CN116805684A - Al, zn, ti and Fe co-doped biphase layered oxide sodium ion battery high-entropy positive electrode material - Google Patents
Al, zn, ti and Fe co-doped biphase layered oxide sodium ion battery high-entropy positive electrode material Download PDFInfo
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- CN116805684A CN116805684A CN202310792507.4A CN202310792507A CN116805684A CN 116805684 A CN116805684 A CN 116805684A CN 202310792507 A CN202310792507 A CN 202310792507A CN 116805684 A CN116805684 A CN 116805684A
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- positive electrode
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- ion battery
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 63
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 57
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 27
- 239000011734 sodium Substances 0.000 claims abstract description 38
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 55
- 150000001875 compounds Chemical class 0.000 claims description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 36
- 239000011572 manganese Substances 0.000 claims description 30
- 239000010936 titanium Substances 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 16
- 238000002360 preparation method Methods 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
- 239000000463 material Substances 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052759 nickel 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
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 239000002482 conductive additive Substances 0.000 claims description 5
- 239000010406 cathode material Substances 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229940009827 aluminum acetate Drugs 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 3
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 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 3
- 239000005486 organic electrolyte Substances 0.000 claims description 3
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 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
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- FOZHTJJTSSSURD-UHFFFAOYSA-J titanium(4+);dicarbonate Chemical compound [Ti+4].[O-]C([O-])=O.[O-]C([O-])=O FOZHTJJTSSSURD-UHFFFAOYSA-J 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 3
- 230000002051 biphasic effect Effects 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 17
- 230000014759 maintenance of location Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 230000001351 cycling effect Effects 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 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
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000009467 reduction 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
- -1 sodium hexafluorophosphate Chemical compound 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a high-entropy positive electrode material of Al, zn, ti and Fe co-doped double-phase layered oxide sodium ion battery, which has a P2/O3 double-phase composite structure, and has a chemical formula of Na 0.796 Ni 0.33‑ x Zn x Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 (0<x.ltoreq.0.1). The anode material provided by the invention has higher capacity, average discharge voltage, energy density and good cycle stability in electrochemical performance, and has simple synthetic route, lower cost and potentialA positive electrode material of a sodium ion battery.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to an Al, zn, ti and Fe co-doped double-phase layered oxide sodium ion battery high-entropy positive electrode material.
Background
Lithium ion batteries have long been considered as the most potential renewable energy source development electrical energy storage systems, which can greatly promote the goal of global carbon emission reduction and energy crisis resolution. However, due to the scarcity, non-uniformity and high cost of lithium resources, the application of lithium ion batteries is severely limited, so that it is not easy to find a battery material with low cost, abundant resources and easy development. The sodium element is used as the fourth element of crust abundance, the cost advantage is far greater than that of the lithium element, and the sodium element has high commercial value. Among the numerous sodium ion battery cathode materials, layered oxides are widely studied for their high electrochemical properties, simple synthesis methods, and low cost. However, the present layered oxides have significant drawbacks such as insufficient capacity retention compared to other crystal structures. The high-entropy layered oxide is used as a novel design concept, and the circulation performance of the anode material can be effectively improved through the two-dimensional ion migration channel between layers.
Disclosure of Invention
Based on the defects existing in the prior art, the technical problem to be solved by the invention is to provide the Al, zn, ti and Fe co-doped double-phase layered oxide sodium ion battery high-entropy cathode material. The positive electrode material provided by the invention has higher capacity, average discharge voltage, energy density and good cycling stability in electrochemical performance, and has a smooth synthetic path and lower cost, and is a potential positive electrode material of a sodium ion battery.
The invention adopts the following technical scheme for realizing the purpose:
the invention firstly provides an Al, zn, ti and Fe co-doped diphase layered oxide sodium ion battery high entropy positive electrode material, the chemical formula of which is Na 0.796 Ni 0.33-x Zn x Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 (0<x.ltoreq.0.1) having a P2/O3 two-phase composite structure.
