CN116936766A - 一种钠离子电池复合正极材料及其制备方法和应用 - Google Patents
一种钠离子电池复合正极材料及其制备方法和应用 Download PDFInfo
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- CN116936766A CN116936766A CN202310969073.0A CN202310969073A CN116936766A CN 116936766 A CN116936766 A CN 116936766A CN 202310969073 A CN202310969073 A CN 202310969073A CN 116936766 A CN116936766 A CN 116936766A
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- sodium
- mnzr
- positive electrode
- oxide
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 32
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 28
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 75
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 26
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 12
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical group CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 11
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 11
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 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 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 235000015165 citric acid Nutrition 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229940071125 manganese acetate Drugs 0.000 claims description 8
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 8
- 235000017281 sodium acetate Nutrition 0.000 claims description 8
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 6
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 6
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000010405 anode material Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000006012 monoammonium phosphate Substances 0.000 claims description 4
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims 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 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 239000005696 Diammonium phosphate Substances 0.000 claims description 3
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-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
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 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
- 238000013329 compounding Methods 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 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
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 229940099690 malic acid Drugs 0.000 claims description 3
- 229960002510 mandelic acid Drugs 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 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
- 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
- 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
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- HWPKGOGLCKPRLZ-UHFFFAOYSA-M monosodium citrate Chemical compound [Na+].OC(=O)CC(O)(C([O-])=O)CC(O)=O HWPKGOGLCKPRLZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000002524 monosodium citrate Substances 0.000 claims description 3
- 235000018342 monosodium citrate Nutrition 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 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
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 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
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
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- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 20
- 239000011247 coating layer Substances 0.000 abstract description 12
- 150000002500 ions Chemical class 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 230000002401 inhibitory effect Effects 0.000 abstract description 5
- 230000005536 Jahn Teller effect Effects 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000013543 active substance Substances 0.000 abstract description 3
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- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract description 2
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- 230000002035 prolonged effect Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 46
