the diffusion capacity of the sodium ions in the material is improved, and the rate capability of the material is improved; and Ti is 4+ The ionic compound is high-valence ions, and the electronic conductivity of the material can be improved by doping the high-valence ions, so that the rate capability of the material is further improved; in addition, ti 4+ The doping into the material can also play a role in stabilizing the structure, so that the cycling stability of the material can also be improved.
4. In the sintering process, the surface coating and doping process can be completed in one step, and the method is simple and convenient for large-scale application.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of O3 phase layered oxide materials prepared in example 4, comparative example 1 and comparative example 4 after three days of exposure to an air atmosphere having a humidity of 55%;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the O3-phase layered oxide material prepared in example 1;
fig. 3 a-d are lattice spacing diagrams of the O3 phase layered oxide materials prepared in example 4, comparative example 1, comparative example 2 and comparative example 4, respectively, under high power transmission electron microscopy.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The invention provides a coating modification method for layered oxide, which comprises coating Na on the surface of layered oxide 4 Ti 5 O 12 The compact coating layer improves the structural stability of the layered oxide and improves the cycle performance and the multiplying power performance of the material.
Specifically, the invention provides a surface-coated layered oxide, which comprises layered oxide Na y TMO 2 Located in the layered oxide Na y TMO 2 Na of surface 4 Ti 5 O 12 A cladding layer, wherein: y is more than 0.8 and less than or equal to 1, and TM is one or more selected from Ti, V, cr, mn, fe, co, ni, cu, zn, li, B, mg, al, K, ca, zr, nb, sn.
In the present invention, layered oxide Na y TMO 2 Is an O3 phase layered oxide, where 0.8 < y.ltoreq.1, e.g. y=0.9, 1, etc. The O3 phase layered oxide has the common problems of poor multiplying power performance, poor cycle performance and the like due to unstable structure.
In the invention, the O3 phase layered oxide Na y TMO 2 The particles may be used in the form of particles of any shape, such as spheres, flakes or irregular particles. Furthermore, the O3 phase layered oxide particles may be in the form of primary particles or secondary particles. The size of the O3 phase layered oxide particles may be any size commonly used in the art. Preferably, the layered oxide Na y TMO 2 The secondary particles of (2) have a particle diameter D50 of 7 to 12 μm, for example, 7, 8, 9, 10, 11, 12 μm, etc.
In the present invention, O3 phase layered oxide Na y TMO 2 The surface is formed with a dense water-insoluble coating layer Na 4 Ti 5 O 12 The presence of such a coating on the one hand counteracts the material and H in the air 2 O、CO 2 O and O 2 The air stability of the layered oxide material is greatly improved by the reaction; on the other hand inhibit the O3 phase layered oxide Na y T M O 2 The structural change caused by sodium ion deintercalation in the circulation process improves the structural stability of the material in the circulation process; in addition, na 4 Ti 5 O 12 The compact coating layer also avoids direct contact between the material and the electrolyte to a certain extent, ensures the interface stability of the material and improves the cycle performance of the material. In the present invention, na 4 Ti 5 O 12 The thickness of the coating layer is preferably 5 to 20nm, for example, 5, 6, 8, 10, 12, 14, 15, 16, 18, 20nm, etc.
In the invention is excellentIn an alternative embodiment, the O3 phase layered oxide Na y TMO 2 Is NaNi i Fe j Mn k M m O 2 Wherein M is one or more of Li, B, mg, al, K, ca, co, V, cr, cu, zn, zr, nb and Sn; 0<i≤0.4,0<j≤0.5,0<k≤0.6,0<m is less than or equal to 0.2, and i+j+k+m=1. For example, i=0.1, 0.2, 0.3, 0.4, or j=0.1, 0.2, 0.3, 0.4, 0.5, or k=0.1, 0.2, 0.3, 0.4, 0.5, 0.6, or m=0.1, 0.2, etc.
The invention also discloses a preparation method of the surface-coated layered oxide, which comprises the following steps:
s1, layered oxide Na y TMO 2 Exposing the powder to an air atmosphere with humidity of more than or equal to 30%;
s2, the layered oxide Na treated in the step S1 y TMO 2 Powder and TiO 2 Ball milling and mixing nanometer powder;
s3, sintering the mixture obtained in the step S2 to obtain the surface-coated layered oxide;
in the above step S1, na y TMO 2 Is an O3 phase layered oxide, wherein: y is more than 0.8 and less than or equal to 1, and TM is one or more selected from Ti, V, cr, mn, fe, co, ni, cu, zn, li, B, mg, al, K, ca, zr, nb, sn.
In the above step S1, the layered oxide Na y TMO 2 The powder may be prepared by methods conventional in the art, such as solid phase sintering.
In a preferred embodiment, the O3 phase layered oxide Na y TMO 2 Is NaNi i Fe j Mn k M m O 2 Wherein M is one or more of Li, B, mg, al, K, ca, co, V, cr, cu, zn, zr, nb and Sn; 0<i≤0.4,0<j≤0.5,0<k≤0.6,0<m is less than or equal to 0.2, and i+j+k+m=1. For example, i=0.1, 0.2, 0.3, 0.4, or j=0.1, 0.2, 0.3, 0.4, 0.5, or k=0.1, 0.2, 0.3, 0.4, 0.5, 0.6, or m=0.1, 0.2, etc.
For layered oxide Na y TMO 2 The powder is mixed with the powder,the catalyst can be prepared by adopting a sodium source and a metal source with a certain molar ratio as raw materials through a sintering method. With NaNi i Fe j Mn k M m O 2 For example, the powder may be prepared by the steps of:
a. precursor source Ni i Fe j Mn k M m (OH) 2 Ball-milling and mixing with a sodium source;
b. pre-sintering the mixture obtained in the step a, and then performing solid-phase sintering to obtain the layered oxide NaNi i Fe j Mn k M m O 2 。
In the step a, the sodium source may be a commonly used sodium-containing compound, including but not limited to one or more selected from sodium carbonate, sodium hydroxide, sodium acetate, sodium oxalate, and sodium nitrate. The sodium source is relative to the precursor source Ni i Fe j Mn k M m (OH) 2 Excess is required, for example 5%, 6%, 7%, 8% excess, etc.
