CN117673332A - 一种Na4Fe2MnxV(2-2x)/3(PO4)2P2O7/C复合材料及其制备方法和应用 - Google Patents
一种Na4Fe2MnxV(2-2x)/3(PO4)2P2O7/C复合材料及其制备方法和应用 Download PDFInfo
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- CN117673332A CN117673332A CN202410130331.0A CN202410130331A CN117673332A CN 117673332 A CN117673332 A CN 117673332A CN 202410130331 A CN202410130331 A CN 202410130331A CN 117673332 A CN117673332 A CN 117673332A
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- Prior art keywords
- sodium
- source
- manganese
- positive electrode
- electrode material
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- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000011734 sodium Substances 0.000 claims abstract description 90
- 239000007774 positive electrode material Substances 0.000 claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 42
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 14
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229920000447 polyanionic polymer Polymers 0.000 claims abstract description 5
- 239000002178 crystalline material Substances 0.000 claims abstract description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims abstract description 3
- 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 claims abstract description 3
- 238000006467 substitution reaction Methods 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 95
- 239000011572 manganese Substances 0.000 claims description 78
- 238000000227 grinding Methods 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 21
- 229910052708 sodium Inorganic materials 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 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 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 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 10
- 239000008103 glucose Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 230000000630 rising effect Effects 0.000 claims description 10
- 239000007921 spray Substances 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
- 238000001816 cooling Methods 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002612 dispersion medium Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- NAAXGLXYRDSIRS-UHFFFAOYSA-L dihydrogen phosphate;manganese(2+) Chemical compound [Mn+2].OP(O)([O-])=O.OP(O)([O-])=O NAAXGLXYRDSIRS-UHFFFAOYSA-L 0.000 claims description 4