- 239000000843 powder Substances 0.000 description 26
- 239000002002 slurry Substances 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- 238000000498 ball milling Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
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- 239000012300 argon atmosphere Substances 0.000 description 5
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- 239000002904 solvent Substances 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
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- H—ELECTRICITY
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Abstract
本申请涉及钠离子电池领域,公开了一种钠离子电池复合正极材料及其制备方法和应用。本申请通过两种以上金属阳离子掺杂稳定Na3MnZr(PO4)3的晶体结构,在其表面形成复合的金属氧化物包覆层,抑制其Jahn‑Teller效应及Mn溶解,同时保持Na3MnZr(PO4)3本体结构,并保护本体Na3MnZr(PO4)3免受电解质腐蚀,提升材料的循环寿命;同时通过电化学活性掺杂层保持表面上的离子和电荷传输通道,从而提升材料的离子/电子电导率,减小充放电极化;此外,作为外壳的复合包覆层能抑制充放电过程中活性物质因体积反复膨胀/收缩而脱离集流体,提升材料稳定性从而提升材料的倍率和循环性能。
Description
技术领域
本申请涉及钠离子电池领域,具体涉及一种钠离子电池复合正极材料及其制备方法和应用。
背景技术
钠离子电池因其储量丰富、价格低廉、工作电压相当以及插层化学性质相似而成为锂离子电池的优良替代品之一。NASICON型Na3MnZr(PO4)3具有稳定的三维结构骨架,其晶体结构对离子插层更为稳定,有利于Na离子快速脱嵌,且具有较高离子电导率和结构稳定性。此外,该材料独特的“诱导效应”使材料具有更高的氧化还原电位和更高的能量密度,是一种具有发展前景的钠离子电池正极材料。尽管有上述优点,但是Na3MnZr(PO4)3还存在电子/离子电导率低、Mn3+的Jahn-Teller效应以及Mn溶解等问题,导致材料具有较差的倍率性能和循环性能,从而严重制约了其有效应用。
发明内容
有鉴于此,本申请的目的在于提供一种钠离子电池复合正极材料及其制备方法,使得所述复合正极材料具有更高的循环能行和倍率性能;
本申请的另外一个目的在于提供一种基于上述正极材料的正极极片和钠离子电池。
为了解决上述技术问题/达到上述目的或者至少部分地解决上述技术问题/达到上述目的,作为本申请的第一个方面,提供了一种钠离子电池复合正极材料,包括外壳和至少一个以上的内核,所述内核为无定形碳包覆的Na3MnZr(PO4)3,所述外壳由金属氧化物和无定形碳复合而成。
可选地,所述Na3MnZr(PO4)3、金属氧化物、无定形碳的质量比为(80-99.8):(0.1-10):(0.1-10)。
可选地,所述金属氧化物选自钛氧化物、锆氧化物、铬氧化物、镍氧化物、钴氧化物、氧化铝、铈氧化物、氧化锌、氧化镁、氧化铜中的两种或三种以上。
作为本申请的第二个方面,提供了所述复合正极材料的制备方法,包括:
按照Na3MnZr(PO4)3化学式的原子比称取钠源、锰源、锆源、磷酸源,同时加入碳源,充分反应后煅烧,形成无定形碳包覆的Na3MnZr(PO4)3;
将用于制备外壳中金属氧化物的原料与所述无定形碳包覆的Na3MnZr(PO4)3混合均匀,干燥后获得前驱体;
所述前驱体进行煅烧后,获得所述复合正极材料。
可选地,所述钠源选自磷酸二氢钠、磷酸氢二钠、磷酸三钠、柠檬酸二氢钠、草酸钠、碳酸钠、氢氧化钠、乙酸钠、十二烷基苯磺酸钠、过硫酸钠、海藻酸钠中的一种或两种以上,所述锰源选自碳酸锰、乙酸锰、硫酸锰、氧化锰、硝酸锰、乙酰丙酮锰中的一种或两种以上,所述锆源选自乙酸锆,所述磷酸源选自磷酸二氢铵、磷酸氢二钠、磷酸三钠、磷酸二铵、磷酸一铵、磷酸三铵、磷酸中的一种或两种以上,所述碳源选自柠檬酸、草酸、酒石酸、乙二酸、己二酸、丙二酸、抗坏血酸、蔗糖、苦杏仁酸、苹果酸、甲醛、乙醛、正丁醛、异丁醛、四乙基乙二醇、异丙醇、水合肼和尿素中的一种或两种以上。