In the step a, the precursor source Ni i Fe j Mn k M m (OH) 2 Mixing with sodium source preferably by ball milling, not only can refine the particles of raw materials, but also can lead the precursor source Ni i Fe j Mn k M m (OH) 2 And more evenly mixed with the sodium source. The rotation speed of ball milling is preferably 300-800 r/min, such as 300, 400, 500, 600, 700, 800 and r/min; the ball milling time is preferably 0.5 to 5 hours, for example 0.5, 1, 2, 3, 4, 5 hours, etc.
In the step b, the mixture is presintered in a sintering furnace (such as a muffle furnace), wherein the presintering temperature is preferably 200-550 ℃, such as 200, 250, 300, 350, 400, 450, 500, 550 ℃, etc.; the pre-sintering time is preferably 1 to 8 hours, for example 1, 2, 3, 4, 5, 6, 7, 8 hours, etc. After the pre-sintering is finished, the temperature is raised again to carry out solid-phase sintering. The temperature rise rate is 1-10 ℃/min, such as 1, 2, 3, 4, 5, 6, 8, 10 ℃/min, etc. The solid phase sintering temperature is preferably 750-1100 ℃, such as 750, 800, 850, 900, 950, 1000, 1050, 1100 ℃, etc.; the solid phase sintering time is 4-20 hours, for example, 4, 5, 6, 8, 10, 12, 15, 16, 18, 20 hours and the like.
After solid phase sintering, the layered oxide NaNi is obtained i Fe j Mn k M m O 2 . The sintered product is further ground to obtain black NaNi i Fe j Mn k M m O 2 And (3) powder.
In the above step S1, the layered oxide Na y TMO 2 The powder needs to be exposed to a humid air environment for a period of time, the purpose of this step being: in moist air, layered oxide Na y TMO 2 The powder will react with H in the air 2 O、CO 2 O and O 2 React to generate Na on the surface 2 CO 3 、NaOH、NaHCO 3 Etc., thereby making it easier to react with TiO in subsequent steps 2 React to generate more complete Na 4 Ti 5 O 12 And a coating layer. In the above-mentioned moist air environment, the air humidity is preferably not less than 30%, for example, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, etc. The exposure time can be adjusted according to the air humidity so that Na y TMO 2 Powder and H in air 2 O、CO 2 O and O 2 The reaction is fully performed. In some embodiments, the exposure time may be 1 to 36 hours, preferably 24 to 36 hours, such as 1, 2, 4, 8, 12, 16, 24, 30, 36 hours, etc.
In the above step S2, tiO 2 The addition amount of the nano powder is preferably layered oxide Na y TMO 2 The mass of the catalyst is 0.4wt% to 0.8wt%, for example, 0.4wt%, 0.5 wt%, 0.6wt%, 0.7 wt%, 0.8wt%, etc. During mixing, the materials are preferably mixed by adopting a ball milling mode, the rotation speed of the ball milling is preferably 300-600 r/min, such as 300, 400, 500, 600r/min and the like, and the time of the ball milling is preferably 2-7 h, such as 2, 3, 4, 5, 6, 7h and the like.
In the step S3, the solid powder mixture after ball milling is placed in a sintering furnace (such as a muffle furnace), and the temperature is raised to perform sintering treatment. Wherein the temperature rising rate is 1-10 ℃/min, such as 1, 2, 3, 4, 5, 6, 8, 10 ℃/min, etc.
In the above step S3, during sinteringIn Ti, ti 4+ The high-temperature diffusion of the material into the bulk phase of the O3 phase layered material forms bulk phase doping, and the interlayer spacing of the material is enlarged, so that the diffusion capacity of sodium ions in the material is improved, and the rate capability of the material is improved; next, ti 4+ The material can be doped with the material to play a role in stabilizing the structure, so that double insurance is performed for improving the cycle stability of the material; again, ti 4+ The O3 phase layered material is doped with high-valence ions, so that the electronic conductivity of the material can be improved, and the rate capability of the material is further improved.
In the above step S3, the sintering temperature and time need to be controlled within a certain range. If the sintering time is too long and the temperature is too high, ti is accelerated 4+ Into the bulk structure of the material, resulting in Ti 4+ Not fully with layered oxide Na y TMO 2 Surface generation of Na 2 CO 3 、NaOH、NaHCO 3 The substances react fully to form complete Na 4 Ti 5 O 12 Coating, in turn, results in residual Na on the surface of the material 2 CO 3 、NaOH、NaHCO 3 NaO is generated by the substances at high temperature, and after the temperature is reduced, the substances continue to react with H in the air 2 O、CO 2 O and O 2 Reactions occur, affecting the air stability of the material. In the invention, the temperature of the sintering treatment is preferably controlled to 600-800 ℃, such as 600, 650, 700, 750, 800 ℃ and the like; the sintering time is preferably controlled to 0.5 to 3.5 hours, for example, 0.5, 1, 1.5, 2, 2.5, 3, 3.5 hours, etc.
In a preferred embodiment of the present invention, the humidity of the environmental conditions is controlled to be 5% or less in the process of synthesizing the above surface-coated layered oxide, because: (1) Certain raw materials (such as sodium carbonate) are easy to absorb water, and the weighing precision is affected; (2) The layered oxide is sensitive to water, is easy to react with water carbon dioxide and oxygen in the air, so that sodium is separated out, and the material is subjected to phase change when serious; (3) Ensure strict experimental conditions, prevent humidity interference and make the experiment not have contrast.
On the basis of the surface-coated layered oxide, the invention also provides a sodium ion battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the diaphragm is arranged to isolate the positive plate from the negative plate.
