CN103165881B - 掺杂磷酸铁锂纳米正极材料及其制备方法 - Google Patents
掺杂磷酸铁锂纳米正极材料及其制备方法 Download PDFInfo
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- CN103165881B CN103165881B CN201110418940.9A CN201110418940A CN103165881B CN 103165881 B CN103165881 B CN 103165881B CN 201110418940 A CN201110418940 A CN 201110418940A CN 103165881 B CN103165881 B CN 103165881B
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- hydroxide
- carbonate
- 1mol
- barium
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010405 anode material Substances 0.000 title claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052788 barium Inorganic materials 0.000 claims abstract description 18
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- 239000011777 magnesium Chemical group 0.000 claims abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010949 copper Chemical group 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- 239000011575 calcium Chemical group 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 239000012467 final product Substances 0.000 claims abstract description 9
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011733 molybdenum Chemical group 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- 239000010955 niobium Chemical group 0.000 claims abstract description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 9
- 239000011669 selenium Chemical group 0.000 claims abstract description 9
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 9
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 239000011701 zinc Chemical group 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000004332 silver Chemical group 0.000 claims abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004411 aluminium Chemical group 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011135 tin Chemical group 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- PWOSZCQLSAMRQW-UHFFFAOYSA-N beryllium(2+) Chemical compound [Be+2] PWOSZCQLSAMRQW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 25
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical group O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 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
