CN116826007A - Layered positive electrode material of sodium ion battery and preparation method and application thereof - Google Patents
Layered positive electrode material of sodium ion battery and preparation method and application thereof Download PDFInfo
- Publication number
- CN116826007A CN116826007A CN202310907149.7A CN202310907149A CN116826007A CN 116826007 A CN116826007 A CN 116826007A CN 202310907149 A CN202310907149 A CN 202310907149A CN 116826007 A CN116826007 A CN 116826007A
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- CN
- China
- Prior art keywords
- ion battery
- positive electrode
- sodium
- electrode material
- oxide
- Prior art date
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- Pending
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 119
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 96
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 49
- 239000011734 sodium Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000004576 sand Substances 0.000 claims abstract description 19
- 230000014759 maintenance of location Effects 0.000 claims abstract description 12
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 3
- 239000007790 solid phase Substances 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 51
- 239000011572 manganese Substances 0.000 claims description 49
- 239000010949 copper Substances 0.000 claims description 37
- 239000010936 titanium Substances 0.000 claims description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 21
- 229910052748 manganese Inorganic materials 0.000 claims description 21
- 229910021645 metal ion Inorganic materials 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 239000010405 anode material Substances 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
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 9
- 230000002572 peristaltic effect Effects 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 8
- 239000010406 cathode material Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 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
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 5
- 229910052810 boron oxide Inorganic materials 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 239000000203 mixture Substances 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
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 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
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099594 manganese dioxide 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
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 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
- 229910000016 manganese(II) carbonate Inorganic materials 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
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 3
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 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
- 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
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 239000010419 fine particle Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 21
- 239000010410 layer Substances 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002482 conductive additive Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 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 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- -1 sodium hexafluorophosphate Chemical compound 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- BQCFCWXSRCETDO-UHFFFAOYSA-N [Fe].[Mn].[Cu] Chemical compound [Fe].[Mn].[Cu] BQCFCWXSRCETDO-UHFFFAOYSA-N 0.000 description 1
- QXZNUMVOKMLCEX-UHFFFAOYSA-N [Na].FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F Chemical compound [Na].FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F QXZNUMVOKMLCEX-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 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
- 238000001694 spray drying Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
Abstract
The application relates to a layered positive electrode material of a sodium ion battery, a preparation method and application thereof, wherein the chemical formula of the layered positive electrode material of the sodium ion battery is Na n Cu y Fe z Mn 1‑x‑y‑z A x O 2 Wherein n is more than 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 0.2, y is more than 0 and less than or equal to 0.3, z is more than 0 and less than or equal to 0.5, and A is one or more of Ni, co, cr, ru, sn, sc, zr, li, ti, mg, zn, ca, al and B; the layered positive electrode material of the sodium ion battery is a material with the working voltage of 3.25V, the specific capacity of 138.53mAh/g under the condition of 0.2C, and the capacity retention rate of the layered positive electrode material of the sodium ion battery is more than 98.5 percent after 200 circles of circulation under 1C, and the specific resistance of the layered positive electrode material of the sodium ion battery is reduced to 1.9 multiplied by 10 ‑3 Omega cm. The material not only has high specific capacity, but also has excellent cycle stability and rate capability. The method adopts a sand milling-solid phase sintering two-step method to prepare the layered positive electrode material of the sodium ion battery, has the advantages of simple preparation method, low raw material price, green and pollution-free performance, and is suitable for commercial production.
Description
Technical Field
The application belongs to the technical field of batteries, and particularly relates to a layered positive electrode material of a sodium ion battery, and a preparation method and application thereof.
Background
Various renewable energy sources such as wind energy, solar energy and tidal energy and clean energy sources rapidly appear due to exhaustion of fossil fuel resources and environmental pollution. In order to integrate these renewable energy sources into the grid, large-scale energy storage systems are of vital importance. Among various energy storage technologies, secondary batteries are widely used in large-scale electric storage due to their advantages of flexibility, high energy conversion efficiency, simple maintenance, and the like. Currently, lithium Ion Batteries (LIBs) occupy the vast majority of the electronic market. However, with the progressive shortage of lithium resources, lithium prices have been swirled. Therefore, more suitable energy storage technologies must be sought to meet future developments. As a novel secondary energy storage device, a Sodium Ion Battery (SIB) has the advantages of low cost and large sodium abundance, and meanwhile, the sodium ion battery and a lithium ion battery have the same working principle and are expected to replace the lithium ion battery in the future.