In the sodium ion battery, the positive plate can be prepared by adopting a common plate preparation process in the field. The preparation method is as follows: mixing the surface-coated layered oxide, the conductive agent and the binder to prepare slurry, coating the slurry on at least one side surface of the positive electrode current collector, and drying and tabletting to obtain the positive electrode plate.
In the preparation method of the positive plate, the type and the content of the conductive agent are not particularly limited, and can be selected according to actual requirements. In some embodiments, the conductive agent includes at least one of conductive carbon black, carbon nanotubes, acetylene black, graphene, ketjen black, carbon nanofibers, and the like. It will be appreciated that other conductive agents capable of performing the functions of the present application may be selected as desired without limitation without departing from the spirit of the present application.
In the preparation method of the positive plate, the types and the content of the binder are not particularly limited, and can be selected according to actual requirements. In some embodiments, the binder includes at least one of polyacrylonitrile, polyvinylidene fluoride, polyvinyl alcohol, sodium carboxymethyl cellulose, polymethacrylate, polyacrylic acid, sodium polyacrylate, polyacrylamide, polyamide, polyimide, polyacrylate, styrene butadiene rubber, sodium alginate, chitosan, polyethylene glycol, guar gum, and the like.
The type of the positive electrode current collector is not particularly limited, and may be selected according to practical requirements, for example, the positive electrode current collector may be an aluminum foil, a nickel foil or a polymer conductive film, and preferably the positive electrode current collector is an aluminum foil.
In the sodium ion battery, the type of separator is not particularly limited, and any separator material used in conventional batteries, such as polyethylene, polypropylene, polyvinylidene fluoride, nonwoven fabric, multilayer composite films thereof, and modified separators such as ceramic modification and PVDF modification of the separator may be used.
In the sodium ion battery, electrolysisThe electrolyte may be one or more of an organic liquid electrolyte, an organic solid electrolyte, a solid ceramic electrolyte, and a gel electrolyte. Preferably, the electrolyte is an organic liquid electrolyte obtained by dissolving sodium salt in a nonaqueous organic solvent; wherein the sodium salt may comprise sodium difluorophosphate (NaPO) 2 F 2 ) Sodium hexafluorophosphate (NaPF) 6 ) One or more of sodium bis (fluorosulfonyl) imide (NaFSI), sodium bis (trifluoromethanesulfonyl) imide (naftsi), and sodium difluoro (NaDFOB) oxalato borate (NaDFOB). The nonaqueous organic solvent may include one or more of cyclic carbonate, chain carbonate, and carboxylate. Wherein the cyclic carbonate can be selected from one or more of Ethylene Carbonate (EC), propylene Carbonate (PC), butylene carbonate and gamma-butyrolactone; the chain carbonate may be selected from one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl Propyl Carbonate (MPC), methyl Acetate (MA), ethyl Acetate (EA), and Ethyl Propionate (EP).
In some embodiments, a certain amount of additives may also be added to the organic liquid electrolyte. The additive may include one or more of Vinylene Carbonate (VC), vinyl carbonate (VEC), vinyl sulfate (DTD), ethylene Sulfite (ES), methylene Methane Disulfonate (MMDS), 1, 3-Propane Sultone (PS), propylene sultone (PES), propylene sulfate (TMS), trimethylsilyl phosphate (TMSP), trimethylsilyl borate (TMSB), fluoroethylene carbonate (FEC).
The invention further provides electric equipment which comprises the sodium ion battery.
In some embodiments, the powered device of the present invention includes, but is not limited to, a backup power source, a motor, an electric car, an electric motorcycle, a moped, a bicycle, an electric tool, a household large-scale battery, and the like.
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents, etc. used, unless otherwise specified, are commercially available.
In the examples below, the symbol "@" represents cladding, na 4 Ti 5 O 12 @NaNi 0.1 Fe 0.2 Mn 0.6 Mg 0.1 O 2 The layered oxide material represents Na 4 Ti 5 O 12 Coating on NaNi 0.1 Fe 0.2 Mn 0.6 Mg 0.1 O 2 The surface of the layered oxide.
1. XRD test method
Grinding the prepared powder material, transferring to a glass sheet object stage, and transferring to an X-ray diffractometer for scanning test, wherein the scanning range is 10-80 degrees, and the scanning speed is 5 degrees/min.
2. TEM test method
And (3) grinding the prepared powder uniformly, performing ultrasonic treatment on the material by using absolute ethyl alcohol as a dispersing agent, dripping the dispersed material on a transmission electron microscope carrier net by using a dropper, and observing.
3. Assembling and testing of button cell
Exposing the anode material for 3 days in an environment with humidity of more than or equal to 55%, grinding the anode material, the conductive agent Super P and the binder PVDF uniformly according to a mass ratio of 9:0.5:0.5, adding a proper amount of NMP to prepare slurry, uniformly coating the slurry on the pretreated aluminum foil, drying the aluminum foil in a blast drying box at 80 ℃ for 1h, and drying the aluminum foil in a vacuum drying box at 120 ℃ for 12h; then cutting into 14mm round positive plates by a cutting machine. Sodium metal sheets with the diameter of 14mm and the thickness of 0.2mm are used as a negative electrode, 0.1mol/L sodium perchlorate solution is used as electrolyte (the solvent is a mixed solvent formed by ethylene carbonate and dimethyl carbonate according to the volume ratio of 1:1), whatman GF/F glass fibers with the diameter of 16mm are used as a diaphragm, and the CR2032 button cell is assembled in a glove box filled with high-purity argon.
The assembled CR2032 coin cell was tested for charge and discharge at a current density of 0.1C using a constant current charge and discharge mode. The test items include: the first charge and discharge, rate capability and 1C charge and discharge capacity retention rate of 100 circles of the material in the sodium ion battery.