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 229910052790 beryllium Inorganic materials 0.000 claims description 5
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 5
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 5
- 229910000011 cadmium carbonate Inorganic materials 0.000 claims description 5
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 5
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 5
- 239000011667 zinc carbonate Substances 0.000 claims description 5
- 235000004416 zinc carbonate Nutrition 0.000 claims description 5
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 3
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 claims description 3
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 3
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims description 3
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 3
- WPJWIROQQFWMMK-UHFFFAOYSA-L beryllium dihydroxide Chemical compound [Be+2].[OH-].[OH-] WPJWIROQQFWMMK-UHFFFAOYSA-L 0.000 claims description 3
- 229910001865 beryllium hydroxide Inorganic materials 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical group [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 claims description 3
- GKDXQAKPHKQZSC-UHFFFAOYSA-L cadmium(2+);carbonate Chemical compound [Cd+2].[O-]C([O-])=O GKDXQAKPHKQZSC-UHFFFAOYSA-L 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229940116318 copper carbonate Drugs 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
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical group [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical group [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 3
- 238000007254 oxidation reaction Methods 0.000 claims 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 125000005619 boric acid group Chemical group 0.000 claims 1
- 125000005586 carbonic acid group Chemical group 0.000 claims 1
- 125000003636 chemical group Chemical group 0.000 claims 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims 1
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims 1
