CN117012956A - 一种铁锰钴基富钠阴离子掺杂的正极材料及其制备方法 - Google Patents
一种铁锰钴基富钠阴离子掺杂的正极材料及其制备方法 Download PDFInfo
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- CN117012956A CN117012956A CN202311244638.5A CN202311244638A CN117012956A CN 117012956 A CN117012956 A CN 117012956A CN 202311244638 A CN202311244638 A CN 202311244638A CN 117012956 A CN117012956 A CN 117012956A
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- China
- Prior art keywords
- sodium
- manganese
- source
- cobalt
- equal
- Prior art date
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- 239000011734 sodium Substances 0.000 title claims abstract description 64
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 23
- 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 title claims abstract description 22
- 150000001450 anions Chemical class 0.000 title abstract description 11
- UOJLTGJDEASXFF-UHFFFAOYSA-N [Mn].[Co].[Fe] Chemical compound [Mn].[Co].[Fe] UOJLTGJDEASXFF-UHFFFAOYSA-N 0.000 title abstract description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 68
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 57
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 41
- 239000011572 manganese Substances 0.000 claims description 29
- 239000001913 cellulose Substances 0.000 claims description 24
- 229920002678 cellulose Polymers 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 18
- 238000001816 cooling Methods 0.000 claims description 18
- 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 18
- 238000012216 screening Methods 0.000 claims description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 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 10
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 10
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 8
- 229940044175 cobalt sulfate Drugs 0.000 claims description 8
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011656 manganese carbonate Substances 0.000 claims description 8
- 235000006748 manganese carbonate Nutrition 0.000 claims description 8
- 229940093474 manganese carbonate Drugs 0.000 claims description 8
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 8
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 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
- 239000000126 substance Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 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 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005715 Fructose Substances 0.000 claims description 4
- 229930091371 Fructose Natural products 0.000 claims description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 4
- 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 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- WRMXOVHLRUVREB-UHFFFAOYSA-N phosphono phosphate;tributylazanium Chemical compound OP(O)(=O)OP([O-])([O-])=O.CCCC[NH+](CCCC)CCCC.CCCC[NH+](CCCC)CCCC WRMXOVHLRUVREB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 claims description 2