The first-circle charge and discharge testing method comprises the following steps: placing the button cell on a Wuhan blue electric cell tester (CT 2001A), and testing the charge and discharge capacity of the button cell at the first circle by adopting the multiplying power of 0.1C, wherein the charge and discharge voltage range is 2.0-4.0V;
the multiplying power performance testing method comprises the following steps: placing the button cell on a Wuhan blue electric cell tester (CT 2001A), wherein the charging and discharging voltage ranges from 2.0V to 4.0V, and activating the first circle by adopting a multiplying power of 0.1C for 3 weeks; performing charge and discharge test for 5 weeks by adopting a 1C multiplying power from the 4 th week, wherein the average value of each circle of charge and discharge of the 1C multiplying power in the period is recorded as 1C discharge capacity; performing charge and discharge test for 5 weeks by adopting a 2C multiplying power from the 9 th week, wherein the average value of each circle of charge and discharge of the 2C multiplying power in the period is recorded as 2C discharge capacity; performing charge and discharge test for 5 weeks by using a 5C rate from the 14 th week, wherein the average value of each circle of charge and discharge of the 5C rate in the period is recorded as 5C discharge capacity;
1C method for testing capacity retention rate of 100 circles of charging and discharging: and placing the button cell on a Wuhan blue electric cell tester (CT 2001A), activating the button cell for 3 weeks by adopting a multiplying power of 0.1C, performing charge-discharge cycle for 100 circles by adopting a multiplying power of 1C from 4 weeks, and recording that the charge and discharge capacity of the 100 th circle are respectively C0 and C1, wherein C1/C0 is 100% of the capacity retention rate of 1C, and the charge-discharge voltage range is 2.0-4.0V.
Example 1
(1) Ni is added with 0.1 Fe 0.2 Mn 0.6 Mg 0.1 (OH) 2 Placing the precursor and sodium acetate in a ball milling tank with the rotating speed of 300r/min according to the molar ratio of 1:1.06, and ball milling for 2 hours to fully mix the precursor and the sodium acetate; placing the mixed powder in a muffle furnace, presintering for 3h at 200 ℃ at a heating rate of 5 ℃/min, then raising the temperature to 800 ℃, carrying out high-temperature solid-phase sintering for 10h, and naturally cooling and grinding to obtain the layered oxide material NaNi 0.1 Fe 0.2 Mn 0.6 Mg 0.1 O 2 Is a black powder of (a).
(2) The layered oxide material NaNi 0.1 Fe 0.2 Mn 0.6 Mg 0.1 O 2 Black powder of (c) at air humidityExposing for 24h in an environment of more than or equal to 30 percent; then NaNi is added 0.1 Fe 0.2 Mn 0.6 Mg 0.1 O 2 Black powder and TiO 0.4wt% of powder mass 2 Placing the nano powder into a ball milling tank, and ball milling for 7 hours at the rotating speed of 300/min to uniformly mix; then placing the powder into a muffle furnace with the temperature rising rate of 3 ℃/min, and sintering at 650 ℃ for 3.5h. Cooling along with the furnace to obtain Na 4 Ti 5 O 12 @ NaNi 0.1 Fe 0.2 Mn 0.6 Mg 0.1 O 2 Layered oxide materials.
Example 2
(1) Ni is added with 0.2 Fe 0.3 Mn 0.45 Al 0.05 (OH) 2 Placing the precursor and sodium carbonate in a ball milling tank with the rotating speed of 700r/min according to the molar ratio of 1:0.503, and ball milling for 0.5h to fully mix the precursor and the sodium carbonate; placing the mixed powder in a muffle furnace, presintering for 2h at 300 ℃ at a heating rate of 5 ℃/min, then raising the temperature to 850 ℃, carrying out high-temperature solid-phase sintering for 15h, and naturally cooling and grinding to obtain the layered oxide material NaNi 0.2 Fe 0.3 Mn 0.45 Al 0.05 O 2 Is a black powder of (a).
(2) The layered oxide material NaNi 0.2 Fe 0.3 Mn 0.45 Al 0.05 O 2 Exposing the black powder of (2) for 36 hours in an environment with the air humidity of more than or equal to 30%; then NaNi is added 0.2 Fe 0.3 Mn 0.45 Al 0.05 O 2 Black powder and 0.55wt% TiO based on the mass of the powder 2 Placing the nano powder into a ball milling tank, and ball milling for 7 hours at the rotating speed of 300/min to uniformly mix; then the mixture is placed in a muffle furnace with the temperature rising rate of 5 ℃/min, and sintered for 2.5 hours at the temperature of 750 ℃. Cooling along with the furnace to obtain Na 4 Ti 5 O 12 @ NaNi 0.2 Fe 0.3 Mn 0.45 Al 0.05 O 2 Layered oxide materials.
Example 3
(1) Ni is added with 0.3 Fe 0.1 Mn 0.5 Cu 0.05 Al 0.05 (OH) 2 The precursor and sodium acetate are placed in a ball milling tank with the rotating speed of 500r/min according to the mol ratio of 1:1.06, and the balls are formedGrinding for 1.5h to fully mix the materials; placing the mixed powder in a muffle furnace, presintering for 2h at 300 ℃ at a heating rate of 5 ℃/min, then raising the temperature to 800 ℃, carrying out high-temperature solid-phase sintering for 15h, and naturally cooling and grinding to obtain the layered oxide material NaNi 0.3 Fe 0.1 Mn 0.5 Cu 0.05 Al 0.05 O 2 Is a black powder of (a).
(2) The layered oxide material NaNi 0.3 Fe 0.1 Mn 0.5 Cu 0.05 Al 0.05 O 2 Exposing the black powder of (2) for 36 hours in an environment with the air humidity of more than or equal to 30%; then NaNi is added 0.3 Fe 0.1 Mn 0.5 Cu 0.05 Al 0.05 O 2 Black powder and 0.75wt% TiO based on the powder mass 2 Placing the nano powder into a ball milling tank, and ball milling for 7 hours at the rotating speed of 300/min to uniformly mix; then placing the powder into a muffle furnace with the temperature rising rate of 5 ℃/min, and sintering for 2 hours at 800 ℃. Cooling along with the furnace to obtain Na 4 Ti 5 O 12 @ NaNi 0.3 Fe 0.1 Mn 0.5 Cu 0.05 Al 0.05 O 2 Layered oxide materials.