Currently, positive electrode materials for sodium ion batteries include layered oxides, tunnel oxides, polyanion compounds, organic positive electrode materials, and the like. The layered oxide has a good periodic layered structure, a high specific capacity, and a large amount of oxidation reaction of lattice oxygen, and thus has been studied more recently. However, the material undergoes multiple phase changes in the process of releasing and embedding sodium ions, and the larger volume change and the serious attenuation of the capacity cause the poor cycling stability.
Disclosure of Invention
The application aims to overcome the defects of the prior art, and provides a sodium ion battery layered anode material with high specific capacity and excellent cycle stability and rate capability, and a preparation method and application thereof.
The application relates to a layered positive electrode material of a sodium ion battery, which has a chemical formula of Na n Cu y Fe z Mn 1-x-y-z A x O 2 Wherein n is more than 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 0.2, y is more than 0 and less than or equal to 0.3, z is more than 0 and less than or equal to 0.5, and A is one or more of Ni, co, cr, ru, sn, sc, zr, li, ti, mg, zn, ca, al and B; the layered positive electrode material of the sodium ion battery is a material with the working voltage of 3-3.3V, the specific capacity of 108.81-138.53 mAh/g under the condition of 0.2C, and the capacity retention rate of 65.13-98.86% after 200 circles of circulation under 1C, and the layered positive electrode material of the sodium ion battery is a material with the resistivity range of 1.9 multiplied by 10 -3 ～6.6×10 -3 Omega cm material. According to the method, the metal ion A is introduced into the transition metal layer or the sodium ion layer of the copper-iron-manganese-based layered oxide material by controlling the reaction conditions, and the content of the doped metal ion A and Mn is regulated and controlled to finally obtain the metal oxide with a chemical formula of Na n Cu y Fe z Mn 1-x-y-z A x O 2 Sodium ion battery layered positive electrode material. The proper doping of metal ions can reduce the distance between transition metal layers or sodium ion layers of the layered oxide, limit the embedding of moisture in air and greatly improve the storage stability of the material. When one or more metal ions of Ni, co, cr, ru, sn, sc, zr, li, ti, mg, zn, ca, al and B are introduced, irreversible phase change of the material can be effectively inhibited in the charge and discharge process, so that the material has high specific capacity and excellent cycle stability and rate capability. Meanwhile, the particle size of the layered positive electrode material of the sodium ion battery is small and uniform.
Further, metal ions in the layered positive electrode material of the sodium ion battery are doped in layered oxygenA transition metal layer or a sodium ion layer of the oxide material; the n is 0.82, the A comprises Ca and Ti, the layered positive electrode material of the sodium ion battery is a material with the working voltage of 3.25V, the specific capacity of more than 138mAh/g under the condition of 0.2C, and the capacity retention rate of more than 98 percent after 200 circles of circulation under 1C, and the layered positive electrode material of the sodium ion battery is a material with the resistivity reduced to 1.9 multiplied by 10 -3 Omega cm material. Can maintain good circulation performance and simultaneously has high specific capacity.
The preparation method of the layered positive electrode material of the sodium ion battery comprises the steps of firstly, uniformly mixing a proper amount of sodium source, copper source, iron source, manganese source and metal element compound in a solvent to obtain a mixed material, and grinding the particle size of the mixed material to 0.2-5 mu m; and drying, and calcining at 600-1000 ℃ for 6-24 hours to obtain the layered anode material of the sodium ion battery. The sodium ion battery layered anode material is prepared by adopting a sand milling-solid phase sintering two-step method, so that the preparation method is simple, the raw materials are low in price, green and pollution-free, and the sodium ion battery layered anode material is suitable for commercial production. The calcination of the material in this temperature range can give a relatively moderate particle size, which has excellent electrochemical properties when used as a positive electrode material. Too low a calcination temperature will have an effect on the phase formation and too high a temperature will consume excessive energy.
Further, according to the preparation method of the layered positive electrode material of the sodium ion battery, the particle size of the ground mixture is 1.5 mu m.
Further, according to the preparation method of the sodium ion battery layered cathode material, the calcining temperature is 700 ℃, and the calcining time is 20 hours.
Further, the sodium source is one or more of sodium nitrate, sodium chloride, sodium acetate, sodium citrate, sodium carbonate and sodium oxide; the copper source is one or more of copper nitrate, copper chloride, copper acetate, copper sulfate, copper carbonate and copper oxide; the iron source is one or more of ferric nitrate, ferric chloride, ferric acetate, ferric sulfate, ferric carbonate and ferric oxide; the manganese source is one or more of manganese nitrate, manganese chloride, manganese acetate, manganese sulfate, manganese carbonate, manganese dioxide, manganese sesquioxide and manganous oxide; the metal element compound is one or more of nickel oxide, cobalt oxide, chromium oxide, ruthenium oxide, tin oxide, scandium oxide, zirconium oxide, lithium carbonate, titanium dioxide, magnesium oxide, zinc oxide, calcium oxide, aluminum oxide and boron oxide.