The invention also provides a preparation method of the Al, zn, ti and Fe co-doped double-phase layered oxide sodium ion battery high-entropy positive electrode material, which is prepared by adopting a solid phase method and comprises the following specific steps:
step 1, mixing a sodium source compound, a nickel source compound, an aluminum source compound, a zinc source compound, an iron source compound, a titanium source compound and a manganese source compound according to a molar ratio, and placing the mixture into a ball milling tank for ball milling to obtain mixture powder;
step 2, calcining the mixture powder in one step to obtain the Al, zn, ti and Fe co-doped biphase layered oxide sodium ion battery high entropy positive electrode material Na 0.796 Ni 0.33-x Zn x Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 。
Preferably: the sodium source compound is selected from one or more of sodium carbonate, sodium hydroxide, sodium oxide, sodium acetate, sodium nitrate, sodium oxalate and sodium citrate; the nickel source compound is selected from one or more of nickel oxide, nickel acetate, nickel nitrate, nickel oxalate and nickel sulfate; the iron source compound is one or more of ferric nitrate, ferric chloride, ferric acetate, ferric sulfate, ferric carbonate and ferric oxide; the zinc source compound is selected from one or more of zinc oxide, zinc acetate, zinc nitrate, zinc oxalate and zinc sulfate; the aluminum source compound is selected from one or more of aluminum oxide, aluminum acetate, aluminum nitrate and aluminum sulfate; the manganese source compound is selected from one or more of manganese dioxide, manganese sesquioxide, manganese acetate, manganese nitrate, manganese oxalate and manganese sulfate; the titanium source compound is selected from one or more of titanium dioxide, titanium acetate, titanium nitrate, titanium oxalate and titanium carbonate.
Preferably: in the step 2, the one-step calcination of the mixture powder is carried out under the air atmosphere, the heating rate is 1-10 ℃/min, the temperature is raised to 800-1000 ℃, the temperature is kept for 10-24 hours, and the final sample is obtained after the temperature is reduced to the room temperature.
The invention also provides a sodium ion battery positive plate which is prepared from a positive electrode material, a conductive additive, a binder and a solvent, wherein the positive electrode material is selected from the Al, zn, ti and Fe co-doped double-phase layered oxide sodium ion battery high-entropy positive electrode material.
The invention also provides a sodium ion battery, which consists of a positive plate, a diaphragm, organic electrolyte and negative metal sodium, wherein the positive plate is made of the Al, zn, ti and Fe co-doped biphase layered oxide sodium ion battery high-entropy positive plate material.
The sodium ion battery provided by the invention can be used in electric automobiles, solar power generation, wind power generation, smart grid peak shaving, distributed power stations or large-scale energy storage devices of communication bases.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a high-entropy positive electrode material of Al, zn, ti and Fe co-doped double-phase layered oxide sodium ion battery, the chemical formula is Na 0.796 Ni 0.33-x Zn x Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 Wherein 0 is<x is less than or equal to 0.1. The invention successfully constructs the high-entropy positive electrode material of the P2/O3 two-phase composite structure, and the provided positive electrode material has higher capacity, average discharge voltage, energy density and good cycling stability in electrochemical performance, and is a positive electrode material of a sodium ion battery with potential. In practical application, the invention has simple synthetic route and lower cost.
Drawings
FIG. 1 is an XRD spectrum of the target product obtained in example 1.
Fig. 2 is an SEM image of the target product obtained in example 1.
FIG. 3 is a charge-discharge curve of the target product obtained in example 1 at a 0.1C rate.
FIG. 4 is a graph showing the cycle stability of the target product obtained in example 1 at a 1C rate.
FIG. 5 is an energy density stability curve of the target product obtained in example 1 at a 1C magnification.
FIG. 6 is a graph showing the average voltage cycling stability of the target product obtained in example 1 at a 1C rate.
FIG. 7 is a graph showing the cycling stability of the target product obtained in example 1 at 5C magnification.
FIG. 8 is an XRD spectrum of the target product obtained in example 2.
Fig. 9 is a charge-discharge curve of the objective product obtained in example 2 at 0.1C magnification.
FIG. 10 is a graph showing the cycling stability of the target product obtained in example 2 at a 1C rate.
FIG. 11 is an XRD spectrum of the target product obtained in example 3.