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- RTBHLGSMKCPLCQ-UHFFFAOYSA-N [Mn].OOO Chemical compound [Mn].OOO RTBHLGSMKCPLCQ-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- -1 cobalt oxyhydroxide Chemical compound 0.000 claims description 2
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims description 2
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims description 2
- JECJVZVHLPZRNM-UHFFFAOYSA-J cobalt(2+);phosphonato phosphate Chemical compound [Co+2].[Co+2].[O-]P([O-])(=O)OP([O-])([O-])=O JECJVZVHLPZRNM-UHFFFAOYSA-J 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 239000011564 manganese citrate Substances 0.000 claims description 2
- 235000014872 manganese citrate Nutrition 0.000 claims description 2
- 229940097206 manganese citrate Drugs 0.000 claims description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 2
- 229940099594 manganese dioxide Drugs 0.000 claims description 2
- 229940077478 manganese phosphate Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- LQKOJSSIKZIEJC-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] LQKOJSSIKZIEJC-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229920001690 polydopamine Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- 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 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- 229940083608 sodium hydroxide Drugs 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000001540 sodium lactate Substances 0.000 claims description 2
- 235000011088 sodium lactate Nutrition 0.000 claims description 2
- 229940005581 sodium lactate Drugs 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 239000001433 sodium tartrate Substances 0.000 claims description 2
- 229960002167 sodium tartrate Drugs 0.000 claims description 2
- 235000011004 sodium tartrates Nutrition 0.000 claims description 2
- OYFUIMQYZOLBMZ-UHFFFAOYSA-J tetrachloromanganese Chemical compound Cl[Mn](Cl)(Cl)Cl OYFUIMQYZOLBMZ-UHFFFAOYSA-J 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims 1
- 229960002413 ferric citrate Drugs 0.000 claims 1
- 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 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- 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 1
- 239000000463 material Substances 0.000 abstract description 19
- 238000009831 deintercalation Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 5
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- BYTVRGSKFNKHHE-UHFFFAOYSA-K sodium;[hydroxy(oxido)phosphoryl] phosphate;iron(2+) Chemical compound [Na+].[Fe+2].OP([O-])(=O)OP([O-])([O-])=O BYTVRGSKFNKHHE-UHFFFAOYSA-K 0.000 abstract description 3
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 238000001694 spray drying Methods 0.000 description 35