- 235000019820 disodium diphosphate Nutrition 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011706 ferric diphosphate Substances 0.000 claims description 4
- 235000007144 ferric diphosphate Nutrition 0.000 claims description 4
- 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 4
- 229940036404 ferric pyrophosphate Drugs 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims description 4
- 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 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 230000008569 process Effects 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
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 235000011008 sodium phosphates Nutrition 0.000 claims description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- MLIKYFGFHUYZAL-UHFFFAOYSA-K trisodium;hydron;phosphonato phosphate Chemical compound [Na+].[Na+].[Na+].OP([O-])(=O)OP([O-])([O-])=O MLIKYFGFHUYZAL-UHFFFAOYSA-K 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 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
- 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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005955 Ferric phosphate Substances 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 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
- 229920002472 Starch Polymers 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 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 2
- UBYFFBZTJYKVKP-UHFFFAOYSA-J [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O Chemical compound [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O UBYFFBZTJYKVKP-UHFFFAOYSA-J 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 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
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 229940032296 ferric chloride Drugs 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- 229960005191 ferric oxide Drugs 0.000 claims description 2
- 229940032958 ferric phosphate Drugs 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 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 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 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
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 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
- 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
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 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
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 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
- 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
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
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- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 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 8
- 229960002303 citric acid monohydrate Drugs 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000011056 performance test Methods 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 5
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
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- 238000012512 characterization method Methods 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
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Abstract
本发明公开了一种Na4Fe2MnxV(2‑2x)/3(PO4)2P2O7/C复合材料及其制备方法和应用,属于钠离子电池技术领域。该Na4Fe2MnxV(2‑2x)/3(PO4)2P2O7/C(0<x<1)复合材料是碳包覆的Mn2+和V3+共掺杂改性的磷酸/焦磷酸铁钠聚阴离子型复合材料。作为钠离子电池正极材料,Mn2+和V3+掺杂到晶体材料的晶胞中部分取代Fe2+晶格位置,有利于Na+的快速迁移,动力学性能得到提升,具备优越的倍率性能;Mn2+/Mn3+和V3+/V4+实现高工作电压输出,提高了材料的能量密度,并适用于高工作电压环境。液固纳米化制备技术有效实现了Fe、Mn和V多元素的均一分布,Mn和V元素掺杂协同机制和精准碳包覆技术提高了材料体相和界面结构的稳定。该复合材料制备方法简单,可规模化放大,适合工业化应用。
Description
技术领域
本发明涉及一种储能用的复合正极材料及其可规模化的制备方法和在钠离子电池中的应用技术,属于钠离子电池材料与电池应用领域。
背景技术
近年来,锂资源受限,原材料价格波动较大,极大程度地阻碍锂离子电池在储能体系中的进一步应用。钠元素在地壳的丰度高达2.74%,且分布广泛,使得钠离子电池具有低成本、不受资源约束等优点,且钠离子电池高效、低温性能好,现已成为储能应用的重要趋势。发展低成本、高安全的钠离子电池体系将在储能领域有着广阔的应用前景。
Na4Fe3(PO4)2P2O7是复合磷酸/焦磷酸盐系聚阴离子型正极材料,其结构稳定、价格低廉、理论容量高达129 mAh g-1,工作电压为3.1 V (vs.Na+/Na),且所组成的钠离子电池具有高安全、长寿命优势,使得Na4Fe3(PO4)2P2O7正极材料在大规模储能应用中极有前景。但该类正极材料仅适用于较低工作电压,导电性较差,特别是能量密度、倍率性能需进一步提高。采用掺杂改性及碳包覆策略,有望进一步提升该类正极材料的电化学性能,以促进其在钠离子电池中的实际应用。
发明内容
针对上述现有技术存在的问题,本发明开发了一种Na4Fe2MnxV(2-2x)/3(PO4)2P2O7/C复合材料及其制备方法,该复合材料作为钠离子电池正极材料时,适用于高工作电压,倍率性能、能量密度和动力学性能得到提升。
在本发明的复合材料中,Mn2+和V3+的掺杂引入,由于V3+和Mn2+两者与Fe2+具有相近的离子半径,不会引起较大的晶格结构变化,部分取代Fe2+晶格位置时,略大的V3+和Mn2+使得晶胞的体积稍微增大,有利于充放电过程中Na+的快速迁移,Na4Fe2MnxV(2-2x)/3(PO4)2P2O7(0<x<1)正极材料表现出优异的动力学性能。Mn和V协同掺杂方法,有利于提升该类化合物的结构稳定性,抑制Mn2+溶出实现高电压下稳定充放电。同时,Na4Fe2MnxV(2-2x)/3(PO4)2P2O7材料协同碳包覆技术,并精准调控碳含量,优化该复合正极材料的导电性。Na4Fe2MnxV(2-2x)/3(PO4)2P2O7/C(0<x<1)复合材料的制备方法与大规模生产技术相一致,完全可匹配和适用于规模化生产及应用。
本发明提供一种Na4Fe2MnxV(2-2x)/3(PO4)2P2O7/C复合材料及其制备方法和应用于钠离子电池,并有望于工业化技术推广和钠离子电池产业化。