Further, according to the preparation method of the layered positive electrode material of the sodium ion battery, the sodium source is sodium carbonate, the copper source is copper oxide, the iron source is ferric oxide, and the manganese source is manganese dioxide.
In the preparation method of the layered positive electrode material of the sodium ion battery, the solvent is water, the mixed material is ground into fine particles by a sand mill, the maximum rotation speed percentage of the sand mill is 40-80%, and the pressure of a feed pump of the sand mill is 0.1-1 MPa. If the ratio is less than this range, the time and energy consumption are high, and if the ratio is more than this range, the sand mill may be damaged.
Further, according to the preparation method of the sodium ion battery layered anode material, the maximum rotation speed percentage of the sand mill is 60%, and the pressure of the feeding pump of the sand mill is 0.5MPa.
Further, the preparation method of the layered positive electrode material of the sodium ion battery adopts a spray dryer and a peristaltic pump in the drying process, wherein the air inlet temperature of the spray dryer is 180-230 ℃, the air outlet temperature is 100-120 ℃, the spraying frequency is 300-500 Hz, and the rotation speed of the peristaltic pump is 10-60 revolutions/min. Too low a temperature would not dry the feed to pelletize and too high a temperature would damage the instrument.
Further, according to the preparation method of the layered positive electrode material of the sodium ion battery, the air inlet temperature of the spray dryer is 200 ℃, the air outlet temperature is 110 ℃, the spraying frequency is 400Hz, and the rotating speed of the peristaltic pump is 60 revolutions per minute.
Use of any of the sodium ion battery layered cathode materials described above for a sodium ion battery.
Further, the application of the sodium ion battery layered positive electrode material provided by the application comprises an electrode plate containing the sodium ion battery layered positive electrode material, wherein the content of the sodium ion battery layered positive electrode material in the electrode plate is 70-90 wt%.
Further, the content of the layered positive electrode material of the sodium ion battery in the electrode plate is 70wt%.
Compared with the prior art, the application has the following beneficial technical effects:
the layered positive electrode material for the sodium ion battery can overcome the defects of the existing layered positive electrode material for the sodium ion battery such as multi-platform effect, large internal resistance, large volume change, poor cyclical stability and the like. By introducing metal ions into the transition metal layer or the sodium ion layer of the layered oxide, the interlayer spacing of the layered oxide can be reduced to 0.63nm, more than 10% is reduced, the embedding of moisture in air is limited, and the storage stability of the material is greatly improved. Meanwhile, introducing one or more of metal ions Ni, co, cr, ru, sn, sc, zr, li, ti, mg, zn, ca, al and B, na + The diffusion coefficient of the anode material is increased by 1-2 orders of magnitude, the ion conductivity of the layered anode material is improved, and the ion conductivity is in direct proportion to the ion mobility, so that Na is quickened + The migration speed of the (c) is increased. After the metal ions are introduced, the electron conductivity of the layered anode material is also improved, thereby reducing Na + The charge transfer resistance at the electrode/electrolyte interface, therefore, improves the rate capability of the layered positive electrode material after doping with metal ions. In addition, after metal ions are introduced, irreversible phase change of the material can be effectively inhibited in the charge-discharge process, and the material has high working voltage and specific capacity and excellent cycle stability and rate capability. The working voltage can reach 3.09-3.3V, the specific capacity is 108.81-138.53 mAh/g under the condition of 0.2C, and the capacity retention rate is 65.13-98.86% after 200 circles of circulation under 1C. Particularly, when Ca and Ti are simultaneously introduced, the performance is more excellent, the specific capacity exceeds 138mAh/g under the condition of 0.2C, and the capacity retention rate exceeds 98% after 200 circles of circulation under 1C.
On the other hand, the material prepared by the preparation method of the layered positive electrode material of the sodium ion battery has the advantages of uniform particle size, uniform element distribution, small shape and size, large contact area with electrolyte and more sufficient reaction. In addition, the method has the advantages of low raw material price, environmental protection, no pollution, simple preparation process and suitability for commercial production.