- 239000001095 magnesium carbonate Substances 0.000 claims 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 claims 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims 1
- 229910001887 tin oxide Inorganic materials 0.000 claims 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract 1
- 229910000398 iron phosphate Inorganic materials 0.000 abstract 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 abstract 1
- 239000011858 nanopowder Substances 0.000 abstract 1
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 11
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 4
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910003378 NaNbO3 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 2
- KOHRTFCSIQIYAE-UHFFFAOYSA-N cadmium;carbonic acid Chemical compound [Cd].OC(O)=O KOHRTFCSIQIYAE-UHFFFAOYSA-N 0.000 description 2
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- -1 niobium sodium Chemical compound 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 2
- MUPJWXCPTRQOKY-UHFFFAOYSA-N sodium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Na+].[Nb+5] MUPJWXCPTRQOKY-UHFFFAOYSA-N 0.000 description 2
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 2
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013048 LiCoC2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
本发明的参杂磷酸铁锂纳米正极材料制备方法，其特征在于：其锂源、铁源、磷酸根源、参杂源M、钡源的原料，按照1mol Li：0‑0.00005mol M：0.0003‑0.003mol Ba：1mol Fe：1mol P比例混合后，在5‑120℃密封搅拌反应器中，反应0.5‑24小时，过滤、洗涤、烘干后得到纳米前驱体，将烘干得到的前驱体置于高温炉内，在氮气氛中，经500‑750℃高温煅烧16‑24h，即得本发明的参杂磷酸铁锂纳米粉末正极材料，其M为钛、银、铌、锗、钙、镁、铝、锆、硒、锶、硼、铜、钒、镍、锌、锑、钼、锡、锰、钴、镉、铋、铍元素之一等元素，所得粉末正极材料，粒度在30‑85nm范围，其首次放电容量大大提高，达160.21mAh/g以上。
Description
技术领域
本发明的掺杂磷酸铁锂纳米正极材料制备方法，属于一种锂电池正极材料制备方法，特别涉及一种磷酸铁锂电池正极材料制备方法。
背景技术
纳米材料是指在三维空间中至少有一维处于纳米尺度范围(1-100nm)或由它们作为基本单元构成的材料，纳米级结构材料简称为纳米材料(nanometer material)，是指其结构单元的尺寸介于1纳米～100纳米范围之间。由于它的尺寸已经接近电子的相干长度，它的性质因为强相干所带来的自组织使得性质发生很大变化。并且，其尺度已接近光的波长，加上其具有大表面的特殊效应，因此其所表现的特性，例如熔点、磁性、光学、导热、导电特性等等，往往不同于该物质在整体状态时所表现的性质。经公开专利检索，目前记载有关锂电池纳米正极材料专利申请3件，其为：兰州大学化学化工学院的00134039.5一种锂离子电池纳米正极材料LiCoC2的制备方法；清华大学；山西省玻璃陶瓷科学研究所的200610011712.9稀土掺杂包碳型纳米正极材料磷酸铁锂及其制备方法；上海交通大学的200710037314.9锂离子电池纳米正极材料的连续水热合成方法。
发明内容
本发明的目的在于：提出一种掺杂磷酸铁锂纳米正极材料及其制备方法。