具体的,本发明的技术方案如下:
一种钠离子电池正极材料,是碳包覆的Mn2+和V3+共掺杂改性的磷酸/焦磷酸铁钠聚阴离子型复合材料,其化学式为Na4Fe2MnxV(2-2x)/3(PO4)2P2O7/C,其中0<x<1,Mn2+和V3+掺杂到晶体材料的晶胞中部分取代Fe2+晶格位置,原位碳层均匀包覆在Na4Fe2MnxV(2-2x)/3(PO4)2P2O7表面,碳含量为1~5wt%。材料结构呈现颗粒状,尺寸为亚微米或微米级,可减少电子/离子的迁移路径,有效提高该类材料的导电性和动力学性能。
上述钠离子电池正极材料中,优选的,0.2<x<0.8。所述Na4Fe2MnxV(2-2x)/3(PO4)2P2O7/C复合材料的粒径D50为0.2~5 μm。
本发明的Na4Fe2MnxV(2-2x)/3(PO4)2P2O7/C复合材料通过将钠源、铁源、锰源、钒源、磷源和碳源在液态分散介质中均匀混合后,经研磨、喷雾干燥得到均一混合的颗粒粉末,然后在400~600 ℃烧结,最后气流粉碎获得,具体的制备方法包括以下步骤:
(1)粗混/粗磨:按照化学计量,将钠源、铁源、锰源、钒源、磷源和碳源在分散介质中均匀混合;
(2)研磨:将步骤(1)混合均匀的浆料置于纳米砂磨机中研磨,调控混合原料粒径在0.2~5 μm;
(3)喷雾干燥:将研磨后的浆料喷雾干燥,获得均一混合的颗粒粉末;
(4)烧结:将上述获得的混合颗粒粉末在惰性气氛或还原气氛中进行烧结,温度为400~600 ℃,保温时长一般为5~15 h;
(5)气流粉碎:冷却至室温后,将粉体置于气流粉碎机中进行粉碎、筛分、除磁等,获得Na4Fe2MnxV(2-2x)/3(PO4)2P2O7/C复合材料。
优选的,步骤(1)中碳源的加入量占所有原料的5~30 wt%;
所述钠源可以选自碳酸钠、焦磷酸钠、草酸钠、醋酸钠、磷酸钠、磷酸二氢钠、磷酸氢二钠、焦磷酸二氢二钠、焦磷酸一氢三钠、柠檬酸钠、甲酸钠、硫酸钠中的一种或几种;
所述铁源可以选自硝酸铁、硝酸亚铁、硫酸铁、硫酸亚铁、草酸铁、草酸亚铁、乙酸铁、磷酸铁、焦磷酸铁、氯化铁、氯化亚铁、四氧化三铁、三氧化二铁、铁粉中的一种或几种;
所述锰源可以选自硝酸锰、硫酸锰、碳酸锰、乙酸锰、柠檬酸锰、草酸锰、氯化锰、焦磷酸锰、磷酸锰、磷酸二氢锰中的一种或几种;
所述钒源可以选自偏钒酸铵、草酸氧钒、五氧化二钒中的一种或几种;
所述磷源可以选自磷酸二氢铵、磷酸氢二铵、焦磷酸钠、磷酸钠、磷酸二氢钠、磷酸氢二钠、磷酸铁、焦磷酸铁、磷酸、焦磷酸、焦磷酸二氢二钠、焦磷酸一氢三钠、焦磷酸锰、磷酸锰、磷酸二氢锰中的一种或几种;
所述碳源可以选自环氧树脂、酚醛树脂、蔗糖、葡萄糖、可溶性淀粉、草酸、柠檬酸、苹果酸、甲醛、乙醛、正丁醛、乳酸、聚乙二醇、环糊精中的一种或几种。
步骤(1)中制备用分散介质为醇或水,可以选自水、甲醇、乙醇、丙醇、异丙醇、乙二醇、正丁醇中的一种或几种;
步骤(2)中研磨时间一般为2-6 h,使得原料粒径在0.2~5 μm即可;
步骤(3)中喷雾进风口温度为200~280 ℃,进料速率为10~50 mL/min;
步骤(4)中烧结时所使用的气氛可以是氮气、氩气、氮/氢混合气、氩/氢混合气中的一种;
优选的,步骤(4)在管式炉中进行,烧结时升温速率为2~10 ℃/min。
相较于现有复合磷酸/焦磷酸盐系聚阴离子型正极材料的研究和应用,本发明的Na4Fe2MnxV(2-2x)/3(PO4)2P2O7/C复合正极材料及其制备方法和应用技术的有益效果如下:
(1)通过Mn和V共掺杂协同,Mn2+和V3+的引入不会大幅度引起原有的晶格结构变化,略大的Mn2+和V3+部分取代Fe2+晶格位置后,有利于Na+的快速传输,动力学性能得到提升,具备优越的倍率性能;
(2)Mn和V共掺杂,Mn2+/Mn3+和V3+/V4+实现高工作电压输出,可进一步提高该类材料的能量密度,并适用于高工作电压环境;
(3)液固纳米化技术有效地实现Fe、Mn和V多元素的均一分布,Mn和V元素掺杂协同机制和精准碳包覆技术有利于提高材料体相和界面结构的稳定;
(4)Na4Fe2MnxV(2-2x)/3(PO4)2P2O7/C复合正极材料的制备方法可归纳为液固混合-研磨纳米化-喷雾干燥-固相反应-筛分除磁过程,工序简单,与现有的工业化生产技术相一致,可规模化放大,且原材料无资源约束,制备工艺及其技术适合工业化应用。
附图说明
图1是本发明对比例1制备得到的Na4Fe2Mn(PO4)2P2O7/C复合正极材料与Na4Fe3(PO4)2P2O7/C复合正极材料在0.1 C时的充放电曲线。
图2是本发明对比例2制备得到的Na4Fe2V0.66(PO4)2P2O7/C复合正极材料与Na4Fe3(PO4)2P2O7/C复合正极材料在0.1 C时的充放电曲线。
图3是本发明实施例1制备得到的Na4Fe2Mn0.85V0.1(PO4)2P2O7/C复合正极材料的SEM图。
图4是本发明实施例1~3制备得到的Na4Fe2Mn0.85V0.1(PO4)2P2O7/C、Na4Fe2Mn0.7V0.2(PO4)2P2O7/C及Na4Fe2Mn0.55V0.3(PO4)2P2O7/C复合正极材料在0.1 C时的充放电曲线。
图5是本发明实施例4~6制备得到的Na4Fe2Mn0.4V0.4(PO4)2P2O7/C、Na4Fe2Mn0.25V0.5(PO4)2P2O7/C及Na4Fe2Mn0.1V0.6(PO4)2P2O7/C复合正极材料在0.1 C时的充放电曲线。