可选地,所述用于制备外壳中金属氧化物的原料选自钛酸四丁酯、硫酸氧钛、乙酸锆、乙酰丙酮锆、九水硝酸铝、六水硝酸铈、四水乙酸镍、四水乙酸钴、六水硝酸钴、乙酸锌、氯化锌、硝酸铜、硫酸铜、氯化铜、四水乙酸镁中的两种或三种以上。
可选地,所述煅烧的温度为500-800℃。
作为本申请的第三个方面,基于本申请所述复合正极材料的优异性能,提出了其在制备正极极片或钠离子电池中的应用。
作为本申请的第四个方面,提供了一种正极极片,包括集流体、导电剂、粘结剂和本申请所述的复合正极材料。
作为本申请的第五个方面,提供了一种钠离子电池,包括负极极片、电解液、隔膜和本申请所述的正极极片。
本申请通过金属阳离子掺杂稳定Na3MnZr(PO4)3的晶体结构,在其表面形成复合的金属氧化物包覆层,抑制其Jahn-Teller效应及Mn溶解,同时保持Na3MnZr(PO4)3本体结构,并保护本体Na3MnZr(PO4)3免受电解质腐蚀,提升材料的循环寿命;同时通过电化学活性掺杂层保持表面上的离子和电荷传输通道,从而提升材料的离子/电子电导率,减小充放电极化;此外,作为外壳的复合包覆层能抑制充放电过程中活性物质因体积反复膨胀/收缩而脱离集流体,提升材料稳定性从而提升材料的倍率和循环性能。
附图说明:
图1所示为本申请复合正极材料的结构示意图;
图2所示为实施例1制备的Na3MnZr(PO4)3/C的XRD图谱;
图3所示为实施例1制备Na3MnZr(PO4)3/C@TiO2@ZrO2的XRD图谱。
具体实施方式:
本申请公开了一种钠离子电池复合正极材料及其制备方法和应用,本领域技术人员可以借鉴本文内容,适当改进工艺参数实现。特别需要指出的是,所有类似的替换和改动对本领域技术人员来说是显而易见的,它们都被视为包括在本申请。本申请的产品、应用和方法已经通过较佳实施例进行了描述,相关人员明显能在不脱离本发明内容、精神和范围内对本文所述的方法进行改动或适当变更与组合,来实现和应用本发明技术。
在本申请的第一个方面中,提供了一种钠离子电池复合正极材料,包括外壳和至少一个以上的内核,所述内核为无定形碳包覆的Na3MnZr(PO4)3,所述外壳由金属氧化物和无定形碳复合而成;结构示意图见图1。
本申请在Na3MnZr(PO4)3表面修饰复合包覆层,掺入的一些金属元素,如Mg、Al、Ti、Ni、Co、Ce、Zn、Cu、V等,可以改变局部原子环境,抑制Jahn-Teller效应提高电化学性能;在体相掺杂的基础上进行混合表面包覆,多种元素共掺杂使材料表面形成一个薄的无序的岩盐壳和掺杂相的偏析表面,能有效抑制表面结构的溶解,增强材料在电解液中耐侵蚀的能力;
多种金属元素之间具有协同效应,在高温条件下存在热驱动,在颗粒表面元素含量成梯度下降,元素之间会形成空位或缺陷更有利于钠离子的传输,包覆具有电化学活性的元素可以提升材料的导电性,还能抑制充放电过程中活性物质因体积反复膨胀/收缩而脱离集流体,提升材料稳定性从而达到提升材料的倍率和循环性能。
在本申请某些实施方式中,所述Na3MnZr(PO4)3、金属氧化物、无定形碳的质量比为(80-99.8):(0.1-10):(0.1-10)。其中,所述Na3MnZr(PO4)3的质量比数值可选为85、90、98或99.8,所述金属氧化物的质量比数值可选为0.1、1、5或10,所述无定形碳的质量比数值可选为0.1、1、5或10。
在本申请某些实施方式中,所述金属氧化物选自钛氧化物、锆氧化物、铬氧化物、镍氧化物、钴氧化物、氧化铝、铈氧化物、氧化锌、氧化镁、氧化铜中的两种或三种以上。在本申请另外一些实施方式中,所述金属氧化物选自TiO2、ZrO2、Al2O3、CeO2、NiO中的两种或三种以上。
在本申请的第二个方面中,提供了所述复合正极材料的制备方法,包括:
按照Na3MnZr(PO4)3化学式的原子比称取钠源、锰源、锆源、磷酸源,同时加入碳源,充分反应后煅烧,形成无定形碳包覆的Na3MnZr(PO4)3;
将用于制备外壳中金属氧化物的原料与所述无定形碳包覆的Na3MnZr(PO4)3混合均匀,干燥后获得前驱体;
所述前驱体进行煅烧后,获得所述复合正极材料。
本申请提出的制备方法,可以有效解决包覆层的均匀性和连续性以及包覆层与活性材料之间可能存在的晶体结构差异问题,利用体相掺杂和表面包覆技术的优势,同时保持高容量、安全、电荷传输和正极材料的稳定性。
在本申请某些实施方式中,所述钠源、锰源、锆源、磷酸源、碳源的化学计量比为3:1:1:3:(0.02-2);其中,所述碳源的化学计量比数值可选为0.02、0.2、1或2。