Drawings
FIG. 1 is a microscopic topography of a layered positive electrode material for sodium ion batteries according to the present application;
FIG. 2 is a charge-discharge curve at 0.2C of the positive electrode material obtained in example 8 of the present application;
FIG. 3 is a charge-discharge curve at 0.2C of the positive electrode material obtained in example 9 of the present application;
FIG. 4 is a charge-discharge curve at 0.2C of the positive electrode material obtained in example 13 of the present application;
FIG. 5 is a charge-discharge curve at 0.2C of the positive electrode material obtained in comparative example 1 of the present application;
FIG. 6 is a graph showing the cycle-capacity retention ratio of the positive electrode material obtained in example 9 of the present application versus that obtained in comparative example 1;
FIG. 7 is a graph showing the comparison of electrochemical impedance spectra of the positive electrode materials obtained in examples 8, 9, and 13 of the present application and comparative example 1;
FIG. 8 is a graph showing the comparison of the diffusion coefficient with the curve measured by the constant current batch titration method for the positive electrode materials obtained in example 9 and comparative example 1 of the present application;
FIG. 9 is a graph showing the ratio of the objective products obtained in examples 8, 9 and 13 of the present application to those obtained in comparative example 1.
Detailed Description
The present application will be described in further detail with reference to specific examples.
The specific embodiment is as follows:
the application relates to a layered positive electrode material of a sodium ion battery, which has a chemical formula of Na n Cu y Fe z Mn 1-x-y-z A x O 2 Wherein n is more than 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 0.2, y is more than 0 and less than or equal to 0.3, z is more than 0 and less than or equal to 0.5, and A is one or more of Ni, co, cr, ru, sn, sc, zr, li, ti, mg, zn, ca, al and B; the layered positive electrode material of the sodium ion batteryThe material is a material with the working voltage of 3-3.3V, the specific capacity of 108.81-138.53 mAh/g under the condition of 0.2C, and the capacity retention rate of 65.13-98.86% after 200 circles of circulation under 1C, and the layered positive electrode material of the sodium ion battery is a material with the resistivity range of 1.9x10 -3 ～6.6×10 -3 Omega cm material; fig. 1 is a microscopic morphology diagram of the layered positive electrode material of the sodium ion battery.
A layered positive electrode material of a sodium ion battery, wherein metal ions in the layered positive electrode material of the sodium ion battery are doped in a transition metal layer or a sodium ion layer of a layered oxide material; the chemical formula is Na n Cu y Fe z Mn 1-x-y-z A x O 2 Wherein n is more than 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 0.3, z is more than or equal to 0 and less than or equal to 0.5, the A comprises Ca and Ti, the layered positive electrode material of the sodium ion battery is a material with the working voltage of 3.25V, the specific capacity of the layered positive electrode material exceeds 138mAh/g under the condition of 0.2C, the capacity retention rate of the layered positive electrode material of the sodium ion battery exceeds 98 percent after 200 circles of circulation under the condition of 1C, and the layered positive electrode material of the sodium ion battery is a material with the resistivity reduced to 1.9x10 -3 Omega cm material.
The preparation method of the layered positive electrode material of the sodium ion battery comprises the steps of firstly, uniformly mixing a proper amount of sodium source, copper source, iron source, manganese source and metal element compound in a solvent to obtain a mixed material, and grinding the particle size of the mixed material to 0.2-5 mu m; and drying, and calcining at 600-1000 ℃ for 6-24 hours to obtain the layered anode material of the sodium ion battery.
The preparation method of the layered positive electrode material of the sodium ion battery comprises the steps of firstly, uniformly mixing a proper amount of sodium source, copper source, iron source, manganese source and metal element compound in a solvent to obtain a mixed material, and grinding the particle size of the mixed material to 0.2-5 mu m; and drying, and calcining at 600-1000 ℃ for 6-24 hours to obtain the layered anode material of the sodium ion battery. The sodium source is one or more of sodium nitrate, sodium chloride, sodium acetate, sodium citrate, sodium carbonate and sodium oxide; the copper source is one or more of copper nitrate, copper chloride, copper acetate, copper sulfate, copper carbonate and copper oxide; the iron source is one or more of ferric nitrate, ferric chloride, ferric acetate, ferric sulfate, ferric carbonate and ferric oxide; the manganese source is one or more of manganese nitrate, manganese chloride, manganese acetate, manganese sulfate, manganese carbonate, manganese dioxide, manganese sesquioxide and manganous oxide; the metal element compound is one or more of nickel oxide, cobalt oxide, chromium oxide, ruthenium oxide, tin oxide, scandium oxide, zirconium oxide, lithium carbonate, titanium dioxide, magnesium oxide, zinc oxide, calcium oxide, aluminum oxide and boron oxide. The solvent is water, the particle size of the mixed material is finely ground by a sand mill, the maximum rotation speed percentage of the sand mill is 40-80%, and the pressure of a feed pump of the sand mill is 0.1-1 MPa. The drying process adopts a peristaltic pump, the air inlet temperature of the spray dryer is 180-230 ℃, the air outlet temperature is 100-120 ℃, the spraying frequency is 300-500 Hz, and the rotating speed of the peristaltic pump is 10-60 revolutions/min.