FIG. 12 is a charge-discharge curve of the target product obtained in example 3 at a 0.1C rate.
FIG. 13 is a graph showing the cycle stability of the target product obtained in example 3 at a 1C rate.
FIG. 14 is an XRD spectrum of the target product obtained in example 4.
FIG. 15 is a charge-discharge curve of the target product obtained in example 4 at a 0.1C rate.
FIG. 16 is a graph showing the cycle stability of the target product obtained in example 4 at a 1C rate.
FIG. 17 is an XRD spectrum of the target product obtained in example 5.
FIG. 18 is a charge-discharge curve of the target product obtained in example 5 at a 0.1C rate.
FIG. 19 is a graph showing the cycle stability of the target product obtained in example 5 at a 1C rate.
FIG. 20 is an XRD spectrum of the target product obtained in example 6.
FIG. 21 is a charge-discharge curve of the target product obtained in example 6 at a 0.1C rate.
FIG. 22 is a graph showing the cycling stability of the target product obtained in example 6 at a 1C rate.
FIG. 23 is an XRD spectrum of the target product obtained in comparative example 1.
FIG. 24 is a graph showing the cycle stability of the target product obtained in comparative example 1 at a 1C rate.
FIG. 25 is an XRD spectrum of the target product obtained in comparative example 2.
FIG. 26 is a graph showing the cycling stability of the target product of comparative example 2 at a 1C rate.
Detailed Description
The invention provides a high-entropy positive electrode material of Al, zn, ti and Fe double-phase co-doped layered oxide sodium ion battery, the chemical formula is Na 0.796 Ni 0.33-x Zn x Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 Wherein 0 is<x is less than or equal to 0.1. The positive electrode material of the sodium ion battery provided by the invention is in a block shape, and the particle size is 2-5 mu m.
The invention also provides a preparation method of the Al, zn, ti and Fe co-doped double-phase layered oxide sodium ion battery high-entropy positive electrode material, which is prepared by adopting a solid phase method. The method comprises the following specific steps:
step 1, mixing a sodium source compound, a nickel source compound, an aluminum source compound, a zinc source compound, an iron source compound, a titanium source compound and a manganese source compound according to a molar ratio, and placing the mixture into a ball milling tank for ball milling to obtain mixture powder;
step 2, calcining the mixture powder in one step under the air atmosphere, heating to 800-1000 ℃ at a heating rate of 1-10 ℃/min, preserving heat for 10-24 hours, and cooling to room temperature to obtain the Al, zn, ti and Fe co-doped diphase layered oxide sodium ion battery high entropy positive electrode material Na 0.796 Ni 0.33-x Zn x Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 。
In the preparation method, the following steps are adopted: the sodium source compound is selected from one or more of sodium carbonate, sodium hydroxide, sodium oxide, sodium acetate, sodium nitrate, sodium oxalate and sodium citrate; the nickel source compound is selected from one or more of nickel oxide, nickel acetate, nickel nitrate, nickel oxalate and nickel sulfate; the iron source compound is one or more of ferric nitrate, ferric chloride, ferric acetate, ferric sulfate, ferric carbonate and ferric oxide; the zinc source compound is selected from one or more of zinc oxide, zinc acetate, zinc nitrate, zinc oxalate and zinc sulfate; the aluminum source compound is selected from one or more of aluminum oxide, aluminum acetate, aluminum nitrate and aluminum sulfate; the manganese source compound is selected from one or more of manganese dioxide, manganese sesquioxide, manganese acetate, manganese nitrate, manganese oxalate and manganese sulfate. The titanium source compound is selected from one or more of titanium dioxide, titanium acetate, titanium nitrate, titanium oxalate and titanium carbonate.
The invention also prepares a positive plate of the sodium ion battery, which is prepared from a positive electrode material, a conductive additive, a binder and a solvent, wherein: the positive electrode material is selected from the Al, zn, ti and Fe co-doped double-phase layered oxide sodium ion battery high-entropy positive electrode material; the conductive additive is selected from one or more of Super-P, carbon black and ketjen black; the binder is selected from one or more of polyvinylidene fluoride, polyacrylic acid, sodium carboxymethyl cellulose and sodium alginate; the solvent is selected from one of N-methyl pyrrolidone or deionized water.