- 239000004576 sand Substances 0.000 description 34
- 239000002002 slurry Substances 0.000 description 34
- 238000010438 heat treatment Methods 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 239000002243 precursor Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 238000005303 weighing Methods 0.000 description 17
- 238000001354 calcination Methods 0.000 description 15
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 14
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 8
- 229940074545 sodium dihydrogen phosphate dihydrate Drugs 0.000 description 8
- 239000004254 Ammonium phosphate Substances 0.000 description 7
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 7
- 235000019289 ammonium phosphates Nutrition 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 229960005191 ferric oxide Drugs 0.000 description 6
- 229960004106 citric acid Drugs 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 4
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229920000447 polyanionic polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 241000234314 Zingiber Species 0.000 description 2
- 235000006886 Zingiber officinale Nutrition 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229960002303 citric acid monohydrate Drugs 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 235000008397 ginger Nutrition 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021569 Manganese fluoride Inorganic materials 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000011645 ferric sodium diphosphate Substances 0.000 description 1
- 235000019851 ferric sodium diphosphate Nutrition 0.000 description 1
- 229940046149 ferrous bromide Drugs 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- BRFMYUCUGXFMIO-UHFFFAOYSA-N phosphono dihydrogen phosphate phosphoric acid Chemical compound OP(O)(O)=O.OP(O)(=O)OP(O)(O)=O BRFMYUCUGXFMIO-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- XWQGIDJIEPIQBD-UHFFFAOYSA-J sodium;iron(3+);phosphonato phosphate Chemical compound [Na+].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O XWQGIDJIEPIQBD-UHFFFAOYSA-J 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- C01B32/00—Carbon; Compounds thereof
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- 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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
本发明涉及一种铁锰钴基富钠阴离子掺杂的正极材料及其制备方法和应用。本发明通过适当增加钠离子形成富钠结构,使得可逆脱嵌钠离子数量增加,以提高正极材料的克容量和能量密度;通过金属空位和阴离子的引入,可以显著减少磷酸铁钠和焦磷酸铁钠杂质,提高材料的纯度和结构稳定性,从而也提高了正极材料的离子电导率和倍率性能、和循环稳定性。同时本发明制备工艺流程绿色环保,简单可控,适合规模化生产。
Description
技术领域
本发明涉及材料技术领域,特别涉及一种铁锰钴基富钠阴离子掺杂的正极材料及其制备方法和应用。
背景技术
锂离子电池因具有比能量高、自放电小、无记忆效应、循环寿命长等优点已经被广泛应用于3C产品和电动汽车等领域,然而锂资源有限,且分布不均匀。与锂处于同一主族的钠,其物理化学性质与锂十分相似,而含量却更为丰富,成本低廉。钠离子电池原理和锂离子电池类似,大部分设备可以通用,因此,钠离子二次电池被视为是锂离子电池理想的替代品,并有望应用于大规模储能设备。