在本申请某些实施方式中,所述钠源选自磷酸二氢钠、磷酸氢二钠、磷酸三钠、柠檬酸二氢钠、草酸钠、碳酸钠、氢氧化钠、乙酸钠、十二烷基苯磺酸钠、过硫酸钠、海藻酸钠中的一种或两种以上,所述锰源选自碳酸锰、乙酸锰、硫酸锰、氧化锰、硝酸锰、乙酰丙酮锰中的一种或两种以上,所述锆源选自乙酸锆,所述磷酸源选自磷酸二氢铵、磷酸氢二钠、磷酸三钠、磷酸二铵、磷酸一铵、磷酸三铵、磷酸中的一种或两种以上,所述碳源选自柠檬酸、草酸、酒石酸、乙二酸、己二酸、丙二酸、抗坏血酸、蔗糖、苦杏仁酸、苹果酸、甲醛、乙醛、正丁醛、异丁醛、四乙基乙二醇、异丙醇、水合肼和尿素中的一种或两种以上。
在本申请某些实施方式中,为了使充分反应钠源、锰源、锆源、磷酸源、碳源充分反应,本申请利用球磨法强大的碰撞、研磨和分散的力量,所有外界条件均被强化,高速旋转使反应体系运动加剧,物质之间碰撞机率增加,接触面积增大,可以大大提高反应的效率,缩短反应时间,获得粒径小且均匀的产物。在本申请另外一些实施方式中,所述球磨转速为200-600r/min,球磨时间2-6h。
在本申请某些实施方式中,为了使钠源、锰源、锆源、磷酸源、碳源分散均匀,还可以加入分散剂,例如水、无水乙醇、乙酸、丙酮、异丙酮等,加入分散剂后进行球磨形成浆料。
在本申请某些实施方式中,形成无定形碳包覆的Na3MnZr(PO4)3的煅烧温度为600-800℃,时间12-14h;在煅烧时在保护性气体氛围下进行,所述保护性气体包括氮气、氢气和惰性气体,例如氩气、氦气、氖气等惰性气体。
在本申请某些实施方式中,所述用于制备外壳中金属氧化物的原料选自钛酸四丁酯、硫酸氧钛、乙酸锆、乙酰丙酮锆、九水硝酸铝、六水硝酸铈、四水乙酸镍、四水乙酸钴、六水硝酸钴、乙酸锌、氯化锌、硝酸铜、硫酸铜、氯化铜、四水乙酸镁中的两种或三种以上;在本申请另外一些实施方式中,各原料的质量相同。
在本申请某些实施方式中,用于制备外壳中金属氧化物的原料首先通过有机溶剂,例如乙醇进行溶解形成溶胶,而加入所述无定形碳包覆的Na3MnZr(PO4)3分散均匀。
在本申请某些实施方式中,所述前驱体煅烧的温度为500-750℃,煅烧时间2-6h。
在本申请的第三个方面中,与单一的碳包覆、体相掺杂等方案相比,本申请所述复合正极材料组装的钠离子电池,在0.1C、2C和5C下的首次放电比容量和循环性能得到明显提高。基于这种优异性能,提出了其在制备正极极片或钠离子电池中的应用。
在本申请的第四个方面中,提供了一种正极极片,包括集流体、导电剂、粘结剂和本申请所述的复合正极材料。
在本申请某些实施方式中,所述正极极片包括集流体和涂覆于集流体上的浆料;其中,所述集流体可选自导电良好的金属箔,例如铝箔;所述浆料包括本申请所述的复合正极材料,以及粘结剂和导电剂,所述粘结剂、导电剂及其用量等按照常规选择,本申请不做具体限制,例如粘结剂为聚偏氟乙烯(PVDF)、丁苯橡胶(SBR)和羧甲基纤维素钠(CMC)等,导电剂为导电炭黑(SP)、乙炔黑等,溶剂为N-甲基吡咯烷酮(NMP)、去离子水等。在本申请另外一些实施方式中,所述正极浆料中复合正极材料、导电剂、粘结剂的质量百分比依次为95%-99%、0.5%-3%和1%-5%。
在本申请的第五个方面中,提供了一种钠离子电池,包括负极极片、电解液、隔膜和本申请所述的正极极片。
在本申请某些实施方式中,负极极片以硬碳为活性材料,导电剂和粘结剂选用常规物质即可,其用量按照常规选择。
在本申请某些实施方式中,所述钠离子电池可通过叠片的方式制备成电芯,电芯烘烤后,将非水电解液注入电芯中,经化成分容后,制备成钠离子电池。
在本申请提供的各组对比实验中,如未特别说明,除各组指出的区别外,其他实验条件、材料等均保持一致,以便具有可对比性。此外,本申请所用材料均可通过市售途径购买获得。
以下就本申请所提供的一种钠离子电池复合正极材料及其制备方法和应用做进一步说明。
实施例1:Na3MnZr(PO4)3/C@复合包覆层(TiO2和ZrO2)
a.制备Na3MnZr(PO4)3/C:将三水乙酸钠、乙酸锆、乙酸锰、磷酸二氢铵、柠檬酸按照化学计量比(3:1:1:3:0.2)配料,以乙醇为分散剂,在行星式球磨机中以400转/分钟的速度球磨4h得到浆料,所得浆料在90℃下恒温干燥24h,干燥后的浆料置于球磨机中再干磨2h得到Na3MnZr(PO4)3的前驱体粉末,将前驱体粉末在氩气气氛下,300℃煅烧2h再升温至750℃煅烧12h,随炉冷却得到Na3MnZr(PO4)3/C粉末,其XRD图谱见图2。
b.以20ml的乙醇为溶剂,称量50mg的钛酸四丁酯和50mg的乙酰丙酮锆溶解于乙醇中,缓慢滴入冰醋酸(抑制钛酸四丁酯水解)控制溶液的pH=1.5,搅拌得到溶胶后,将步骤a中制备的Na3MnZr(PO4)3/C粉体取9.8g倒入稀释后的溶胶中,再加入5ml乙醇稀释(防止胶体聚集),分散均匀,然后进行喷雾干燥,得到核壳结构的复合材料前驱体粉末。