Example 4
(1) Ni is added with 0.15 Fe 0.25 Mn 0.55 Zr 0.05 (OH) 2 Placing the precursor and sodium acetate in a ball milling tank with the rotating speed of 300r/min according to the molar ratio of 1:1.06, and ball milling for 2 hours to fully mix the precursor and the sodium acetate; placing the mixed powder in a muffle furnace, presintering for 2h at 300 ℃ at a heating rate of 5 ℃/min, then raising the temperature to 900 ℃, carrying out high-temperature solid-phase sintering for 12h, and naturally cooling and grinding to obtain the layered oxide material NaNi 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Is a black powder of (a).
(2) The layered oxide material NaNi 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Exposing the black powder of (2) in an environment with the air humidity of more than or equal to 30 percent for 24 hours; then NaNi is added 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Black powder and TiO 0.6wt% of powder mass 2 The nano powder is placed in a ball milling tankBall milling for 7 hours at the rotating speed of 300/min and uniformly mixing; then the mixture is placed in a muffle furnace with the temperature rising rate of 3 ℃/min, and sintered for 2.5 hours at the temperature of 750 ℃. Cooling along with the furnace to obtain Na 4 Ti 5 O 12 @ NaNi 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Layered oxide materials.
Comparative example 1
Ni is added with 0.15 Fe 0.25 Mn 0.55 Zr 0.05 (OH) 2 Placing the precursor and sodium acetate in a ball milling tank with the rotating speed of 300r/min according to the molar ratio of 1:1.06, and ball milling for 2 hours to fully mix the precursor and the sodium acetate; placing the mixed powder in a muffle furnace, presintering for 2h at 300 ℃ at a heating rate of 5 ℃/min, then raising the temperature to 900 ℃, carrying out high-temperature solid-phase sintering for 12h, and naturally cooling and grinding to obtain the layered oxide material NaNi 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Is a black powder of (a).
Comparative example 2
(1) Ni is added with 0.15 Fe 0.25 Mn 0.55 Zr 0.05 (OH) 2 Placing the precursor and sodium acetate in a ball milling tank with the rotating speed of 300r/min according to the molar ratio of 1:1.06, and ball milling for 2 hours to fully mix the precursor and the sodium acetate; placing the mixed powder in a muffle furnace, presintering for 2h at 300 ℃ at a heating rate of 5 ℃/min, then raising the temperature to 900 ℃, carrying out high-temperature solid-phase sintering for 12h, and naturally cooling and grinding to obtain the layered oxide material NaNi 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Is a black powder of (a).
(2) The layered oxide material NaNi 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Exposing the black powder of (2) in an environment with the air humidity of more than or equal to 30 percent for 24 hours; then NaNi is added 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Black powder and TiO 0.2wt% of powder mass 2 Placing the nano powder into a ball milling tank, and ball milling for 7 hours at the rotating speed of 300/min to uniformly mix; then the mixture is placed in a muffle furnace with the temperature rising rate of 3 ℃/min, and sintered for 2.5 hours at the temperature of 750 ℃. Cooling along with the furnace to obtain Na 4 Ti 5 O 12 @ NaNi 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Layered oxide materials.
Comparative example 3
(1) Ni is added with 0.15 Fe 0.25 Mn 0.55 Zr 0.05 (OH) 2 Placing the precursor and sodium acetate in a ball milling tank with the rotating speed of 300r/min according to the molar ratio of 1:1.06, and ball milling for 2 hours to fully mix the precursor and the sodium acetate; the mixed powder is placed in a muffle furnace to be presintered for 2 hours at the temperature of 300 ℃ at the heating rate of 5 ℃/min, then the temperature is increased to 900 ℃ to be sintered for 12 hours in a high-temperature solid phase, and the layered oxide material NaNi is obtained after natural cooling and grinding 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Is a black powder of (a).
(2) The layered oxide material NaNi 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Exposing the black powder of (2) in an environment with the air humidity of more than or equal to 30 percent for 24 hours; then NaNi is added 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Black powder and TiO 1wt% of powder mass thereof 2 Placing the nano powder into a ball milling tank, and ball milling for 7 hours at the rotating speed of 300/min to uniformly mix; then the mixture is placed in a muffle furnace with the temperature rising rate of 3 ℃/min, and sintered for 2.5 hours at the temperature of 750 ℃. Cooling along with the furnace to obtain Na 4 Ti 5 O 12 @ NaNi 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Layered oxide materials.
Comparative example 4
(1) Ni is added with 0.15 Fe 0.25 Mn 0.55 Zr 0.05 (OH) 2 Placing the precursor and sodium acetate in a ball milling tank with the rotating speed of 300r/min according to the molar ratio of 1:1.06, and ball milling for 2 hours to fully mix the precursor and the sodium acetate; placing the mixed powder in a muffle furnace, presintering for 2h at 300 ℃ at a heating rate of 5 ℃/min, then raising the temperature to 900 ℃, carrying out high-temperature solid-phase sintering for 12h, and naturally cooling and grinding to obtain the layered oxide material NaNi 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Is a black powder of (a).
(2) To be layered oxideMaterial NaNi 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Exposing the black powder of (2) in an environment with the air humidity of more than or equal to 30 percent for 24 hours; then NaNi is added 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Black powder and TiO 4.5wt% based on the powder mass 2 Placing the nano powder into a ball milling tank, and ball milling for 7 hours at the rotating speed of 300/min to uniformly mix; then placing the powder into a muffle furnace with the temperature rising rate of 3 ℃/min, and sintering for 12h at 900 ℃. Cooling along with the furnace to obtain NaNi doped with Ti element 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Layered oxide materials.