图6是Na4Fe2Mn0.85V0.1(PO4)2P2O7/C、Na4Fe2Mn0.25V0.5(PO4)2P2O7/C及Na4Fe3(PO4)2P2O7/C复合正极材料的倍率性能比较。
具体实施方式
下面结合附图,通过实例进一步详细描述本发明,以使本领域技术人员根据本说明书的内容轻松地了解本发明的优势。
对比例1
Na4Fe2Mn(PO4)2P2O7/C复合正极材料及其制备方法和应用:
将26.59 g Na4P2O7、30.16 g FePO4和11.50 g MnCO3加入250 mL去离子水中均匀混合。同时加入碳源,为葡萄糖、一水柠檬酸和聚乙二醇的一种或几种,碳源占总重量的20wt%。粗混/粗磨制备过程在蓝氏研磨机中进行,转速为30 Hz,时间为2 h;粗混/粗磨均匀后的浆料转至纳米研磨机中进行细磨,转速2200 r/min,时间为4 h;随后,将浆料在250 ℃下喷雾干燥得到前驱体粉末,并放置石墨坩埚中,在高纯氮气保护下,在管式炉中进行烧结:升温速率为3 ℃/min,温度升至565 ℃,恒温烧结10 h。最后,将冷却获得的粉体材料置于气流粉碎机中进行粉碎、筛分、除磁,即可获得Na4Fe2Mn(PO4)2P2O7/C复合正极材料。
电池性能测试:
将上述方法制备的Na4Fe2Mn(PO4)2P2O7/C复合正极材料进行电池性能测试:Na4Fe2Mn(PO4)2P2O7/C复合材料、乙炔黑和聚偏氟乙烯(PVDF)按质量比例90:5:5以N-甲基吡咯烷酮(NMP)为分散剂均匀混合,随后将分散均匀的浆料涂覆在铝箔集流体上,厚度为250μm。涂覆后的极片分别于80 ℃下干燥2 h和120 ℃下干燥整夜,裁成直径为11 mm的圆片作为电极片,并与玻璃纤维隔膜、钠负极片组装成CR2032纽扣钠电池进行测试,电解液为 1 M(mol L-1) NaClO4溶于体积比为1:1的碳酸二甲酯(DMC)和碳酸乙烯酯(EC)溶液,并添加5wt%的氟代碳酸乙烯酯(FEC)作为添加剂。电池性能充放电测试在蓝电测试系统进行,充放电压区间为1.7~4.5 V,图1为该复合正极材料在0.1 C时的充放电曲线,首次放电容量为113.1 mAh g-1,首次库伦效率为91.87%,在~4.0 V和~3.8 V均分别呈现出较高的充电和放电平台,工作电压较于Na4Fe3(PO4)2P2O7/C复合正极极具优势。
对比例2
Na4Fe2V0.66(PO4)2P2O7/C复合正极材料及其制备方法和应用:
将26.59 g Na4P2O7、30.16 g FePO4和7.72 g NH4VO3加入250 mL去离子水中均匀混合。同时加入碳源,为葡萄糖、一水柠檬酸和聚乙二醇的一种或几种,碳源占总重量的20wt%。粗混/粗磨制备过程在蓝氏研磨机中进行,转速为30 Hz,时间为2 h;粗混/粗磨均匀后的浆料转至纳米研磨机中进行细磨,转速2200 r/min,时间为4 h;随后,将浆料在250 ℃下喷雾干燥得到前驱体粉末,并放置石墨坩埚中,在高纯氮气保护下,在管式炉中进行烧结:升温速率为3 ℃/min,温度升至565 ℃,恒温烧结10 h。最后,将冷却获得的粉体材料置于气流粉碎机中进行粉碎、筛分、除磁,即可获得Na4Fe2V0.66(PO4)2P2O7/C复合正极材料。
Na4Fe2V0.66(PO4)2P2O7/C复合正极材料的电池性能测试按照对比例1中所述方法进行,充放电压区间为1.7~4.5 V,图2为该复合正极材料在0.1 C时的充放电曲线,首次放电容量为115 mAh g-1,首次库伦效率为92.07%,在~4.0 V和~3.8 V仍较于Na4Fe3(PO4)2P2O7/C复合正极材料呈现出较高的充电和放电工作电压。
实施例1
Na4Fe2Mn0.85V0.1(PO4)2P2O7/C复合正极材料及其制备方法和应用:
将26.59 g Na4P2O7、30.16 g FePO4、9.77 g MnCO3和1.17 g NH4VO3加入250 mL去离子水中均匀混合。同时加入碳源,为葡萄糖、一水柠檬酸和聚乙二醇的一种或几种,碳源占总重量的20 wt%。粗混/粗磨制备过程在蓝氏研磨机中进行,转速为30 Hz,时间为2 h;粗混/粗磨均匀后的浆料转至纳米研磨机中进行细磨,转速2200 r/min,时间为4 h;随后,将浆料在250 ℃下喷雾干燥得到前驱体粉末,并放置石墨坩埚中,在高纯氮气保护下,在管式炉中进行烧结:升温速率为3 ℃/min,温度升至565 ℃,恒温烧结10 h。最后,将冷却获得的粉体材料置于气流粉碎机中进行粉碎、筛分、除磁,即可获得Na4Fe2Mn0.85V0.1(PO4)2P2O7/C复合正极材料。
图3为Na4Fe2Mn0.85V0.1(PO4)2P2O7/C复合正极材料微观结构表征,为200~300 nm颗粒结构。其电池性能测试按照对比例1中所述方法进行,充放电压区间为1.7~4.5V,图4显示了该复合正极材料在0.1 C时的充放电曲线,首次放电容量为119.7 mAh g-1,首次库伦效率为94.53%,在~4.0 V呈现出较高的充电工作电压平台;放电时,明显出现了~3.8 V和3.4 V两个放电平台电压,Mn和V协同掺杂使该正极具备两个较高的放电平台。与Na4Fe3(PO4)2P2O7/C复合正极材料相比,本实施例制备的Na4Fe2Mn0.85V0.1(PO4)2P2O7/C复合正极材料倍率性能提升明显,即在大电流倍率5 C下充放电,比容量仍高至82.1 mAh g-1,高于Na4Fe3(PO4)2P2O7/C复合正极材料的66.5 mAh g-1,如图6所示。
实施例2