目前钠离子电池以正极材料分磷酸盐、氟磷酸盐、普鲁士蓝及其衍生物、氧化物三种技术路线。其中磷酸盐正极材料具有突出的热稳定性和结构稳定性,循环性能好,铁基磷酸盐正极材料成本低,有望用于储能型钠离子电池正极材料。
目前,铁基混合聚阴离子型化合物Na4Fe3(PO4)2P2O7受广泛的关注,它具有较高的理论比容量、小的体积变化并且成本低、安全性高、环境友好、储量丰富的优点,使该材料在大规模储能系统方面具有很大的优势。然而,作为聚阴离子型化合物,Na4Fe3(PO4)2P2O7同样也存在平均工作电压较低、克容量低、电导率低、杂相的问题。
发明内容
本发明目的在于解决现有技术中铁基混合聚阴离子型化合物Na4Fe3(PO4)2P2O7所存在的克容量低、电导率低、平均工作电压较低的问题,提出了一种铁锰钴基富钠阴离子掺杂的正极材料及其制备方法和应用,所得到的正极材料结构稳定性、导电性高、电压平台高、倍率性能好、循环性好、克容量高。
为了解决上述技术问题,本发明是通过如下技术方案得以实现的。
本发明第一方面提供了一种钠离子电池正极材料,其化学式为Na4+xFey1Mny2Coy3(PO4)2P2O7Mz/C;其中M选自F、Br、Cl中的一种或多种;0.001≤x≤0.5,0.1≤y1≤3,0.1≤y2≤2.5,0<y3≤0.5,0<z≤0.2;且x、y1、y2、y3、z满足如下条件:
0<x/(2(3-y1-y2-y3)+z)<1.1;2.7≤y1+y2+y3≤3。
应理解的是,在无特别说明的情况下,本发明上下文中所述x、y1、y2、y3、z等代表钠离子电池正极材料中各元素物质的量的相对比例,例如当x=0.1,y1=1.6,y2=1.2,y3=0.1,z=0.1且M选自F时,所述钠离子电池正极材料的分子式即为Na4.1Fe1.6Mn1.2Co0.1(PO4)2P2O7F0.1/C。
作为优选地,0.002≤x≤0.45,0.2≤y1≤2.8,0.15≤y2≤2,0<y3≤0.4,0.003≤z≤0.1;0.01<x/(2(3-y1-y2-y3)+z)<1;2.8≤y1+y2+y3≤2.98。
作为优选地,0.003≤x≤0.40,0.3≤y1≤2.7,0.2≤y1≤1.5,0<y3≤0.2,0.04≤z≤0.08;0.03≤x/(2(3-y1-y2-y3)+z)≤0.9;2.8≤y1+y2+y3≤2.95。
作为优选地,C在正极材料Na4+xFey1Mny2Coy3(PO4)2P2O7Mz/C中的质量比为α,其中0<α<0.2。
本发明第二方面提供了上述钠离子电池正极材料的制备方法,包括如下步骤:
(1)将钠源、铁源、锰源、钴源、磷源、碳源、M源、溶剂进行充分混合;其中M源选自氟源、溴源、氯源中的一种或多种;
(2)将步骤(1)混合后的原料进行干燥,随后进行高温烧结处理,最后降温至室温后经粉碎、筛分即得。
作为优选地,步骤(1)中所述钠源选自碳酸钠、碳酸氢钠、硝酸钠、磷酸钠、酒石酸钠、磷酸二氢钠、磷酸一氢钠、焦磷酸二氢钠、海藻酸钠、乳酸钠、氢氧化钠、甲酸钠、柠檬酸钠、草酸钠、醋酸钠中的一种或多种。
作为优选地,步骤(1)中所述铁源选自磷酸铁、焦磷酸铁、醋酸铁、硝酸亚铁、氯化亚铁、硝酸铁、氧化铁、硫酸铁、氯化铁、铁粉、柠檬酸铁、柠檬酸亚铁、硫酸亚铁、四氧化三铁、三氧化二铁、氧化亚铁、乙酸铁、硫酸亚铁铵中的一种或多种。
作为优选地,步骤(1)中所述锰源选自氢氧化锰、羟基氧化锰、磷酸锰、硫酸锰、乙酸锰、二氧化锰、三氧化二锰、四氧化三猛、碳酸锰、柠檬酸锰、锰粉、四氯化锰、硝酸锰、醋酸锰中的一种或多种。
作为优选地,步骤(1)中所述钴源选自磷酸钴、焦磷酸钴、醋酸钴、硝酸钴、氯化钴、三氧化二钴、硫酸钴、氢氧化钴、羟基氧化钴中的一种或多种。
作为优选地,步骤(1)中所述磷源选自磷酸、磷酸铁、磷酸一氢钠、磷酸二氢钠、磷酸钠、磷酸一氢铵、焦磷酸二氢钠、磷酸二氢铵、磷酸铵中的一种或多种。
作为优选地,步骤(1)中所述碳源选自葡萄糖、果糖、淀粉、纤维素、麦芽糖、PEO、柠檬酸、聚多巴胺、树脂、草酸、抗坏血酸、甲醛、乳酸、苹果酸、乙二酸、己二酸、乙醛、正丁醛中一种或多种。
作为优选地,步骤(1)中所述氟源选自氟源为氟化钠、氟化铁、氟化亚铁、氟化锰、氟化钴、氟化铵中的一种或多种。
作为优选地,步骤(1)中所述溴源选自溴化钠、溴化铁、溴化亚铁、溴化锰、溴化钴、溴化铵中的一种或多种。
作为优选地,步骤(1)中所述氯源选自氯化钠、氯化铁、氯化亚铁、氯化钴、氯化锰、氯化铵中的一种或多种。
作为优选地,步骤(1)中所述溶剂选自水、乙醇、丙醇、NMP、丙酮、乙醚中的一种或多种。
作为优选地,步骤(1)中所述钠源、铁源、锰源、钴源、磷源、M源按照Na、Fe、Mn、Co、P、M摩尔比为4+x:y1:y2:y3:4:z进行混合。对于碳源的用量,本领域技术人员可根据得碳率进行确定并添加,例如可按照原材料质量的0-2倍进行添加。
作为优选地,步骤(1)中所述混合选自机械混合、球磨混合、溶液分散、溶解中的一种或多种。
作为优选地,步骤(2)中所述干燥选自喷雾干燥、鼓风干燥、真空干燥、冷冻干燥、自然晒干中一种或多种。
作为优选地,步骤(2)中所述高温烧结的温度为200-600℃,时间为2-48h。
作为优选地,步骤(2)中所述高温烧结于惰性气体氛围下进行。
作为优选地,步骤(2)中所述惰性气体选自氩气、氮气中的一种或多种。
本发明第三方面提供了一种钠离子电池,包含上述钠离子电池正极材料和/或根据上述制备方法制备得到的钠离子电池正极材料。
本发明通过大量研究发现,在铁元素的基础上进一步掺杂特定含量的金属元素锰和/或钴,可以形成过渡金属空位,以扭曲周围元素的化学键,拓展钠离子脱嵌通道,提高钠离子的传输速度,进而提高充放电过程中正极材料的离子导电率。同时,在正极材料中掺杂适宜的阴离子(氟、溴、氯等)可以扭曲周围其他元素的化学键,提高周围电子云密度,进而提高材料离子电导率和电子电导率。正极材料的离子电导率和电子电导率的提高,则可以提升材料的充放电反应动力学,有助于提高材料的倍率性能和比容量。
然而,几种金属元素掺杂量对于材料电化学性能有关键影响,当铁元素相对量y1过小、锰元素相对量y2和钴元素相对量y3过大时,高含量的锰元素会导致姜泰勒效应,使得正极材料的稳定性降低,且钴元素难以发挥全部容量,在一定电压范围内正极材料克容量较低,同时会增加材料成本;而当铁元素相对量y1过大、锰元素相对量y2和钴元素相对量y3过小时,则会导致正极材料的中值电压和能量密度显著降低;同时当金属元素空位太多时,会导致材料结构不稳定,降低正极材料的循环性能,如果空位太少时,正极材料的杂质比较多,不利于材料克容量和倍率性能发挥;阴离子含量太高则会影响材料结构稳定性,降低正极材料的循环性能。本发明则通过研究发现,通过控制y1、y2、y3、z在如下范围:0.1≤y1≤3,0.1≤y2≤2.5,0<y3≤0.5,0<z≤0.2,同时2.7≤y1+y2+y3≤3时,能够有效降低姜泰勒效应,提高正极材料稳定性和克容量,同时增加正极材料的中值电压和能量密度。