掺杂改性的磷酸铁锂正极材料，通过掺杂可将电导率提高，高倍率充放电性能也得到改善，在一定程度上抑制了容量衰减的作用。掺杂途径可提高、改善锂离子正极材料性能，已是公认的一种可行的方式，其制成纳米级产品其性能将更优秀。
鉴于掺杂途径可提高、改善锂离子正极材料性能，已是公认的一种可行的方式。根据钡/锂的化学性质，电学性能，晶体结构特征，是最相近似的元素的特点：钡，是碱土金属中最活泼的元素，由于它很活泼，且容易被氧化，应保存在煤油和液体石蜡中。电离能5.212电子伏特，第一电离能502.9kJ/mol；晶体结构：晶胞为体心立方晶胞，每个晶胞含有2个金属原子；
晶胞参数：a＝502.8pm；b＝502.8pm；c＝502.8pm；α＝90°；β＝90°；γ＝90°。锂，金属元素，可与大量无机试剂和有机试剂发生反应。与氧、氮、硫等均能化合，由于易受氧化而变暗，且密度比煤油小，故应存放于液体石蜡中。电离能5.392电子伏特，第一电离能520.2kJ/mol；晶体结构：晶胞为体心立方晶胞，每个晶胞含有2个金属原子；晶胞参数：a＝351pm；b＝351pm；c＝351pm；α＝90°；β＝90°；γ＝90°。钡应是最易于起锂位掺杂作用的。通过钡掺杂进行试验、在用钡掺杂的情况，可再加入1-2个其它元素，构成2元或3元掺杂，以获得性能较好的锂电池正极材料，其制成纳米级产品其性能将更优秀。
本发明的掺杂磷酸铁锂纳米正极材料，其特征在于：粉末立度在30-85nm范围，其化学组成或化学通式可表述为：LiMxBayFePO4，x＝0-0.00005，y＝0.0003-0.003；其中Li、M、Ba、Fe、P的mol比为：1mol Li∶0-0.00005mol M∶0.0003-0.003mol Ba∶1mol Fe∶1mol P。M是掺杂元素，其掺杂元素M：可是掺杂元素钛、银、铌、锗、钙、镁、铝、锆、硒、锶、硼、铜、钒、镍、锌、锑、钼、锡、锰、钴、镉、铋、铍之一或不少于2种元素，
本发明的掺杂磷酸铁锂纳米正极材料制备方法，其特征在于：其锂源、铁源、磷酸根源、掺杂源M、钡源的原料，按照1mol Li∶0-0.00005mol M∶0.0003-0.003mol Ba∶1mol Fe∶1mol P比例混合后，在5-120℃密封搅拌反应器中，反应0.5-24小时，过滤、洗涤、烘干后得到纳米前驱体，将烘干得到的前驱体置于高温炉内，在氮气氛中，经500-750℃高温煅烧16-24h，即得本发明的掺杂磷酸铁锂纳米粉末正极材料。其M为钛、银、铌、锗、钙、镁、铝、锆、硒、锶、硼、铜、钒、镍、锌、锑、钼、锡、锰、钴、镉、铋、铍元素之一或不少于2种元素。
其锂源为碳酸锂、氢氧化锂之一，
铁源为草酸亚铁，
磷酸根源为磷酸二氢铵或磷酸氢二铵之一，
钡源为碳酸钡、氢氧化钡、氯化钡、硝酸钡、氧化钡、硫化钡之一。
掺杂元素M源为如下元素源之一或不少于2种元素源的混合物，
掺杂元素M源：
钛源为、为偏钛酸、二氧化钛、四氯化钛等；
银源为、为硝酸银AgNO3、氧化银Ag2O等，
铌源为，铌铌酸钠(NaNbO3)，铌酸NbO3，五氧化二铌(Nb2O5)等；
锗源为氧化锗GeO2等；
钙源为、为碳酸钙等；
镁源为、为氧化镁(MgO)，碳酸镁(MgCO3)，氢氧化镁(Mg(OH)2)等；
铝源为、为氢氧化铝(Al(OH)3)等；
锆源为，碳酸锆铵(ZrO(CO3)2(NH4)2·nH2O)，氢氧化锆(ZrO(OH)2nH2O)、四氯化锆(ZrCl4)等；
硒源、为硒粉等；
锶源，为金属锶，氢氧化锶(Sr(OH)2)、碳酸锶SrCO3、等；
硼源，为硼酸等；
铜源，为碱式碳酸铜Cu2(OH)2CO3、氢氧化铜Cu(OH)等；
钒源，为五氧化二钒V2O5等；
镍源，为氢氧化镍Ni(OH)2、碳酸镍NiCO3等；
锌源，为碳酸锌ZnCO3、氧化锌ZnO等；
锑源，为三氧化二锑Sb2O3等；
钼源，为三氧化钼MoO3、钼酸铵(NH4)6Mo7O24·4H2等；
锡源，为二氧化锡SnO2等；
锰源，为碳酸亚锰MnCO3，、氢氧化锰Mn(OH)2、二氧化锰MnO2等；
钴源为草酸钴CoC2O4、碳酸钴CoCO3、氧化钴CoO、氢氧化钴Co(OH)2等；
镉源，为氢氧化镉Cd(OH)2、氧化镉CdO、碳酸镉CdCO3等；
铋源，为三氧化二铋Bi2O3、硝酸铋Bi(NO3)3.5H2O等；
铍源，为氢氧化铍Be(OH)2、氧化铍BeO等；
本发明与现有技术相比的有益效果：
本发明的掺杂磷酸铁锂纳米正极材料制备方法，所得纳米粉末正极材料，立度在30-85nm范围，其首次放电容量大大提高，达160.21mAh/g以上。
具体实施方式
下面结合实施例对本发明作进一步说明，但本发明的实施方式不限于此。
实施例1
本发明的掺杂磷酸铁锂纳米正极材料制备方法，其锂源可用：碳酸锂、氢氧化锂等锂盐，铁源可用：草酸亚铁等，磷酸根源可用：磷酸二氢铵或磷酸氢二铵等，钡源可用：碳酸钡、氢氧化钡、氯化钡、硝酸钡、氧化钡、硫化钡等钡盐，掺杂元素源化合物。