Use of a layered positive electrode material for a sodium-ion battery as defined in any one of the preceding claims, for a sodium-ion battery.
The use of the sodium ion battery layered positive electrode material according to any one of the above, wherein the sodium ion battery comprises an electrode plate containing the sodium ion battery layered positive electrode material, and the content of the sodium ion battery layered positive electrode material in the electrode plate is 70-90 wt%.
The preparation method of the electrode plate of the layered positive electrode material of the sodium ion battery comprises the following steps: the electrode plate contains the layered positive electrode material of the sodium ion battery, a conductive additive, a binder and a corresponding solvent, and the preparation method comprises the steps of pulping, smearing and drying the material.
In the above method, the conductive additive is one or more of carbon black, super-P and ketjen black, preferably carbon black. The binder and the corresponding solvent are one or more of polyvinylidene fluoride (PVDF) (N-methylpyrrolidone (NMP) is taken as a solvent), sodium carboxymethylcellulose (CMC), sodium Alginate (SA), polyacrylic acid (PAA), styrene-butadiene rubber/sodium carboxymethylcellulose and gelatin (all taking water as a solvent), and preferably polyvinylidene fluoride (PVDF) (N-methylpyrrolidone (NMP) is taken as a solvent).
In the method, the content of the layered positive electrode material is 70-90 wt%, preferably 70wt%; the carbon black content of the conductive additive is 5-20wt%, preferably 20wt%; the binder PVDF content is 5 to 10% by weight, preferably 10% by weight.
A sodium ion battery comprises metallic sodium as a negative electrode, a diaphragm, an organic electrolyte and the electrode plate. The organic electrolyte is carbonate electrolyte with the concentration of 0.1-2M, preferably 1M, and the solvent in the carbonate electrolyte is at least one selected from dimethyl carbonate, diethyl carbonate, methylethyl carbonate, ethylene carbonate and propylene carbonate, preferably a mixed solvent of ethylene carbonate and diethyl carbonate; the solute is at least one selected from sodium hexafluorophosphate, sodium perchlorate and sodium bis (trifluoromethylsulfonyl) imide (NaTFSI), preferably sodium hexafluorophosphate. The operating temperature of the sodium ion battery is 25 ℃.
Example 1:
preparation of Na 0.82 Cu 0.22 Fe 0.32 Mn 0.36 Ti 0.1 O 2 The positive electrode material is formed by a process of forming a positive electrode material,
accurately weigh corresponding proportion of Na 2 CO 3 、CuO、Fe 2 O 3 、MnO 2 、TiO 2 Adding solvent water to prepare the solid content of 60%, pouring the mixture into a sand mill, wherein the maximum rotation speed percentage of the sand mill is 60%, the feeding pump pressure is 0.5MPa, and pumping the slurry into a spray dryer for drying after the particle size of the slurry is ground to be 1.5 mu m. The air inlet temperature of the spray dryer is 200 ℃, the air outlet temperature is 110 ℃, the spraying frequency is 400Hz, and the rotating speed of the peristaltic pump is 60 revolutions per minute. Calcining the spray-dried material at 700 ℃ for 20 hours in a box furnace to obtain Na in the embodiment 1 0.82 Cu 0.22 Fe 0.32 Mn 0.36 Ti 0.1 O 2 And a positive electrode material.
Example 2:
preparation of Na 0.82 Cu 0.22 Fe 0.32 Mn 0.36 Li 0.1 O 2 The positive electrode material of example 2 differs from that of example 1 only in that the corresponding proportion of carbonic acid of example 2 is usedLithium was substituted for the titanium oxide in example 1 to prepare the positive electrode material in this example 2.
Example 3:
preparation of Na 0.82 Cu 0.22 Fe 0.32 Mn 0.41 Mg 0.05 O 2 The positive electrode material of example 3 was prepared by substituting the magnesium oxide of example 3 for the titanium oxide of example 1 in the corresponding proportion and adjusting the manganese content accordingly, only with respect to the difference between the positive electrode material of example 1 and the positive electrode material of example 3.
Example 4:
preparation of Na 0.82 Cu 0.22 Fe 0.32 Mn 0.41 Al 0.05 O 2 The positive electrode material of example 4 was prepared by substituting the titanium oxide of example 1 with the aluminum oxide of example 4 in the corresponding proportion and adjusting the manganese content accordingly, only with the difference of example 1.