Comparative example 5
(1) Ni is added with 0.15 Fe 0.25 Mn 0.55 Zr 0.05 (OH) 2 Placing the precursor and sodium acetate in a ball milling tank with the rotating speed of 300r/min according to the molar ratio of 1:1.06, and ball milling for 2 hours to fully mix the precursor and the sodium acetate; placing the mixed powder in a muffle furnace, presintering for 2h at 300 ℃ at a heating rate of 5 ℃/min, then raising the temperature to 900 ℃, carrying out high-temperature solid-phase sintering for 12h, and naturally cooling and grinding to obtain the layered oxide material NaNi 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Is a black powder of (a).
(2) NaNi is processed by 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Black powder and TiO 0.6wt% of powder mass 2 Placing the nano powder into a ball milling tank, and ball milling for 7 hours at the rotating speed of 300/min to uniformly mix; then placing the powder into a muffle furnace with the temperature rising rate of 3 ℃/min, and sintering at 550 ℃ for 8 hours. Cooling with furnace to obtain TiO 2 @NaNi 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 Layered oxide materials.
Characterization of materials
Characterization tests are performed below for the O3 phase layered oxide materials prepared in the examples and comparative examples.
FIG. 1 is an X-ray diffraction pattern of the O3 phase layered oxide materials prepared in example 4, comparative example 1 and comparative example 4 after being exposed to an air atmosphere having a humidity of 55% for three days. As can be seen from the figures, the materials prepared in comparative examples 1 and 4 show characteristic peaks of new phases in XRD diffractograms after three days of exposure to air, whereas the material prepared in example 4 has no characteristic peaks of new phases. This shows that the material prepared in example 4 has better structural stability in air.
Fig. 2 is a transmission electron microscope image of the material prepared in example 1. As can be seen from FIG. 2, the surface of the layered oxide is coated with Na 4 Ti 5 O 12 A coating layer; it can be seen from FIG. 3 that while coating, there is a part of Ti 4+ Doping is into the lattice of the layered oxide material.
Fig. 3 a-d are high power transmission electron micrographs of the O3 phase layered oxide materials prepared in example 4, comparative example 1, comparative example 2 and comparative example 4, respectively. As can be seen from FIG. 3, the interlayer spacing of the material of example 4 is increased compared to that of comparative example 1 because of Ti at high temperature 4+ The material can diffuse into the bulk phase of the O3 phase layered material to form bulk phase doping, so that the interlayer spacing of the material is enlarged; while the interlayer spacing of the material of comparative example 2 was unchanged from that of comparative example 1, indicating that in comparative example 2, ti 4+ Is not doped into the material and therefore the interlayer spacing is not enlarged. In comparative example 4, the interlayer spacing of the material was increased, indicating Ti 4+ Into the bulk phase of the layered oxide.
Electrochemical performance test
The results of the electrochemical tests of examples 1 to 4 and comparative examples 1 to 5 are shown in Table 1.
TABLE 1
Group of | Whether new phases form after 3 days of exposure to the environment | 0.1C first-turn discharge capacity mAh/g | 1C discharge capacity mAh/g | 2C discharge capacity mAh/g | 5C discharge capacity mAh/g | 1C 100 cycles capacity retention% |
Example 1 | Whether or not | 131.23 | 122.37 | 113.7 | 100.3 | 95.3 |
Example 2 | Whether or not | 133.65 | 126.34 | 118.95 | 104.23 | 94.1 |
Example 3 | Whether or not | 137.32 | 129.54 | 121.22 | 110.1 | 92.3 |
Example 4 | Whether or not | 135.61 | 127.72 | 120.34 | 111.11 | 94.8 |
Comparative example 1 | Is that | 137.79 | 125.25 | 111.74 | 100.25 | 78.6 |
Comparative example 2 | Whether or not | 134.52 | 123.38 | 116.69 | 107.31 | 86.4 |
Comparative example 3 | Whether or not | 124.69 | 115.12 | 105.11 | 98.86 | 91.6 |
Comparative example 4 | Is that | 127.46 | 117.3 | 111.25 | 94.33 | 84.4 |
Comparative example 5 | Is that | 134.1 | 125.1 | 116.5 | 105.3 | 90.5 |
Examples 1-4, which employ the surface coating method provided by the invention, have excellent air stability, and after the material is exposed to an environment with an air humidity of 55% for 3 days, the XRD pattern of the material shows no new phase generation, which indicates that the material prepared by the method has excellent air stability in air. In addition, the material prepared by the method has excellent rate performance and cycle stability.
Comparative example 1 has the same layered oxide material as example 4, but does not employ the surface coating method provided by the present invention. The material of comparative example 1 was exposed to an atmosphere with an air humidity of 55% for 3 days, and the XRD diffraction peak was shifted and a new diffraction peak was generated, indicating that the air stability of the material without surface coating was poor. And the rate performance and the cycle stability of the material prepared in comparative example 1 are greatly different from those of example 4. This shows that Ti is prepared by the surface coating method provided by the invention 4+ Na doped into the surface phase 4 Ti 5 O 12 @NaNi 0.15 Fe 0.25 Mn 0.55 Zr 0.05 O 2 The material can improve the air stability, the multiplying power performance and the circulation stability of the material.
Comparative example 2 with lower TiO content 2 Surface coating was performed to improve both rate performance and capacity retention compared to the material of comparative example 1, but Ti in comparative example 2 4+ Does not dope the material, is simply Na 4 Ti 5 O 12 The coating layer improves the electrochemical performance; comparative example 2 thus compares with the practiceIn example 4, the rate performance and the capacity retention were limited.
Comparative example 3 with higher TiO content 2 The surface coating has improved rate performance and capacity retention compared with comparative example 1, but the discharge capacity of the material is greatly reduced, indicating excessive TiO 2 Surface coating is detrimental to the performance of the material. The reason for this is: on the one hand, too much TiO 2 The formed coating layer is too thick, so that the transmission of ions and electrons is affected; on the other hand, too much TiO 2 Can result in excessive non-electrochemical active ions Ti 4+ Doping of the precursor phase with these Ti 4+ It is difficult to perform the oxidation-reduction reaction. Thus, too much TiO 2 The gram capacity of the material is affected, and the electrochemical performance of the material is reduced.