The invention also provides a preparation method of the positive plate of the sodium ion battery, which is prepared by mixing a positive electrode material, a conductive additive, a binder and a solvent according to a certain proportion, and then performing a smear and a drying process.
The specific method of mixing, smearing and drying is not particularly limited in the present invention, and may be any method known to those skilled in the art.
The invention also provides a sodium ion battery, which consists of a positive plate, a diaphragm, electrolyte and negative metal sodium, wherein: the positive plate adopts the positive plate of the sodium ion battery. The electrolyte is carbonate electrolyte with the concentration of 0.5-2M, preferably 1M; the solvent in the organic electrolyte is at least one selected from diethyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propylene carbonate and fluorinated ethylene carbonate, preferably a mixed solvent of propylene carbonate and fluorinated ethylene carbonate; the solute in the electrolyte is at least one selected from sodium perchlorate, sodium hexafluorophosphate and sodium bistrifluoromethylsulfonylimide, and is preferably sodium perchlorate. The separator is preferably glass fiber.
The invention also provides application of the sodium ion battery in large-scale energy storage devices such as electric automobiles, solar power generation, wind power generation, smart grid peak shaving, distributed power stations or communication bases and the like.
The invention has the following advantages:
(1) Synthesized Al, zn, ti and Fe co-doped diphase layered oxide sodium ion battery high entropy positive electrode material with a chemical formula of Na 0.796 Ni 0.33-x Zn x Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 Wherein 0 is<x is less than or equal to 0.1, and enriches the material system of the sodium ion battery.
(2) Na of the invention 0.796 Ni 0.33-x Zn x Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 (0<x is less than or equal to 0.1), the positive electrode material has excellent cycle stability and low cost, and is an ideal positive electrode material for sodium ion batteries.
(3) Preferred Na of the invention 0.796 Ni 0.3 Zn 0.03 Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 The positive electrode material has best comprehensive performance, and the positive electrode material has the following characteristics of 1C (1 C=173 mAg -1 ) The capacity retention rate of the lithium ion battery is 84.7% after 200 circles of circulation under the current density, and 81.6% after 1000 circles of circulation under the high multiplying power of 5C, so that the lithium ion battery is suitable for large-scale energy storage equipment and is an ideal positive electrode material for preparing an energy storage device of a sodium ion battery.
(4) The cathode material synthesized by the method has the advantages of low cost, simple synthesis method, excellent cycle stability and the like, and has certain commercialized application prospect.
In order to further understand the present invention, the following examples are provided to illustrate the Al, zn, ti and Fe co-doped layered oxide sodium ion battery positive electrode material, the preparation method and the application thereof, and the scope of the present invention is not limited by the following examples.
Example 1
Step 1, preparing Na by a solid phase method 0.796 Ni 0.3 Zn 0.03 Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 Positive electrode material
Mixing sodium carbonate, nickel oxide, zinc oxide, manganese dioxide, aluminum oxide, ferric oxide and titanium dioxide in stoichiometric ratio, placing the mixture into a ball milling tank for ball milling to obtain mixture powder, placing the mixture powder into a muffle furnace, heating the mixture powder to 950 ℃ in an air atmosphere at a heating rate of 2 ℃/min, and calcining the mixture powder for 15h to obtain a target product Na 0.796 Ni 0.3 Zn 0.03 Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 。
Step 2, preparing Na 0.796 Ni 0.3 Zn 0.03 Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 Positive plate
Na prepared above 0.796 Ni 0.3 Zn 0.03 Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 Mixing the positive electrode material with Super P and polyvinylidene fluoride as a binder according to the mass ratio of 7:2:1, adding a certain amount of N-methylpyrrolidone as a solvent, and performing the steps of pulping by a mixing machine, smearing, drying and the like to obtain the material containing Na 0.796 Ni 0.3 Zn 0.03 Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 Positive plate of sodium ion battery of active material.
Step 3, assembling the target product Na 0.796 Ni 0.3 Zn 0.03 Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 A sodium ion battery that is the positive electrode.