Example 5:
preparation of Na 0.82 Cu 0.22 Fe 0.32 Mn 0.41 Zn 0.05 O 2 The positive electrode material of example 5 was prepared by substituting the titanium oxide of example 1 with zinc oxide of the corresponding proportion of example 5 and adjusting the manganese content accordingly, and the positive electrode material of example 5 was prepared.
Example 6:
preparation of Na 0.82 Cu 0.22 Fe 0.32 Mn 0.41 Ca 0.05 O 2 The positive electrode material of example 6 was prepared by substituting the calcium oxide of example 1 with the calcium oxide of example 6 in the corresponding proportion and adjusting the manganese content accordingly, and the positive electrode material of example 6 was prepared.
Example 7:
preparation of Na 0.82 Cu 0.22 Fe 0.32 Mn 0.41 B 0.05 O 2 The positive electrode material, example 7 and example 1 differ only in that the boron oxide of the corresponding proportion in example 7 was used instead of the oxide of example 1Titanium and correspondingly adjusting the manganese content to prepare the positive electrode material in the example 7.
Example 8:
preparation of Na 0.82 Cu 0.22 Fe 0.32 Mn 0.31 Li 0.05 Ti 0.1 O 2 The positive electrode material of example 8 was prepared by substituting the lithium carbonate and the titanium oxide of example 1 with the lithium carbonate and the titanium oxide of example 8 in the corresponding proportions, and adjusting the manganese content accordingly, only with the difference between the positive electrode material of example 8 and example 1.
Example 9:
preparation of Na 0.82 Cu 0.22 Fe 0.32 Mn 0.31 Ca 0.05 Ti 0.1 O 2 The positive electrode material of example 9 was prepared by substituting calcium oxide in the corresponding proportion in example 9 for lithium carbonate in example 8, as the positive electrode material of example 9.
Example 10:
preparation of Na 0.82 Cu 0.22 Fe 0.32 Mn 0.31 B 0.05 Ti 0.1 O 2 The positive electrode material of example 10 was prepared by substituting the lithium carbonate of example 8 with boron oxide of the corresponding proportion of example 10, and the positive electrode material of example 10 was prepared.
Example 11:
preparation of Na 0.82 Cu 0.22 Fe 0.32 Mn 0.31 Zn 0.05 Ti 0.1 O 2 The positive electrode material of example 11 was prepared by substituting the lithium carbonate of example 8 with zinc oxide of the corresponding proportion of example 11, and the positive electrode material of example 11 was prepared.
Example 12:
preparation of Na 0.82 Cu 0.22 Fe 0.32 Mn 0.31 Al 0.05 Ti 0.1 O 2 The positive electrode material, example 12 differs from example 8 only in that the example was replaced with alumina in the corresponding proportion in example 128, and preparing the positive electrode material in the example 12.
Example 13:
preparation of Na 0.82 Cu 0.22 Fe 0.32 Mn 0.31 Mg 0.05 Ti 0.1 O 2 The positive electrode material of example 13 was prepared by substituting the lithium carbonate of example 8 with the magnesium oxide of example 13 in the corresponding proportion, and the positive electrode material of example 13 was prepared.
Example 14:
preparation of Na 0.82 Cu 0.22 Fe 0.32 Mn 0.26 Ti 0.2 O 2 The positive electrode material of example 14 was prepared by adjusting the contents of manganese and titanium correspondingly, as compared with example 1.
Example 15:
preparation of Na 0.82 Cu 0.3 Fe 0.32 Mn 0.28 Ti 0.1 O 2 The positive electrode material of example 15 was prepared by adjusting the contents of copper, manganese and titanium correspondingly to the difference between the positive electrode material of example 1 and the positive electrode material of example 15.
Example 16:
preparation of Na 0.82 Cu 0..22 Fe 0.5 Mn 0.18 Ti 0.1 O 2 The positive electrode material of example 16 was prepared by adjusting the contents of iron, manganese and titanium correspondingly, as compared with example 1.
Example 17:
preparation of NaCu 0.22 Fe 0.32 Mn 0.36 Ti 0.1 O 2 The positive electrode material of example 17 was prepared by adjusting the sodium content in accordance with the difference between the positive electrode material of example 17 and example 1.
Comparative example 1:
preparation of Na 0.82 Cu 0.22 Fe 0.32 Mn 0.46 O 2 Positive electrode material
Accurate weighingTaking corresponding proportion of Na 2 CO 3 、CuO、Fe 2 O 3 、MnO 2 Adding solvent water to prepare the solid content of 60%, pouring the mixture into a sand mill, wherein the maximum rotation speed percentage of the sand mill is 60%, the feeding pump pressure is 0.5MPa, and pumping the slurry into a spray dryer for drying after the particle size of the slurry is ground to be 1.5 mu m. The air inlet temperature of the spray dryer is 200 ℃, the air outlet temperature is 110 ℃, the spraying frequency is 400Hz, and the rotating speed of the peristaltic pump is 60 revolutions per minute. The material obtained by spray drying was calcined in a box furnace at 700 ℃ for 20 hours to obtain the positive electrode material in comparative example 1.