Comparative example 4 has the same layered oxide material as example 4, except that the sintering time and temperature are increased, the rate performance and capacity retention of the material are improved to some extent relative to comparative example 1, but the first-turn discharge capacity of the material is significantly reduced relative to example 4, and a new phase is formed upon three days of exposure to air. Indicating that after the sintering temperature is increased and the sintering time is prolonged, ti 4+ All enter the bulk phase of the surface layer of the material without forming a coating on the surface of the material. Therefore, due to excessive Ti 4+ Into the bulk phase of the material, affecting the exertion of the reversible capacity of the material.
Comparative example 5 has the same layered oxide material as example 4, except that TiO is used 2 The layered oxide material was coated, and the capacity retention of the material was significantly improved as compared to comparative example 1, but the first-turn discharge capacity and rate performance of the material were slightly reduced as compared to example 4, and a new phase was formed after three days of exposure to air. Description of TiO 2 The coating material did not improve much the air stability and the electrochemical performance was not as pronounced as in example 4.
The test results show that the surface-coated modified O3-phase layered oxide provided by the invention not only improves the air stability of the O3-phase layered oxide material, but also improves the rate capability and the cycle stability of the material.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (9)
1. A method for preparing a surface-coated layered oxide, comprising the steps of:
s1, layered oxide Na y TMO 2 The powder is exposed to the air environment with the humidity more than or equal to 30 percent;
s2, the layered oxide Na treated in the step S1 y TMO 2 Powder and TiO 2 Ball milling and mixing nanometer powder;
s3, sintering the mixture obtained in the step S2 to obtain the surface-coated layered oxide;
in the step S1, y is more than 0.8 and less than or equal to 1, and TM is one or more than one of Ti, V, cr, mn, fe, co, ni, cu, zn, li, B, mg, al, K, ca, zr, nb, sn; the layered oxide Na y TMO 2 The time of exposing the powder to the air environment with the humidity of more than or equal to 30 percent is 1 to 36 hours;
in step S3: the sintering treatment temperature is 600-800 ℃, and the sintering treatment time is 0.5-3.5 h.
2. The method for producing a surface-coated layered oxide according to claim 1, wherein in step S1: the Na is y TMO 2 Is NaNi i Fe j Mn k M m O 2 M is one or more of Li, B, mg, al, K, ca, co, V, cr, cu, zn, zr, nb and Sn; wherein: 0<i≤0.4,0<j≤0.5,0<k≤0.6,0<m is less than or equal to 0.2, and i+j+k+m=1;
and/or the layered oxide Na y TMO 2 The powder is exposed to the air environment with the humidity of more than or equal to 30 percent for 24-36 hours.
3. The method for producing a surface-coated layered oxide according to claim 2, wherein in step S1, the layered oxide NaNi i Fe j Mn k M m O 2 The preparation method of (2) comprises the following steps:
a. precursor Ni i Fe j Mn k M m (OH) 2 Ball-milling and mixing with a sodium source;
b. pre-sintering the mixture obtained in the step a, and then performing solid-phase sintering to obtain the layered oxide NaNi i Fe j Mn k M m O 2 ;
Wherein: in the step a, the sodium source is selected from one or more of sodium carbonate, sodium hydroxide, sodium acetate, sodium oxalate and sodium nitrate;
and/or in the step b, the temperature of the presintering is 200-550 ℃, and the presintering time is 1-8 hours; the temperature of the solid phase sintering is 750-1100 ℃, and the time of the solid phase sintering is 4-20 h.
4. The method for producing a surface-coated layered oxide according to claim 1, wherein in step S2: the TiO 2 The addition amount of the nano powder is the layered oxide Na y TMO 2 0.4-0.8 wt% of the weight of the material;
and/or the rotation speed of the ball milling is 300-600 r/min, and the ball milling time is 2-7 h.
5. A surface-coated layered oxide, characterized in that it is produced by the method of claim 1, comprising a layered oxide Na y TMO 2 Located in the layered oxide Na y TMO 2 Na of surface 4 Ti 5 O 12 A cladding layer, wherein: y is more than 0.8 and less than or equal to 1, and TM is one or more selected from Ti, V, cr, mn, fe, co, ni, cu, zn, li, B, mg, al, K, ca, zr, nb, sn.
6. The surface-coated layered oxide according to claim 5, wherein the Na y TMO 2 Is NaNi i Fe j Mn k M m O 2 M is one or more of Li, B, mg, al, K, ca, co, V, cr, cu, zn, zr, nb and Sn; wherein: 0<i≤0.4,0<j≤0.5,0<k≤0.6,0<m is less than or equal to 0.2, and i+j+k+m=1;
and/or the layered oxide Na y TMO 2 The particle diameter D50 of the particles is 7-12 mu m;
and/or, the Na 4 Ti 5 O 12 The thickness of the coating layer is 5-20 nm.
7. A positive electrode sheet comprising the surface-coated layered oxide produced by the production method according to any one of claims 1 to 4, or comprising the surface-coated layered oxide according to any one of claims 5 to 6.