选用：碳酸锂(Li2CO3)(99.73％)，碳酸钡(BaCO3)(99.8％)，草酸亚铁(FeC2O4.2H2O)(99.06％)，磷酸氢二铵(NH4H2PO4)(98％)为原料和掺杂元素源化合物；按照1mol Li∶0-0.00005mol M∶0.0003-0.003mol Ba∶1mol Fe∶1mol P比例混合后，在5-120℃密封搅拌反应器中，反应0.5-24小时，过滤、洗涤、烘干后得到纳米前驱体，将烘干得到的前驱体置于高温炉内，在氮气氛中，经500-750℃高温煅烧16-24h，即得本发明的掺杂磷酸铁锂纳米粉末正极材料。其掺杂元素M：可是掺杂元素钛、银、铌、锗、钙、镁、铝、锆、硒、锶、硼、铜、钒、镍、锌、锑、钼、锡、锰、钴、镉、铋、铍之一，
所述掺杂元素M源：
钛源为、为偏钛酸、二氧化钛、四氯化钛等；
银源为、为硝酸银AgNO3、氧化银Ag2O等，
铌源为，铌铌酸钠(NaNbO3)，铌酸NbO3，五氧化二铌(Nb2O5)等；
锗源为氧化锗GeO2等；
钙源为、为碳酸钙等；
镁源为、为氧化镁(MgO)，碳酸镁(MgCO3)，氢氧化镁(Mg(OH)2)等；
铝源为、为氢氧化铝(Al(OH)3)等；
锆源为，碳酸锆铵(ZrO(CO3)2(NH4)2·nH2O)，氢氧化锆(ZrO(OH)2nH2O)、四氯化锆(ZrCl4)等；
硒源、为硒粉等；
锶源，为金属锶，氢氧化锶(Sr(OH)2)、碳酸锶SrCO3、等；
硼源，为硼酸等；
铜源，为碱式碳酸铜Cu2(OH)2CO3、氢氧化铜Cu(OH)等；
钒源，为五氧化二钒V2O5等；
镍源，为氢氧化镍Ni(OH)2、碳酸镍NiCO3等；
锌源，为碳酸锌ZnCO3、氧化锌ZnO等；
锑源，为三氧化二锑Sb2O3等；
钼源，为三氧化钼MoO3、钼酸铵(NH4)6Mo7O24·4H2等；
锡源，为二氧化锡SnO2等；
锰源，为碳酸亚锰MnCO3，、氢氧化锰Mn(OH)2、二氧化锰MnO2等；
钴源为草酸钴CoC2O4、碳酸钴CoCO3、氧化钴CoO、氢氧化钴Co(OH)2等；
镉源，为氢氧化镉Cd(OH)2、氧化镉CdO、碳酸镉CdCO3等；
铋源，为三氧化二铋Bi2O3、硝酸铋Bi(NO3)3.5H2O等；
铍源，为氢氧化铍Be(OH)2、氧化铍BeO等；
实施例2
Li2CO3(99.7)，BaCO3(99.8％)，FeC2O4.2H2O(99.06％)，NH4H2PO4(98％)原料和掺杂元素M源，按照1mol Li∶0.00002mol M∶0.0003mol Ba∶1mol Fe∶1mol P比例混合后，在5-10℃密封搅拌反应器中，反应24小时，过滤、洗涤、烘干后得到纳米前驱体，将烘干得到的前驱体置于高温炉内，在氮气氛中，经500-750℃高温煅烧16-24h，即得本发明的掺杂磷酸铁锂纳米粉末正极材料。其掺杂元素M与实施例1的相同。
实施例3
Li2CO3(99.7)，BaCO3(99.8％)，FeC2O4.2H2O(99.06％)，NH4H2PO4(98％)原料和掺杂元素M源，按照1mol Li∶0.00002mol M∶0.0003mol Ba∶1mol Fe∶1mol P比例混合后，在20-30℃密封搅拌反应器中，反应20小时，过滤、洗涤、烘干后得到纳米前驱体，将烘干得到的前驱体置于高温炉内，在氮气氛中，经500-750℃高温煅烧16-24h，即得本发明的掺杂磷酸铁锂纳米粉末正极材料。其掺杂元素M与实施例1的相同。
实施例4
Li2CO3(99.73％)，BaCO3(99.8％)，FeC2O4.2H2O(99.06％)，NH4H2PO4(98％)原料和掺杂元素M源，按照1mol Li∶0.00004mol M∶0.001mol Ba∶1mol Fe∶1mol P比例混合后，在50-80℃密封搅拌反应器中，反应5小时，过滤、洗涤、烘干后得到纳米前驱体，将烘干得到的前驱体置于高温炉内，在氮气氛中，经500-750℃高温煅烧16-24h，即得本发明的掺杂磷酸铁锂纳米粉末正极材料。其掺杂元素M与实施例1的相同。
实施例5
Li2CO3(99.73％)，BaCO3(99.8％)，FeC2O4.2H2O(99.06％)，NH4H2PO4(98％)原料和掺杂元素M源(偏钛酸和硝酸银1∶1mol的混合物)，按照1mol Li∶0.00005mol M∶0.003molBa∶1mol Fe∶1mol P比例混合后，在100-120℃密封搅拌反应器中，反应0.5小时，过滤、洗涤、烘干后得到纳米前驱体，将烘干得到的前驱体置于高温炉内，在氮气氛中，经500-750℃高温煅烧16-24h，即得本发明的掺杂磷酸铁锂纳米粉末正极材料。其掺杂元素M与实施例1的相同。
实施例5(仅钡掺杂)
Li2CO3(99.73％)，BaCO3(99.8％)，FeC2O4.2H2O(99.06％)，NH4H2PO4(98％)原料和掺杂元素M源，按照1mol Li∶0molM∶0.003mol Ba∶1mol Fe∶1mol P比例混合后，在100-120℃密封搅拌反应器中，反应0.5小时，过滤、洗涤、烘干后得到纳米前驱体，将烘干得到的前驱体置于高温炉内，在氮气氛中，经500-750℃高温煅烧16-24h，即得本发明的掺杂磷酸铁锂纳米粉末正极材料。其掺杂元素M与实施例1的相同。