Assembling the prepared target product positive electrode plate and the metal sodium negative electrode into a sodium ion battery, wherein GF/F is a battery diaphragm, and the electrolyte is carbonate electrolyte (1M NaClO) 4 Comprises 5vol% of FEC).
Fig. 1 is an XRD spectrum of the target product obtained in example 1, and it can be seen that the synthesized material has good crystallinity and is a two-phase mixed structure of P2 and O3.
FIG. 2 is an SEM image of the target product obtained in example 1, and it can be seen from the figure that the material has a block structure, the particle size of the particles is 2-5 μm, and the particles are uniformly distributed.
FIG. 3 shows the target product obtained in example 1 at 0.1C (1C=173 mAg -1 ) As can be seen from the charge-discharge curve under the current density, the material has higher specific capacity of 159.4mAh g when applied to sodium ion batteries -1 。
FIG. 4 is a graph showing the cycle stability of the target product obtained in example 1 at a 1C rate. As can be seen from the graph, the initial specific capacity of the target product obtained in the embodiment is 125.7mAh g -1 The capacity retention rate after 200 circles of circulation is 84.7%, and the circulation stability is good.
FIG. 5 is a graph showing the energy density stability of the target product obtained in example 1 at a magnification of 1C, wherein the initial specific energy of the target product obtained in this example is 416Whkg -1 The capacity retention rate after 200 circles of circulation is 80.9%, and the circulation stability is good.
Fig. 6 is a graph showing the cycle stability of the average voltage of the target product obtained in example 1 at a 1C rate, and it can be seen that the initial average discharge voltage of the target product obtained in this example is 3.44V, and the capacity retention rate after 200 cycles is 93.0%, thus having good cycle stability.
FIG. 7 is a graph showing the cycling stability of the target product obtained in example 1 at 5C magnification. As can be seen from the graph, the initial specific capacity of the target product obtained in the embodiment is 88.1mAh g -1 The capacity retention rate after 1000 circles is 81.6%, and the cycle stability is good.
Example 2
The preparation process was the same as in example 1, except that the raw material ratios were set according to Na 0.796 Ni 0.31 Zn 0.02 Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 Is added in stoichiometric proportions.
Fig. 8 shows XRD patterns of the positive electrode material obtained in example 2, and it can be seen from the figure that the synthesized layered oxide positive electrode material has better crystallinity and is a two-phase mixed structure of P2 and O3.
Fig. 9 shows a sodium ion battery assembled with the positive electrode material obtained in example 2 at 0.1C (1c=173 mAg -1 ) As can be seen from the graph, the material has a charge-discharge curve under current density of 153.5mAhg in a sodium ion battery -1 Is provided.
FIG. 10 is a graph showing the cycling stability of the target product obtained in example 2 at a 1C rate. As can be seen from the graph, the initial specific capacity of the target product obtained in the embodiment is 135.5mAh g -1 The capacity retention rate after 200 circles of circulation is 73.9%, and the circulation stability is good.
Example 3
The preparation process was the same as in example 1, except that the raw material ratios were set according to Na 0.796 Ni 0.29 Zn 0.04 Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 Is added in stoichiometric proportions.
Fig. 11 shows XRD patterns of the positive electrode material obtained in example 3, and it can be seen from the figures that the synthesized layered oxide positive electrode material has better crystallinity and is a two-phase mixed structure of P2 and O3.
Fig. 12 shows the positive electrode material of example 3 assembled sodium ion battery at 0.1C (1c=173 mAg -1 ) The charge-discharge curve under current density shows that the material has 142.4mAhg in sodium ion battery -1 Is provided.
FIG. 13 is a graph showing the cycle stability of the target product obtained in example 3 at a 1C rate. As can be seen from the graph, the initial specific capacity of the target product obtained in the embodiment is 125.0mAh g -1 The capacity retention rate after 200 circles of circulation is 76.6%, and the circulation stability is good.
Example 4
The preparation process was the same as in example 1, except that the raw material ratios were set according to Na 0.796 Ni 0.28 Zn 0.05 Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 Is added in stoichiometric proportions.