c.将步骤b制备的复合材料前驱体粉末在氮气气氛下,750℃煅烧4h,得到最终产物—复合正极材料Na3MnZr(PO4)3/C@TiO2@ZrO2(Na3MnZr(PO4)3、金属氧化物、无定形碳的质量比=98:1:1),其XRD图谱见图3。
实施例2:Na3MnZr(PO4)3/C@复合包覆层(TiO2和NiO)
a.制备Na3MnZr(PO4)3/C:将三水乙酸钠、乙酸锆、乙酸锰、磷酸二氢铵、柠檬酸按照化学计量比(3:1:1:3:0.02)配料,以乙醇为分散剂,在行星式球磨机中以400转/分钟的速度球磨4h得到浆料,所得浆料在90℃下恒温干燥24h,干燥后的浆料置于球磨机中再干磨2h得到Na3MnZr(PO4)3的前驱体粉末,将前驱体粉末在氩气气氛下,300℃煅烧2h再升温至750℃煅烧12h,随炉冷却得到Na3MnZr(PO4)3/C粉末。
b.以20ml的乙醇为溶剂,称量5mg的钛酸四丁酯和5mg的四水乙酸镍溶解于乙醇中,缓慢滴入冰醋酸(抑制钛酸四丁酯水解)控制溶液的pH=1.5,搅拌得到溶胶后,将步骤a中制备的Na3MnZr(PO4)3/C粉体取0.998g倒入稀释后的溶胶中,再加入5ml乙醇稀释(防止胶体聚集),分散均匀,然后进行喷雾干燥,得到核壳结构的复合材料前驱体粉末。
c.将步骤b制备的复合材料前驱体粉末在氮气气氛下,750℃煅烧6h,得到最终产物—复合正极材料Na3MnZr(PO4)3/C@TiO2@NiO(Na3MnZr(PO4)3、金属氧化物、无定形碳的质量比=99.8:0.1:0.1)。
实施例3:Na3MnZr(PO4)3/C@复合包覆层(CeO2和Al2O3)
a.制备Na3MnZr(PO4)3/C:将三水乙酸钠、乙酸锆、乙酸锰、磷酸二氢铵、柠檬酸按照化学计量比(3:1:1:3:2)配料,以乙醇为分散剂,在行星式球磨机中以400转/分钟的速度球磨4h得到浆料,所得浆料在90℃下恒温干燥24h,干燥后的浆料置于球磨机中再干磨2h得到Na3MnZr(PO4)3的前驱体粉末,将前驱体粉末在氩气气氛下,300℃煅烧2h再升温至750℃煅烧12h,随炉冷却得到Na3MnZr(PO4)3/C粉末。
b.以20ml的水为溶剂,称量0.25g的硝酸铈和0.25g的九水硝酸铝溶解于水中,控制溶液的pH=5(使氢氧化铝完全沉淀),将步骤a中制备的Na3MnZr(PO4)3/C粉体取0.85g倒入悬浊液中,分散均匀,然后进行喷雾干燥,得到核壳结构的复合材料前驱体粉末。
c.将步骤b制备的复合材料前驱体粉末在氮气气氛下,750℃煅烧5h,得到最终产物—复合正极材料Na3MnZr(PO4)3/C@CeO2@Al2O3(Na3MnZr(PO4)3、金属氧化物、无定形碳的质量比=85:10:5)。
实施例4:Na3MnZr(PO4)3/C@复合包覆层(TiO2,CeO2和NiO)
a.制备Na3MnZr(PO4)3/C:将三水乙酸钠、乙酸锆、乙酸锰、磷酸二氢铵、柠檬酸按照化学计量比(3:1:1:3:1)配料,以乙醇为分散剂,在行星式球磨机中以400转/分钟的速度球磨4h得到浆料,所得浆料在90℃下恒温干燥24h,干燥后的浆料置于球磨机中再干磨2h得到Na3MnZr(PO4)3的前驱体粉末,将前驱体粉末在氩气气氛下,300℃煅烧2h再升温至750℃煅烧12h,随炉冷却得到Na3MnZr(PO4)3/C粉末。
b.以20ml的乙醇为溶剂,称量0.33g的钛酸四丁酯,0.33g的硝酸铈和0.33g的四水乙酸镍溶解于乙醇中,缓慢滴入冰醋酸(抑制钛酸四丁酯水解)控制溶液的pH=1.5,搅拌得到溶胶后,将步骤a中制备的Na3MnZr(PO4)3/C粉体取0.85g倒入稀释后的溶胶中,再加入5ml乙醇稀释(防止胶体聚集),分散均匀,然后进行喷雾干燥,得到核壳结构的复合材料前驱体粉末。
c.将步骤b制备的复合材料前驱体粉末在氮气气氛下,750℃煅烧6h,得到最终产物—复合正极材料Na3MnZr(PO4)3/C@TiO2@CeO2@NiO(Na3MnZr(PO4)3、金属氧化物、无定形碳的质量比=85:5:10)。
实施例5:Na3MnZr(PO4)3/C@复合包覆层(CeO2和Al2O3)
a.制备Na3MnZr(PO4)3/C:将三水乙酸钠、乙酸锆、乙酸锰、磷酸二氢铵、柠檬酸按照化学计量比(3:1:1:3:1)配料,以乙醇为分散剂,在行星式球磨机中以400转/分钟的速度球磨4h得到浆料,所得浆料在90℃下恒温干燥24h,干燥后的浆料置于球磨机中再干磨2h得到Na3MnZr(PO4)3的前驱体粉末,将前驱体粉末在氩气气氛下,300℃煅烧2h再升温至750℃煅烧12h,随炉冷却得到Na3MnZr(PO4)3/C粉末。