Comparative example 2:
preparation of Na 0.82 Cu 0.22 Fe 0.32 Mn 0.21 Ti 0.25 The positive electrode material of comparative example 2 was prepared by adjusting the contents of manganese and titanium correspondingly only with respect to example 1.
Comparative example 3:
preparation of Na 0.82 Cu 0.35 Fe 0.32 Mn 0.23 Ti 0.1 The positive electrode material of comparative example 3 was prepared by adjusting the content of copper and manganese correspondingly to the difference between the positive electrode material of comparative example 3 and example 1.
Comparative example 4:
preparation of Na 0.82 Cu 0.22 Fe 0.55 Mn 0.13 Ti 0.1 The positive electrode material of comparative example 4 was prepared by adjusting the contents of iron and manganese correspondingly only with respect to example 1.
The positive electrode material prepared by the above examples and comparative examples is mixed with carbon black and polyvinylidene fluoride binder (PVDF) according to the mass ratio of 7:2:1, and a certain amount of N-methyl pyrrolidone is added as a solvent, and the positive electrode plate of the sodium ion battery containing the corresponding active substances is obtained after the steps of pulping by a mixing machine, smearing, drying and the like. Assembling the prepared positive plate of the sodium ion battery and the metal sodium negative electrode into a sodium ion battery in a glove box, wherein GF/F is a battery diaphragm, and the electrolyte is carbonate electrolyte (1M NaPF) 6 EC/DEC (volume)1:1) solution).
The sodium ion battery is placed in a constant temperature box at 25 ℃ for electrochemical detection, the voltage window is 2.0-4.1V, and the following results are obtained through measurement:
table 1 results of electrochemical performance test of the positive electrode materials obtained in examples and comparative examples
As can be seen from table 1 above, the cathode materials in the comparative examples were poor in electrochemical properties, low in operating voltage and large in resistivity. When one or more of metal ions Ni, co, cr, ru, sn, sc, zr, li, ti, mg, zn, ca, al and B are introduced, and x is more than or equal to 0 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 0.3, and z is more than 0 and less than or equal to 0.5, the obtained positive electrode materials in the examples 1-17 have excellent performance, and the capacity at the first circle of 0.2C is improved compared with the comparative example. The doped metal ions can effectively inhibit irreversible phase change of the material in the charge-discharge process, so that the layered anode material has high specific capacity. However, when x is not more than 0 and less than or equal to 0.2, y is more than 0 and less than or equal to 0.3, z is more than 0 and less than or equal to 0.5, the electrochemical performance of the material is reduced, the working voltage is reduced, and the resistivity is increased. FIGS. 2-4 show that the specific capacities of example 8, example 9, and example 13 at 0.2C are 121.11mAh/g, 138.53mAh/g, and 117.78mAh/g, respectively, each greater than the specific capacity 108.71mAh/g of comparative example 1 of FIG. 5. Fig. 6 shows the cycle retention of example 9 and comparative example 1 at 1C, indicating that the cycle stability of the positive electrode material is improved when Ca and Ti are simultaneously doped, and the capacity retention of 200 cycles at 1C can reach 98.86%.
As can be seen from the comparison of the electrochemical impedance spectra in FIG. 7 in combination with the results of the above Table 1, the introduction of one or more of the metal ions Ni, co, cr, ru, sn, sc, zr, li, ti, mg, zn, ca, al, B improves the electron conductivity and the ion-electricity of the layered cathode materialConductivity is reduced by Na + The charge transfer resistance at the electrode/electrolyte interface improves the rate capability of the layered cathode material. Fig. 9 shows that the rate performance after the metal ions were introduced is better than that of comparative example 1. The curve and diffusion coefficient plot of the constant current batch titration method of FIG. 8 shows Na after simultaneous introduction of metal ions Ca and Ti + The diffusion coefficient of the anode material is increased by 1-2 orders of magnitude, the ion conductivity of the anode material is improved, and the ion conductivity is in direct proportion to the ion mobility, so that Na is quickened + The migration speed of the (c) is increased.