采用现有技术的测试设备及现有技术的测试方法，对以上实施例1-6的磷酸铁锂纳米粉末正极材料，进行测试结果为：粉末立度在30-85nm范围，首次放电容量达160.21mAh/g以上。
Claims (3)
1.一种掺杂磷酸铁锂纳米正极材料，其特征在于：粉末粒度在30-85nm范围，用化学组成表述为：LiMxBayFePO4，x＝0.00002-0.00004，y＝0.0003；其中Li、M、Ba、Fe、P的mol比为：1mol Li∶0.00002-0.00004mol M∶0.0003mol Ba∶1mol Fe∶1mol P，其M为钛、银、铌、锗、钙、镁、铝、锆、硒、锶、硼、铜、钒、镍、锌、锑、钼、锡、锰、钴、镉、铋、铍元素中不少于2种元素混合物。
2.一种掺杂磷酸铁锂纳米正极材料制备方法，其特征在于：其锂源、铁源、磷酸根源、掺杂元素M源、钡源的原料，按照1mol Li∶0.00002-0.00004mol M∶0.0003mol Ba∶1mol Fe∶1mol P比例混合后，在5-120℃密封搅拌反应器中，反应0.5-24小时，过滤、洗涤、烘干后得到纳米前驱体，将烘干得到的前驱体置于高温炉内，在氮气氛中，经500-750℃高温煅烧16-24h，即得本发明的掺杂磷酸铁锂纳米粉末正极材料，其M为钛、银、铌、锗、钙、镁、铝、锆、硒、锶、硼、铜、钒、镍、锌、锑、钼、锡、锰、钴、镉、铋、铍元素之一或不少于2种元素。
3.根据权利要求2所述的掺杂磷酸铁锂纳米正极材料制备方法，其特征在于：其锂源为碳酸锂、氢氧化锂之一，其铁源为草酸亚铁，磷酸根源为磷酸二氢铵或磷酸氢二铵之一，钡源为碳酸钡、氢氧化钡、氯化钡、硝酸钡、氧化钡、硫化钡之一，掺杂元素M源为如下元素源的不少于2种元素源的混合物，钛源为偏钛酸、二氧化钛、四氯化钛之一，银源为硝酸银、氧化银之一，铌源为铌酸钠、铌酸、五氧化二铌之一，锗源为氧化锗，钙源为碳酸钙，镁源为氧化镁，碳酸镁，氢氧化镁之一，铝源为氢氧化铝，锆源为碳酸锆铵、氢氧化锆、四氯化锆之一，硒源为硒粉，锶源为金属锶、氢氧化锶、碳酸锶之一，硼源为硼酸，铜源为碱式碳酸铜、氢氧化铜之一，钒源为五氧化二钒，镍源为氢氧化镍、碳酸镍之一，锌源为碳酸锌、氧化锌之一，锑源为三氧化二锑，钼源为三氧化钼、钼酸铵之一，锡源为氧化锡，锰源为碳酸亚锰、氢氧化锰、二氧化锰之一，钴源为草酸钴、碳酸钴、氧化钴、氢氧化钴之一，镉源为氢氧化镉、氧化镉、碳酸镉之一，铋源为三氧化二铋、硝酸铋之一，铍源为氢氧化铍、氧化铍之一。
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| CN103594685B (zh) * | 2013-08-20 | 2015-09-23 | 湖北文理学院 | 一种锂离子电池正极材料改性三氧化钼的制备方法 |
| CN105514427A (zh) * | 2015-12-23 | 2016-04-20 | 邬石根 | 一种掺杂Ti的LiFe1-xTixPO4电极材料 |
| CN107473197A (zh) * | 2017-09-08 | 2017-12-15 | 绵阳梨坪科技有限公司 | 一种提高电池性能掺杂磷酸亚铁锂材料的制备方法 |
| CN108083330B (zh) * | 2017-12-08 | 2019-10-25 | 蒋央芳 | 一种掺杂纳米二氧化钛的磷酸铁的制备方法 |
| CN108046791B (zh) * | 2018-01-12 | 2020-08-04 | 河北工业大学 | 一种以纳米MnZn铁氧体粉体制备铁氧体的方法 |
| CN109216694B (zh) * | 2018-08-04 | 2021-06-29 | 浙江金鹰瓦力新能源科技有限公司 | 一种改性锰酸锂正极材料及其制备方法 |
| CN110021752B (zh) * | 2019-01-24 | 2022-10-25 | 湖北锂诺新能源科技有限公司 | 一种锂、铝和氟共掺杂磷酸铁锂正极材料及制备方法 |
| CN111063952B (zh) * | 2019-11-30 | 2021-02-09 | 山东同大新能源有限公司 | 一种磷酸铁锂锂离子电池及其化成工艺 |
| CN111342018B (zh) * | 2020-03-10 | 2022-09-16 | 四川联伍新能源科技有限公司 | 一种碳包覆含锂过渡金属磷酸盐正极材料及其制备方法 |
| CN114715858B (zh) * | 2022-04-02 | 2023-08-25 | 宁夏大学 | 硒化硫钒铜固溶体制备方法、负极材料和钠离子电池 |
| CN116826040A (zh) * | 2022-11-11 | 2023-09-29 | 中科致良新能源材料(浙江)有限公司 | 一种具有纳米多孔结构的磷酸锰铁及其制备方法和用途 |
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