现有技术中磷酸焦磷酸复合聚阴离子正极材料Na4Ma(PO4)2P2O7内钠离子与阴离子的摩尔比通常为定值。本发明则通过在正极材料中增加钠离子含量使之成为富钠结构,能够使得可逆脱嵌钠离子数量增加,进而提高正极材料的克容量和能量密度。然而对于钠离子的增量x有严格要求,如果x过大,材料表面残钠显著增加,会导致材料充放电过程中产气发生,循环性能下降;而x过小,材料晶格内钠含量低,可逆脱嵌钠量降低,则会导致正极材料的克容量降低。本发明通过研究发现,通过控制0.001≤x≤0.5,且0<x/(2(3-y1-y2-y3)+z)<1.1时,可以有效避免因钠离子含量过低导致的克容量下降,同时可以避免因残钠增加导致的循环性能大幅度降低。
总的来说,本发明通过适当增加钠离子形成富钠结构,使得可逆脱嵌钠离子数量增加,以提高正极材料的克容量和能量密度;通过金属空位和阴离子的引入,可以显著减少磷酸铁钠和焦磷酸铁钠杂质,提高材料的纯度和结构稳定性,从而也提高了正极材料的离子电导率和倍率性能、和循环稳定性。同时本发明制备工艺流程绿色环保,简单可控,适合规模化生产。
附图说明
图1为实施例1前驱体材料形貌图。
图2为实施例1钠离子电池正极材料形貌图。
具体实施方式
为使本发明的目的、技术方案及效果更加清楚、明确,以下参照实施例对本发明作进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
实施例1
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:F摩尔比为4.03:2.25:0.5:0.2:4:0.05称取二水合磷酸二氢钠、三氧化二铁、碳酸锰、硫酸钴和氟化铵进行混合,加入水以及果糖,其中果糖为其他固体成分总质量的20%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃,所得材料如图1所示;随后于氮气条件下,以2℃/min的速率升温至550℃,高温煅烧处理24h,再以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.03Fe2.25Mn0.5Co0.2(PO4)2P2O7F0.05/C,如图2所示。
实施例2
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:F摩尔比为4.08:2.55:0.3:0.1:4:0.05称取碳酸钠、九水合硝酸铁、四氧化三锰、硝酸钴、二水合磷酸二氢钠、氟化钠进行混合,加入水以及一水合柠檬酸,其中一水合柠檬酸为其他固体成分总质量的35%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃;随后于氮气条件下,以2℃/min的速率升温至540℃,高温煅烧处理12h,再以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.08Fe2.55Mn0.3Co0.1(PO4)2P2O7F0.05/C。
实施例3
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:Cl摩尔比为4.14:2.55:0.3: 0.1:4:0.05称取九水合硝酸铁、四氧化三锰、硝酸钴、二水合磷酸二氢钠、氯化钠进行混合,加入水以及柠檬酸,其中柠檬酸为其他固体成分总质量的50%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃;随后于氮气条件下,以2℃/min的速率升温至260℃,恒温处理2h,再以2℃/min的速率升温至550℃,高温煅烧处理10h,以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.14Fe2.55Mn0.3Co0.1(PO4)2P2O7Cl0.05/C。
实施例4
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:Br摩尔比为4.09:2.55:0.3:0.1:4:0.05称取碳酸氢钠、磷酸、硝酸铁、硝酸锰、三氧化二钴和溴化铵进行混合,加入水以及纤维素,其中纤维素为其他固体成分总质量的20%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃;随后于氮气条件下,以2℃/min的速率升温至550℃,高温煅烧处理24h,再以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.09Fe2.55Mn0.3Co0.1(PO4)2P2O7Br0.05/C。
实施例5
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:F:Cl:Br摩尔比为4.07:2.55:0.3:0.1:4:0.03:0.01:0.01称取碳酸氢钠、磷酸、硝酸铁、硝酸锰、三氧化二钴、氟化铵、氯化铵、溴化铵进行混合,加入水以及淀粉,其中淀粉为其他固体成分总质量的20%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃;随后于氮气条件下,以2℃/min的速率升温至550℃,高温煅烧处理24h,再以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.07Fe2.55Mn0.3Co0.1(PO4)2P2O7F0.03Cl0.01Br0.01/C。
实施例6
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:F摩尔比为4.03:1.4:1.4:0.2:4:0.05称取硝酸钠、磷酸铵、氧化铁、氧化锰、醋酸钴和氟化铵进行混合,加入水以及葡萄糖,其中葡萄糖为其他固体成分总质量的20%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃;随后于氮气条件下,以2℃/min的速率升温至550℃,高温煅烧处理24h,再以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.03Fe1.4Mn1.4Co0.2(PO4)2P2O7F0.05/C。
实施例7