Fig. 14 shows XRD patterns of the positive electrode material obtained in example 4, and it can be seen from the figure that the synthesized layered oxide positive electrode material has better crystallinity and is a two-phase mixed structure of P2 and O3.
Fig. 15 shows the positive electrode material of example 4 assembled sodium ion battery at 0.1C (1c=173 mAg -1 ) As can be seen from the graph, the material has a charge-discharge curve under current density of 145.5mAhg in a sodium ion battery -1 Is provided.
FIG. 16 is a graph showing the cycle stability of the target product obtained in example 4 at a 1C rate. As can be seen from the graph, the initial specific capacity of the target product obtained in the embodiment is 128.7mAh g -1 The capacity retention rate after 200 circles of circulation is 80.4%, and the circulation stability is good.
Example 5
The preparation process was the same as in example 1, except that the raw material ratios were set according to Na 0.796 Ni 0.26 Zn 0.07 Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 Is added in stoichiometric proportions.
Fig. 17 shows XRD patterns of the positive electrode material obtained in example 5, and it can be seen from the patterns that the synthesized layered oxide positive electrode material has good crystallinity.
Fig. 18 shows the positive electrode material of example 5 assembled sodium ion battery at 0.1C (1c=173 mAg -1 ) As can be seen from the charge-discharge curve under the current density, the material has 156mAhg in the sodium ion battery -1 Is provided.
FIG. 19 is a graph showing the cycle stability of the target product obtained in example 5 at a 1C rate. As can be seen from the graph, the initial specific capacity of the target product obtained in the embodiment is 105.3mAh g -1 The capacity retention rate after 200 circles of circulation is 74.8%, and the circulation stability is good.
Example 6
The preparation process was the same as in example 1, except that the raw material ratios were set according to Na 0.796 Ni 0.23 Zn 0.1 Mn 0.47 Al 0.03 Fe 0. 1 Ti 0.07 O 2 Is added in stoichiometric proportions.
Fig. 20 shows XRD patterns of the positive electrode material obtained in example 6, and it can be seen from the figure that the synthesized layered oxide positive electrode material has better crystallinity and is a two-phase mixed structure of P2 and O3.
Fig. 21 shows the positive electrode material of example 6 assembled sodium ion battery at 0.1C (1c=173 mAg -1 ) As can be seen from the graph, the material has a charge-discharge curve under current density of 142.2mAhg in a sodium ion battery -1 Is provided.
FIG. 22 is a graph showing the cycling stability of the target product obtained in example 6 at a 1C rate. As can be seen from the graph, the initial specific capacity of the target product obtained in the embodiment is 101.5mAh g -1 The capacity retention rate after 200 circles of circulation is 76.6%, and the circulation stability is good.
Comparative example 1
The preparation was the same as in example 1, except that the raw materials were freed of alumina and zinc oxide in the ratio Na 0.766 Ni 0.33 Mn 0.5 Fe 0.1 Ti 0.07 O 2 Is added in stoichiometric proportions.
Fig. 23 shows XRD patterns of the positive electrode material obtained in comparative example 1, and it can be seen from the figures that the synthesized layered oxide positive electrode material has good crystallinity and is a two-phase mixed structure of P2 and O3.
FIG. 24 is a graph showing the cycle stability of the target product obtained in comparative example 1 at a 1C rate. As can be seen from the graph, the initial specific capacity of the target product obtained in this comparative example is 131.3mAh g -1 The capacity retention rate after 200 cycles was 58.4%, and the cycle stability was not satisfactory.
Comparative example 2
The preparation process was the same as in example 1, except that the raw material was freed of zinc oxide in the ratio Na 0.796 Ni 0.33 Mn 0.4 7 Al 0.03 Fe 0.1 Ti 0.07 O 2 Is added in stoichiometric proportions.
Fig. 25 shows XRD patterns of the positive electrode material obtained in comparative example 2, and it can be seen from the figures that the synthesized layered oxide positive electrode material has better crystallinity and is a two-phase mixed structure of P2 and O3.