8. A sodium ion battery comprising the positive electrode sheet of claim 7.
9. A powered device comprising the sodium ion battery of claim 8.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310434242.0A CN116143199B (en) | 2023-04-21 | 2023-04-21 | Surface-coated layered oxide, preparation method thereof, positive plate, sodium ion battery and electric equipment |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310434242.0A CN116143199B (en) | 2023-04-21 | 2023-04-21 | Surface-coated layered oxide, preparation method thereof, positive plate, sodium ion battery and electric equipment |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116143199A CN116143199A (en) | 2023-05-23 |
CN116143199B true CN116143199B (en) | 2023-08-08 |
Family
ID=86351065
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310434242.0A Active CN116143199B (en) | 2023-04-21 | 2023-04-21 | Surface-coated layered oxide, preparation method thereof, positive plate, sodium ion battery and electric equipment |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116143199B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116364898B (en) * | 2023-06-01 | 2023-09-01 | 宜宾锂宝新材料有限公司 | Sodium ion positive electrode material, preparation method thereof and sodium ion battery |
CN116525813B (en) * | 2023-06-27 | 2023-10-27 | 宁波容百新能源科技股份有限公司 | Layered oxide, preparation method thereof and sodium ion battery positive electrode plate |
CN117154047A (en) * | 2023-09-14 | 2023-12-01 | 齐鲁工业大学(山东省科学院) | ZrO (ZrO-like grain) 2 Surface coating, zr 4+ Process for the preparation of doped layered oxides and use thereof |
CN118398802A (en) * | 2024-01-08 | 2024-07-26 | 深圳市贝特瑞新能源技术研究院有限公司 | Preparation method, testing method and battery |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113937286A (en) * | 2020-06-29 | 2022-01-14 | 溧阳中科海钠科技有限责任公司 | Coating modified sodium ion battery positive electrode material, preparation method thereof and battery |
CN115863610A (en) * | 2023-01-05 | 2023-03-28 | 厦门海辰储能科技股份有限公司 | Positive electrode material, positive electrode piece, electrode assembly, energy storage device and electric equipment |
CN115986097A (en) * | 2023-03-16 | 2023-04-18 | 江苏正力新能电池技术有限公司 | Positive electrode material and preparation method thereof, positive plate, sodium ion battery and power utilization equipment |
-
2023
- 2023-04-21 CN CN202310434242.0A patent/CN116143199B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113937286A (en) * | 2020-06-29 | 2022-01-14 | 溧阳中科海钠科技有限责任公司 | Coating modified sodium ion battery positive electrode material, preparation method thereof and battery |
CN115863610A (en) * | 2023-01-05 | 2023-03-28 | 厦门海辰储能科技股份有限公司 | Positive electrode material, positive electrode piece, electrode assembly, energy storage device and electric equipment |
CN115986097A (en) * | 2023-03-16 | 2023-04-18 | 江苏正力新能电池技术有限公司 | Positive electrode material and preparation method thereof, positive plate, sodium ion battery and power utilization equipment |
Non-Patent Citations (1)
Title |
---|
钠离子电池层状过渡金属氧化物正极材料研究;左文华;中国博士学位论文全文数据库 工程科技I辑;第49-53页 * |
Also Published As
Publication number | Publication date |
---|---|
CN116143199A (en) | 2023-05-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN116143199B (en) | Surface-coated layered oxide, preparation method thereof, positive plate, sodium ion battery and electric equipment | |
US10388954B2 (en) | Olivine-type cathode active material precursor for lithium battery, olivine-type cathode active material for lithium battery, method for preparing the same and lithium battery with the same | |
CN109546123B (en) | Vanadium pentoxide-coated core-shell structure gradient nickel-cobalt-manganese positive electrode material and preparation method thereof | |
CN110729458B (en) | Positive active material, preparation method thereof, positive pole piece and lithium ion secondary battery | |
JP5701854B2 (en) | Electrode active material composite and secondary battery including the same | |
JP2023550443A (en) | Positive electrode prelithiation agent and its preparation method and application | |
KR20170075596A (en) | Positive electrode active material for rechargeable lithium battery, method for menufacturing the same, and rechargeable lithium battery including the same | |
JP2023534756A (en) | Lithium ion battery positive electrode lithium replenishment additive and its preparation method and lithium ion battery | |
CN113363483A (en) | Olivine-structure positive electrode material, preparation method and application thereof, and lithium ion battery | |
JP2020064858A (en) | Nickel-based active material precursor for lithium secondary battery, method for producing the same, nickel-based active material formed therefrom for lithium secondary battery, and lithium secondary battery including positive electrode including the same | |
KR101763478B1 (en) | Negative electrode active material for lithium secondary battery, method for preparing the same, and lithium secondary battery comprising the same | |
CN116169300A (en) | Oxygen vacancy metal oxide coated and modified layered oxide, preparation method thereof, positive plate, sodium ion battery and electric equipment | |
KR20100073295A (en) | Preparation method of znsb-c composite and anode materials for secondary batteries containing the same composite | |
EP4253325A1 (en) | Positive electrode material, battery, and electronic device | |
JP2024522031A (en) | Composite positive electrode active material, positive electrode and lithium battery using the same, and manufacturing method thereof | |
CN115304104B (en) | Manganese series lithium supplementing additive, preparation method and application thereof | |
CN117174873A (en) | Preparation method of positive electrode material, positive electrode plate, sodium ion battery and power utilization device | |
CN116216694A (en) | Hard carbon material and preparation method thereof | |
WO2022270539A1 (en) | Composite carbon particles and use thereof | |
CN115133018A (en) | Preparation method and application of positive electrode lithium supplement additive | |
CN117457887B (en) | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery | |
CN115954482B (en) | Layered oxide composite material, preparation method thereof, positive plate and sodium ion battery | |
CN117199365A (en) | Positive electrode lithium supplementing material, preparation method thereof, positive electrode plate and secondary battery | |
CN116344813A (en) | Composite lithium supplementing material and preparation method and application thereof | |
CN117855400A (en) | Low-gas-yield long-cycle monocrystal ternary cathode material and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CP03 | Change of name, title or address | ||
CP03 | Change of name, title or address |
Address after: No. 68, Xin'anjiang Road, Southeast Street, Changshu City, Suzhou City, Jiangsu Province, 215000 Patentee after: Jiangsu Zhengli New Energy Battery Technology Co.,Ltd. Country or region after: China Address before: No. 68, Xin'anjiang Road, Southeast Street, Changshu City, Suzhou City, Jiangsu Province, 215000 Patentee before: Jiangsu Zenergy Battery Technologies Co.,ltd Country or region before: China |