b.以20ml的水为溶剂,称量0.25g的四水乙酸镍和0.25g的九水硝酸铝溶解于水中,控制溶液的pH=5(使氢氧化铝完全沉淀),将步骤a中制备的Na3MnZr(PO4)3/C粉体取0.90g倒入悬浊液中,分散均匀,然后进行喷雾干燥,得到核壳结构的复合材料前驱体粉末。
c.将步骤b制备的复合材料前驱体粉末在氮气气氛下,750℃煅烧5h,得到最终产物—复合正极材料Na3MnZr(PO4)3/C@NiO@Al2O3(Na3MnZr(PO4)3、金属氧化物、无定形碳的质量比=90:5:5)。
对比例1:Na3MnZr(PO4)3/C
参照实施例1中的方法制备Na3MnZr(PO4)3/C粉末。
对比例2:Na3MnZr(PO4)3/C@TiO2
参照实施例1的方法,不同之处在于不需要在步骤b中加入乙酰丙酮锆,称量50mg的钛酸四丁酯,其余步骤同实施例1,Na3MnZr(PO4)3、金属氧化物、无定形碳的质量比=98:1:1。
对比例3:Na3MnZr(PO4)3/C@ZrO2
参照实施例1的方法,不同之处在于不需要在步骤b中加入钛酸四丁酯和冰醋酸,称量50mg的乙酰丙酮锆,其余步骤同实施例1,Na3MnZr(PO4)3、金属氧化物、无定形碳的质量比=98:1:1。
实验例:
以实施例1以及对比例1-3制备的复合正极材料为正极活性材料,采用相同的电池组装工艺组装成钠离子电池,在0.1C和2C以及5C下进行首次放电比容量和循环性能的测试,结果见表1;
表1倍率性能和循环性能比较
由表1可以清楚看到,采用本申请所述复合正极材料制备的钠离子电池,其在0.1C、2C和5C条件下,首次放电比容量均明显高于三个对比例,并且随着倍率增高,这种差异越发明显;
同时,在0.1C循环200圈、2C循环1000圈、5C循环1000圈后,电池容量保持率也显著高于其他三个对比例。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种钠离子电池复合正极材料,其特征在于,包括外壳和至少一个以上的内核,所述内核为无定形碳包覆的Na3MnZr(PO4)3,所述外壳由金属氧化物和无定形碳复合而成。
2.根据权利要求1所述的复合正极材料,其特征在于,所述Na3MnZr(PO4)3、金属氧化物、无定形碳的质量比为(80-99.8):(0.1-10):(0.1-10)。
3.根据权利要求1或2所述的复合正极材料,其特征在于,所述金属氧化物选自钛氧化物、锆氧化物、铬氧化物、镍氧化物、钴氧化物、氧化铝、铈氧化物、氧化锌、氧化镁、氧化铜中的两种或三种以上。
4.权利要求1所述的复合正极材料的制备方法,其特征在于,包括:
按照Na3MnZr(PO4)3化学式的原子比称取钠源、锰源、锆源、磷酸源,同时加入碳源,充分反应后煅烧,形成无定形碳包覆的Na3MnZr(PO4)3;
将用于制备外壳中金属氧化物的原料与所述无定形碳包覆的Na3MnZr(PO4)3混合均匀,干燥后获得前驱体;
所述前驱体进行煅烧后,获得所述复合正极材料。
5.根据权利要求4所述的制备方法,其特征在于,所述钠源选自磷酸二氢钠、磷酸氢二钠、磷酸三钠、柠檬酸二氢钠、草酸钠、碳酸钠、氢氧化钠、乙酸钠、十二烷基苯磺酸钠、过硫酸钠、海藻酸钠中的一种或两种以上,所述锰源选自碳酸锰、乙酸锰、硫酸锰、氧化锰、硝酸锰、乙酰丙酮锰中的一种或两种以上,所述锆源选自乙酸锆,所述磷酸源选自磷酸二氢铵、磷酸氢二钠、磷酸三钠、磷酸二铵、磷酸一铵、磷酸三铵、磷酸中的一种或两种以上,所述碳源选自柠檬酸、草酸、酒石酸、乙二酸、己二酸、丙二酸、抗坏血酸、蔗糖、苦杏仁酸、苹果酸、甲醛、乙醛、正丁醛、异丁醛、四乙基乙二醇、异丙醇、水合肼和尿素中的一种或两种以上。
6.根据权利要求4所述的制备方法,其特征在于,所述用于制备外壳中金属氧化物的原料选自钛酸四丁酯、硫酸氧钛、乙酸锆、乙酰丙酮锆、九水硝酸铝、六水硝酸铈、四水乙酸镍、四水乙酸钴、六水硝酸钴、乙酸锌、氯化锌、硝酸铜、硫酸铜、氯化铜、四水乙酸镁中的两种或三种以上。
7.根据权利要求4所述的制备方法,其特征在于,所述煅烧的温度为500-800℃。
8.权利要求1-3任意一项所述的复合正极材料在制备正极极片或钠离子电池中的应用。
9.一种正极极片,其特征在于,包括集流体、导电剂、粘结剂和权利要求1-3任意一项所述的复合正极材料。
10.一种钠离子电池,其特征在于,包括负极极片、电解液、隔膜和权利要求9所述的正极极片。
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