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:F摩尔比为4.05:0.3:2.5:0.2:4:0.06称取碳酸氢钠、磷酸、硝酸铁、硝酸锰、三氧化二钴和氟化铵进行混合,加入水以及纤维素,其中纤维素为其他固体成分总质量的20%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃;随后于氮气条件下,以2℃/min的速率升温至550℃,高温煅烧处理24h,再以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.05Fe0.3Mn2.5Co0.2(PO4)2P2O7F0.06/C。
实施例8
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:F摩尔比为4.14:2.15:0.3:0.5:4:0.05称取碳酸氢钠、磷酸铵、硝酸铁、硝酸锰、三氧化二钴和氟化铵进行混合,加入水以及纤维素,其中纤维素为其他固体成分总质量的20%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃;随后于氮气条件下,以2℃/min的速率升温至550℃,高温煅烧处理24h,再以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.14Fe2.15Mn0.3Co0.5(PO4)2P2O7F0.05/C。
实施例9
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:F摩尔比为4.07:2.5:0.3:0.1:4:0.05称取碳酸氢钠、磷酸铵、硝酸铁、硝酸锰、三氧化二钴和氟化铵进行混合,加入水以及纤维素,其中纤维素为其他固体成分总质量的20%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃;随后于氮气条件下,以2℃/min的速率升温至550℃,高温煅烧处理24h,再以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.07Fe2.5Mn0.3Co0.1(PO4)2P2O7F0.05/C。
实施例10
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:F摩尔比为4.16:2.45:0.3:0.1:4:0.05称取碳酸氢钠、磷酸铵、硝酸铁、硝酸锰、三氧化二钴和氟化铵进行混合,加入水以及纤维素,其中纤维素为其他固体成分总质量的20%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃;随后于氮气条件下,以2℃/min的速率升温至550℃,高温煅烧处理24h,再以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.16Fe2.45Mn0.3Co0.1(PO4)2P2O7F0.05/C。
实施例11
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:F摩尔比为4.07:2.55:0.2:0.05:4:0.05称取碳酸氢钠、磷酸铵、硝酸铁、硝酸锰、三氧化二钴和氟化铵进行混合,加入水以及纤维素,其中纤维素为其他固体成分总质量的20%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃;随后于氮气条件下,以2℃/min的速率升温至550℃,高温煅烧处理24h,再以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.07Fe2.55Mn0.2Co0.05(PO4)2P2O7F0.05/C。
实施例12
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:Cl:Br摩尔比为4.02:2.55:0.3:0.1:4:0.03:0.02称取碳酸氢钠、磷酸铵、硝酸铁、硝酸锰、三氧化二钴、氯化铵和溴化铵进行混合,加入水以及纤维素,其中纤维素为其他固体成分总质量的20%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃;随后于氮气条件下,以2℃/min的速率升温至550℃,高温煅烧处理24h,再以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.02Fe2.55Mn0.3Co0.1(PO4)2P2O7Cl0.03Br0.02/C。
对比例1
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:F摩尔比为4.07:2.45:0.1:0.1:4:0.05称取二水合磷酸二氢钠、三氧化二铁、碳酸锰、硫酸钴和氟化铵进行混合,加入水以及纤维素,其中纤维素为其他固体成分总质量的20%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃;随后于氮气条件下,以2℃/min的速率升温至550℃,高温煅烧处理24h,再以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.07Fe2.9Mn0.1Co0.1(PO4)2P2O7F0.05/C。
对比例2
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:F摩尔比为4.18:2.7:0.2:0.05:4:0.05称取二水合磷酸二氢钠、三氧化二铁、碳酸锰、硫酸钴和氟化铵进行混合,加入水以及纤维素,其中纤维素为其他固体成分总质量的20%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃;随后于氮气条件下,以2℃/min的速率升温至550℃,高温煅烧处理24h,再以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.18Fe2.7Mn0.2Co0.05(PO4)2P2O7F0.05/C。
对比例3
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:F摩尔比为4.1:2.7:0.1:0.2:4:0.03称取二水合磷酸二氢钠、三氧化二铁、碳酸锰、硫酸钴和氟化铵进行混合,加入水以及纤维素,其中纤维素为其他固体成分总质量的20%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃;随后于氮气条件下,以2℃/min的速率升温至550℃,高温煅烧处理24h,再以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.1Fe2.7Mn0.1Co0.2(PO4)2P2O7F0.03/C。