FIG. 26 is a graph showing the cycling stability of the target product of comparative example 2 at a 1C rate. As can be seen from the graph, the initial specific capacity of the target product obtained in this comparative example is 122mAh g -1 The capacity retention rate after 200 cycles was 73.4%, and the cycle stability was not satisfactory.
The performance comparison data of the target products obtained in the above examples and comparative examples are shown in Table 1.
TABLE 1
Comparing the above data, it can be known that the layered oxide sodium ion battery high entropy positive electrode material doped with Zn, ti, fe and Al elements has a great improvement on the cycle stability, wherein the preferred Na of the invention 0.796 Ni 0.3 Zn 0.03 Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 Positive electrode materialThe best overall performance is that at 1C (1C=173 mAg -1 ) The capacity retention rate of the lithium ion battery is 84.7% after 200 circles of circulation under the current density, and 81.6% after 1000 circles of circulation under the high multiplying power of 5C, so that the lithium ion battery is an ideal positive electrode material for preparing an energy storage device of a sodium ion battery.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The Al, zn, ti and Fe co-doped double-phase layered oxide sodium ion battery high-entropy positive electrode material is characterized in that: the chemical formula of the positive electrode material is Na 0.796 Ni 0.33-x Zn x Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 ，0<x≤0.1。
2. The Al, zn, ti and Fe co-doped biphasic layered oxide sodium ion battery high entropy cathode material according to claim 1, wherein: the positive electrode material is a high-entropy material with a P2/O3 two-phase composite structure.
3. A method for preparing the positive electrode material according to claim 1 or 2, comprising the specific steps of:
step 1, mixing a sodium source compound, a nickel source compound, an aluminum source compound, a zinc source compound, an iron source compound, a titanium source compound and a manganese source compound according to a molar ratio, and placing the mixture into a ball milling tank for ball milling to obtain mixture powder;
step 2, calcining the mixture powder in one step to obtain the Al, zn, ti and Fe co-doped biphase layered oxide sodium ion battery high entropy positive electrode material Na 0.796 Ni 0.33-x Zn x Mn 0.47 Al 0.03 Fe 0.1 Ti 0.07 O 2 。
4. A method of preparation according to claim 3, characterized in that: the sodium source compound is selected from one or more of sodium carbonate, sodium hydroxide, sodium oxide, sodium acetate, sodium nitrate, sodium oxalate and sodium citrate; the nickel source compound is selected from one or more of nickel oxide, nickel acetate, nickel nitrate, nickel oxalate and nickel sulfate; the iron source compound is one or more of ferric nitrate, ferric chloride, ferric acetate, ferric sulfate, ferric carbonate and ferric oxide; the zinc source compound is selected from one or more of zinc oxide, zinc acetate, zinc nitrate, zinc oxalate and zinc sulfate; the aluminum source compound is selected from one or more of aluminum oxide, aluminum acetate, aluminum nitrate and aluminum sulfate; the manganese source compound is selected from one or more of manganese dioxide, manganese sesquioxide, manganese acetate, manganese nitrate, manganese oxalate and manganese sulfate; the titanium source compound is selected from one or more of titanium dioxide, titanium acetate, titanium nitrate, titanium oxalate and titanium carbonate.
5. A method of preparation according to claim 3, characterized in that: in the step 2, the one-step calcination of the mixture powder is carried out under the air atmosphere, the heating rate is 1-10 ℃/min, the temperature is raised to 800-1000 ℃, the temperature is kept for 10-24 hours, and the final sample is obtained after the temperature is reduced to the room temperature.
6. The positive plate of the sodium ion battery is prepared from a positive electrode material, a conductive additive, a binder and a solvent, and is characterized in that: the positive electrode material is selected from Al, zn, ti and Fe co-doped double-phase layered oxide sodium ion battery high-entropy positive electrode materials as claimed in claim 1 or 2.
7. A sodium ion battery is composed of a positive plate, a diaphragm, an organic electrolyte and negative metallic sodium, and is characterized in that: the positive plate is the positive plate of the sodium ion battery of claim 6.
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| CN117447197B (en) * | 2023-12-25 | 2024-02-27 | 上海南极星高科技股份有限公司 | Preparation method of high-entropy pseudobrookite titanate ceramic |
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