Claims (9)
1. A layered positive electrode material of a sodium ion battery is characterized in that the chemical formula of the layered positive electrode material of the sodium ion battery is Na n Cu y Fe z Mn 1-x-y-z A x O 2 Wherein n is more than 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 0.2, y is more than 0 and less than or equal to 0.3, z is more than 0 and less than or equal to 0.5, and A is one or more of Ni, co, cr, ru, sn, sc, zr, li, ti, mg, zn, ca, al and B; the layered positive electrode material of the sodium ion battery is a material with the working voltage of 3-3.3V, the specific capacity of 108.81-138.53 mAh/g under the condition of 0.2C, and the capacity retention rate of 65.13-98.86% after 200 circles of circulation under 1C, and the layered positive electrode material of the sodium ion battery is a material with the resistivity range of 1.9 multiplied by 10 -3 ～6.6×10 -3 Omega cm material.
2. The layered cathode material of a sodium ion battery of claim 1, wherein the metal ions in the layered cathode material of a sodium ion battery are doped in a transition metal layer or a sodium ion layer of a layered oxide material; the A comprises Ca and Ti, the layered positive electrode material of the sodium ion battery is a material with the specific capacity exceeding 138mAh/g under the working voltage of 3.25V and the 0.2C, and the capacity retention rate exceeding 98 percent after 200 circles of circulation under 1C, and the layered positive electrode material of the sodium ion battery is a material with the resistivity reduced to 1.9 multiplied by 10 -3 Omega cm material.
3. A method for preparing the layered positive electrode material of sodium ion battery according to claim 1 or 2, wherein the method is a sand milling-solid phase sintering two-step method, and the method comprises the steps of firstly uniformly mixing a proper amount of sodium source, copper source, iron source, manganese source and metal element compound in a solvent to obtain a mixed material, and grinding the particle size of the mixed material to 0.2-5 μm; and drying, and calcining at 600-1000 ℃ for 6-24 hours to obtain the layered anode material of the sodium ion battery.
4. The method for preparing a layered cathode material for a sodium ion battery according to claim 3, wherein the sodium source is one or more of sodium nitrate, sodium chloride, sodium acetate, sodium citrate, sodium carbonate and sodium oxide; the copper source is one or more of copper nitrate, copper chloride, copper acetate, copper sulfate, copper carbonate and copper oxide; the iron source is one or more of ferric nitrate, ferric chloride, ferric acetate, ferric sulfate, ferric carbonate and ferric oxide; the manganese source is one or more of manganese nitrate, manganese chloride, manganese acetate, manganese sulfate, manganese carbonate, manganese dioxide, manganese sesquioxide and manganous oxide; the metal element compound is one or more of nickel oxide, cobalt oxide, chromium oxide, ruthenium oxide, tin oxide, scandium oxide, zirconium oxide, lithium carbonate, titanium dioxide, magnesium oxide, zinc oxide, calcium oxide, aluminum oxide and boron oxide.
5. The method for preparing a layered cathode material for a sodium ion battery according to claim 4, wherein the sodium source is sodium carbonate, the copper source is copper oxide, the iron source is iron oxide, and the manganese source is manganese dioxide.
6. The method for preparing a layered positive electrode material for a sodium ion battery according to claim 5, wherein the solvent is water, the mixture is ground into fine particles by a sand mill, the maximum rotation speed percentage of the sand mill is 40-80%, and the pressure of a feed pump of the sand mill is 0.1-1 MPa.
7. The method for preparing the layered positive electrode material of the sodium ion battery according to claim 6, wherein a spray dryer and a peristaltic pump are adopted in the drying process, the air inlet temperature of the spray dryer is 180-230 ℃, the air outlet temperature is 100-120 ℃, the spraying frequency is 300-500 Hz, and the rotation speed of the peristaltic pump is 10-60 rpm.
8. Use of a layered positive electrode material for a sodium-ion battery according to any one of claims 1 to 7, wherein the layered positive electrode material for a sodium-ion battery.
9. The use of a layered positive electrode material for a sodium-ion battery according to claim 8, wherein the sodium-ion battery comprises an electrode sheet containing the layered positive electrode material for a sodium-ion battery, and the content of the layered positive electrode material for a sodium-ion battery in the electrode sheet is 70-90 wt%.
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| CN117254020A (en) * | 2023-11-13 | 2023-12-19 | 江门市科恒实业股份有限公司 | Aluminum phosphate coated calcium-doped sodium ion battery positive electrode material and preparation method thereof |
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| CN117254020A (en) * | 2023-11-13 | 2023-12-19 | 江门市科恒实业股份有限公司 | Aluminum phosphate coated calcium-doped sodium ion battery positive electrode material and preparation method thereof |
| CN117254020B (en) * | 2023-11-13 | 2024-03-08 | 江门市科恒实业股份有限公司 | Aluminum phosphate coated calcium-doped sodium ion battery positive electrode material and preparation method thereof |
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