对比例4
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:F摩尔比为4.2:2.55:0.25:0.2:4:0.05称取二水合磷酸二氢钠、三氧化二铁、碳酸锰、硫酸钴和氟化铵进行混合,加入水以及纤维素,其中纤维素为其他固体成分总质量的20%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃;随后于氮气条件下,以2℃/min的速率升温至550℃,高温煅烧处理24h,再以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.2Fe2.55Mn0.25Co0.2(PO4)2P2O7F0.05/C。
对比例5
一种钠离子电池正极材料,其制备方法包括如下步骤:
(1)按照Na:Fe:Mn:Co:P:F摩尔比为4.03:2.8:0.5:0.3:4:0.05称取二水合磷酸二氢钠、三氧化二铁、碳酸锰、硫酸钴和氟化铵进行混合,加入水以及柠檬酸,其中柠檬酸为其他固体成分总质量的30%,利用砂磨机剂混合处理2h,制得均匀浆料;其中砂磨机的转速为3000rpm,气压为0-0.15MPa。
(2)将步骤(1)制得的均匀浆料进行喷雾干燥,得到黄色前驱体;喷雾干燥的进风温度为190℃,出风温度为120℃;随后于氮气条件下,以2℃/min的速率升温至300℃,恒温处理2h,再以2℃/min的速率升温至530℃,高温煅烧处理12h,以2℃/min的速率降温至室温,最后经粉碎、筛分,即得钠离子电池正极材料Na4.03Fe2.8Mn0.5Co0.3(PO4)2P2O7F0.05/C。
验证例1
分别取实施例1-12及对比例1制备得到的钠离子电池正极材料,分别与导电炭黑(Super P)和偏二氟乙烯(PVDF)按质量比80:10:10于N-甲基吡咯烷酮(NMP)溶液中进行制浆并涂布在铝箔上,真空干燥后切成直径为12mm极片(载量为5-10mg/cm2),以金属钠片为负极,1mol/L的NaPF6/聚碳酸酯(PC):乙烯碳酸酯(EC):碳酸二甲酯(DMC)(体积比1:1:1)+5% FEC溶液做电解液,玻璃纤维隔膜,在氩气手套箱中组装成CR2032扣电池。取制备获得的纽扣电池对其0.1C充电克容量(mAh/g)、0.1C放电克容量(mAh/g)、0.1C首效(%)、1C放电克容量(mAh/g)、15C克容量(mAh/g)、平均电压(V)、500圈循环容量保持率(1C/%)等电化学性能进行测试,其中充放电容量测试以及首效测试的电压范围为1.5-4.3V。检测结果如下表1所示。
表1 实施例1-12及对比例1电化学性能测试结果
0.1C充电克容量(mAh/g) | 0.1C放电克容量(mAh/g) | 0.1C首效(%) | 1C放电克容量(mAh/g) | 15C克容量(mAh/g) | 平均电压(V) | 500圈循环性能(1C,%) | |
实施例1 | 110.5 | 108.1 | 97.8 | 102.7 | 91.9 | 3.2 | 98.5 |
实施例2 | 121.5 | 118.3 | 97.4 | 112.4 | 100.6 | 3.2 | 99.7 |
实施例3 | 117.5 | 112.4 | 95.7 | 106.8 | 95.5 | 3.2 | 98.9 |
实施例4 | 115.3 | 110.2 | 95.6 | 104.7 | 93.7 | 3.2 | 99.1 |
实施例5 | 116.2 | 112.5 | 96.8 | 106.9 | 95.6 | 3.2 | 99.2 |
实施例6 | 112.1 | 108.4 | 96.7 | 103.0 | 92.1 | 3.4 | 98.5 |
实施例7 | 108.6 | 103.0 | 94.8 | 97.9 | 87.6 | 3.5 | 98.3 |
实施例8 | 106.1 | 101.8 | 95.9 | 96.7 | 86.5 | 3.3 | 98.8 |
实施例9 | 117.4 | 112.7 | 96.0 | 107.1 | 95.8 | 3.2 | 99.5 |
实施例10 | 113.5 | 108.2 | 95.3 | 102.8 | 92.0 | 3.2 | 98.4 |
实施例11 | 114.5 | 107.9 | 94.2 | 102.5 | 91.7 | 3.2 | 98.1 |
实施例12 | 110.6 | 104.7 | 94.7 | 99.5 | 89.0 | 3.2 | 99.2 |
对比例1 | 115.4 | 110.7 | 95.9 | 105.2 | 94.1 | 3.1 | 99.5 |
对比例2 | 110.5 | 105.2 | 95.2 | 99.9 | 89.4 | 3.2 | 97.4 |
对比例3 | 109.5 | 102.9 | 94.0 | 97.8 | 87.5 | 3.2 | 97.8 |
对比例4 | 85.3 | 74.2 | 87.0 | 70.5 | 63.1 | 3.2 | 87.4 |
对比例5 | 107.9 | 101.3 | 93.9 | 96.2 | 86.1 | 3.1 | 97.8 |
从表1可见,根据本发明实施例制备得到的掺阴离子富钠复合型焦磷酸磷酸铁钠正极材料的钠离子电池,通过特定含量锰和钴元素的添加,可以形成过渡金属空位,以扭曲周围元素的化学键,拓展钠离子脱嵌通道,提高钠离子的传输速度;同时,通过适宜含量卤族元素阴离子的添加,能够有效提高周围电子云密度,进而提高材料离子电导率和电子电导率;此外,通过适当增加钠离子形成富钠结构,使得可逆脱嵌钠离子数量增加。本发明相对于对比例来说能够显著减少磷酸铁钠和焦磷酸铁钠杂质,提高材料的纯度和结构稳定性,进而提高正极材料的充放电克容量、首次库伦效率、倍率性能和循环性能。
以上具体实施方式部分对本发明所涉及的分析方法进行了具体的介绍。应当注意的是,上述介绍仅是为了帮助本领域技术人员更好地理解本发明的方法及思路,而不是对相关内容的限制。在不脱离本发明原理的情况下,本领域技术人员还可以对本发明进行适当的调整或修改,上述调整和修改也应当属于本发明的保护范围。
Claims (10)
1.一种钠离子电池正极材料,其特征在于,其化学式为Na4+xFey1Mny2Coy3(PO4)2P2O7Mz/C;其中M选自F、Br、Cl中的一种或多种;0.001≤x≤0.5,0.5≤y1≤3,0.1≤y2≤2.5,0<y3≤0.5,0<z≤0.2;且x、y1、y2、y3、z满足如下条件:
0<x/(2(3-y1-y2-y3)+z)<1.1;2.7≤y1+y2+y3≤3。
2.根据权利要求1所述的钠离子电池正极材料的制备方法,其特征在于,包括如下步骤:
(1)将钠源、铁源、锰源、钴源、磷源、碳源、M源、溶剂进行充分混合;其中M源选自氟源、溴源、氯源中的一种或多种;所述钠源、铁源、锰源、钴源、磷源、M源按照Na、Fe、Mn、Co、P、M摩尔比为4+x:y1:y2:y3:4:z进行混合;
(2)将步骤(1)混合后的原料进行干燥,随后进行高温烧结处理,最后降温至室温后经粉碎、筛分即得。
3.根据权利要求2所述的制备方法,其特征在于,步骤(1)中所述钠源选自碳酸钠、碳酸氢钠、硝酸钠、磷酸钠、酒石酸钠、磷酸二氢钠、磷酸一氢钠、焦磷酸二氢钠、海藻酸钠、乳酸钠、氢氧化钠、甲酸钠、柠檬酸钠、草酸钠、醋酸钠中的一种或多种。
4.根据权利要求2所述的制备方法,其特征在于,步骤(1)中所述铁源选自磷酸铁、焦磷酸铁、醋酸铁、硝酸亚铁、氯化亚铁、硝酸铁、氧化铁、硫酸铁、氯化铁、铁粉、柠檬酸铁、柠檬酸亚铁、硫酸亚铁、四氧化三铁、三氧化二铁、氧化亚铁、乙酸铁、硫酸亚铁铵中的一种或多种。
5.根据权利要求2所述的制备方法,其特征在于,步骤(1)中所述锰源选自氢氧化锰、羟基氧化锰、磷酸锰、硫酸锰、乙酸锰、二氧化锰、三氧化二锰、四氧化三猛、碳酸锰、柠檬酸锰、锰粉、四氯化锰、硝酸锰、醋酸锰中的一种或多种。
6.根据权利要求2所述的制备方法,其特征在于,步骤(1)中所述钴源选自磷酸钴、焦磷酸钴、醋酸钴、硝酸钴、氯化钴、三氧化二钴、硫酸钴、氢氧化钴、羟基氧化钴中的一种或多种。
7.根据权利要求2所述的制备方法,其特征在于,步骤(1)中所述磷源选自磷酸、磷酸铁、磷酸一氢钠、磷酸二氢钠、磷酸钠、磷酸一氢铵、焦磷酸二氢钠、磷酸二氢铵、磷酸铵中的一种或多种。
8.根据权利要求2所述的制备方法,步骤(1)中所述碳源选自葡萄糖、果糖、淀粉、纤维素、麦芽糖、PEO、柠檬酸、聚多巴胺、树脂、草酸、抗坏血酸、甲醛、乳酸、苹果酸、乙二酸、己二酸、乙醛、正丁醛中一种或多种。
9.根据权利要求2所述的制备方法,其特征在于,步骤(2)中所述高温烧结的温度为200-600℃,时间为2-48h。
10.一种钠离子电池,其特征在于,包含根据权利要求1所述的钠离子电池正极材料和/或根据权利要求2-9任一项所述制备方法制备得到的钠离子电池正极材料。
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CN117936755A (zh) * | 2024-03-21 | 2024-04-26 | 四川易纳能新能源科技有限公司 | 一种高能量密度型聚阴离子正极材料及其制备方法和钠离子电池正极极片 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110061233A (zh) * | 2019-05-22 | 2019-07-26 | 中南大学 | 一种掺氟碳包覆的磷酸焦磷酸铁钠@介孔碳复合材料及其制备和在钠离子电池中的应用 |
CN114256459A (zh) * | 2021-12-14 | 2022-03-29 | 上海电力大学 | 一种氟代混合焦磷酸铁锰钠二元正极材料、制备方法及其在钠离子电池中的应用 |
CN114538403A (zh) * | 2022-01-27 | 2022-05-27 | 上海交通大学 | 钠离子电池正极材料磷酸焦磷酸铁钠的制备方法及其应用 |
CN114613998A (zh) * | 2022-03-16 | 2022-06-10 | 北京理工大学 | 碳包覆钠离子电池正极材料Na4Fe3-xMx(PO4)2P2O7/C及其制备方法 |
CN115132981A (zh) * | 2022-04-07 | 2022-09-30 | 深圳沃伦特新能源科技有限公司 | 一种二元掺杂的铁基氟磷酸盐钠离子正极材料及其制备方法 |
CN116169264A (zh) * | 2023-02-10 | 2023-05-26 | 西安理工大学 | 碳包覆富钠型焦磷酸磷酸铁钠复合正极材料、制法和应用 |
CN116621149A (zh) * | 2023-05-24 | 2023-08-22 | 深圳华钠新材有限责任公司 | 一种钠离子电池氟化焦磷酸铁钠活性材料的制备方法 |
-
2023
- 2023-09-26 CN CN202311244638.5A patent/CN117012956A/zh active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110061233A (zh) * | 2019-05-22 | 2019-07-26 | 中南大学 | 一种掺氟碳包覆的磷酸焦磷酸铁钠@介孔碳复合材料及其制备和在钠离子电池中的应用 |
CN114256459A (zh) * | 2021-12-14 | 2022-03-29 | 上海电力大学 | 一种氟代混合焦磷酸铁锰钠二元正极材料、制备方法及其在钠离子电池中的应用 |
CN114538403A (zh) * | 2022-01-27 | 2022-05-27 | 上海交通大学 | 钠离子电池正极材料磷酸焦磷酸铁钠的制备方法及其应用 |
CN114613998A (zh) * | 2022-03-16 | 2022-06-10 | 北京理工大学 | 碳包覆钠离子电池正极材料Na4Fe3-xMx(PO4)2P2O7/C及其制备方法 |
CN115132981A (zh) * | 2022-04-07 | 2022-09-30 | 深圳沃伦特新能源科技有限公司 | 一种二元掺杂的铁基氟磷酸盐钠离子正极材料及其制备方法 |
CN116169264A (zh) * | 2023-02-10 | 2023-05-26 | 西安理工大学 | 碳包覆富钠型焦磷酸磷酸铁钠复合正极材料、制法和应用 |
CN116621149A (zh) * | 2023-05-24 | 2023-08-22 | 深圳华钠新材有限责任公司 | 一种钠离子电池氟化焦磷酸铁钠活性材料的制备方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117936755A (zh) * | 2024-03-21 | 2024-04-26 | 四川易纳能新能源科技有限公司 | 一种高能量密度型聚阴离子正极材料及其制备方法和钠离子电池正极极片 |
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