Na4Fe2Mn0.7V0.2(PO4)2P2O7/C复合正极材料及其制备方法和应用:
将26.59 g Na4P2O7、30.16 g FePO4、8.05 g MnCO3和2.34 g NH4VO3加入250 mL去离子水中均匀混合。同时加入碳源,为葡萄糖、一水柠檬酸和聚乙二醇的一种或几种,碳源占总重量的20 wt%。粗混/粗磨制备过程在蓝氏研磨机中进行,转速为30 Hz,时间为2 h;粗混/粗磨均匀后的浆料转至纳米研磨机中进行细磨,转速2200 r/min,时间为4h;随后,将浆料在250 ℃下喷雾干燥得到前驱体粉末,并放置石墨坩埚中,在高纯氮气保护下,在管式炉中进行烧结:升温速率为3 ℃/min,温度升至565 ℃,恒温烧结10 h。最后,将冷却获得的粉体材料置于气流粉碎机中进行粉碎、筛分、除磁,即可获得Na4Fe2Mn0.7V0.2(PO4)2P2O7/C复合正极材料。
Na4Fe2Mn0.7V0.2(PO4)2P2O7/C复合正极材料的电池性能测试按照对比例1中所述方法进行,充放电压区间为1.7~4.5 V,如图4所示,该复合正极材料在0.1 C时的充放电曲线仍呈现出较高的充/放电工作电压。
实施例3
Na4Fe2Mn0.55V0.3(PO4)2P2O7/C复合正极材料及其制备方法和应用:
将26.59 g Na4P2O7、30.16 g FePO4、6.32 g MnCO3和4.65 g VOC2O4加入250 mL去离子水中均匀混合。同时加入碳源,为葡萄糖、一水柠檬酸和聚乙二醇的一种或几种,碳源占总重量的20 wt%。粗混/粗磨制备过程在蓝氏研磨机中进行,转速为30 Hz,时间为2 h;粗混/粗磨均匀后的浆料转至纳米研磨机中进行细磨,转速2200 r/min,时间为4 h;随后,将浆料在250 ℃下喷雾干燥得到前驱体粉末,并放置石墨坩埚中,在高纯氮气保护下,在管式炉中进行烧结:升温速率为3 ℃/min,温度升至565 ℃,恒温烧结10 h。最后,将冷却获得的粉体材料置于气流粉碎机中进行粉碎、筛分、除磁,即可获得Na4Fe2Mn0.55V0.3(PO4)2P2O7/C复合正极材料。如图4所示,Na4Fe2Mn0.55V0.3(PO4)2P2O7/C复合正极材料在相同的测试条件下,同样获得较高的工作电压平台。
实施例4
Na4Fe2Mn0.4V0.4(PO4)2P2O7/C复合正极材料及其制备方法和应用:
将26.59 g Na4P2O7、30.16 g FePO4、6.92 g (CH3COO)2Mn和4.68 g NH4VO3加入250mL去离子水中均匀混合。同时加入碳源,为葡萄糖、一水柠檬酸和聚乙二醇的一种或几种,碳源占总重量的20 wt%。粗混/粗磨制备过程在蓝氏研磨机中进行,转速为30 Hz,时间为2h;粗混/粗磨均匀后的浆料转至纳米研磨机中进行细磨,转速2200 r/min,时间为4 h;随后,将浆料在250 ℃下喷雾干燥得到前驱体粉末,并放置石墨坩埚中,在高纯氮气保护下,在管式炉中进行烧结:升温速率为3 ℃/min,温度升至565 ℃,恒温烧结10 h。最后,将冷却获得的粉体材料置于气流粉碎机中进行粉碎、筛分、除磁,即可获得Na4Fe2Mn0.4V0.4(PO4)2P2O7/C复合正极材料。
Na4Fe2Mn0.4V0.4(PO4)2P2O7/C复合正极材料的电池性能测试按照对比例1中所述方法进行,充放电压为1.7~4.5 V。Na4Fe2Mn0.4V0.4(PO4)2P2O7/C复合正极材料中,Mn和V的掺杂量相当,如图5所示,该复合正极材料的首圈库伦效率高至95.7%。
实施例5
Na4Fe2Mn0.25V0.5(PO4)2P2O7/C复合正极材料及其制备方法和应用:
将26.59 g Na4P2O7、30.16 g FePO4、4.33g (CH3COO)2Mn和7.75 g VOC2O4加入250mL去离子水中均匀混合。同时加入碳源,为葡萄糖、一水柠檬酸和聚乙二醇的一种或几种,碳源占总重量的20 wt%。粗混/粗磨制备过程在蓝氏研磨机中进行,转速为30 Hz,时间为2h;粗混/粗磨均匀后的浆料转至纳米研磨机中进行细磨,转速2200 r/min,时间为4 h;随后,将浆料在250 ℃下喷雾干燥得到前驱体粉末,并放置石墨坩埚中,在高纯氮气保护下,在管式炉中进行烧结:升温速率为3 ℃/min,温度升至565 ℃,恒温烧结10 h。最后,将冷却获得的粉体材料置于气流粉碎机中进行粉碎、筛分、除磁,即可获得Na4Fe2Mn0.25V0.5(PO4)2P2O7/C复合正极材料。
Na4Fe2Mn0.25V0.5(PO4)2P2O7/C复合正极材料的电池性能测试按照对比例1中所述方法进行,充放电压为1.7~4.5 V,图5显示了该复合正极材料在0.1 C时的充放电曲线,首次放电容量为119.7 mAh g-1,首次库伦效率为92.52%,在~4.0 V呈现出较高的充电工作电压平台;放电时,仍保持在~3.8 V和~3.4 V两个高放电平台电压。如图6所示,本实施例制备的Na4Fe2Mn0.25V0.5(PO4)2P2O7/C复合正极材料倍率性能优越,5 C大电流倍率下充放电的比容量高至84.5 mAh g-1,优于Na4Fe3(PO4)2P2O7/C复合正极材料。且随着V掺杂含量增加,倍率性能得到进一步的提升。
实施例6
Na4Fe2Mn0.1V0.6(PO4)2P2O7/C复合正极材料及其制备方法和应用:
将26.59 g Na4P2O7、30.16 g FePO4、1.73 g (CH3COO)2Mn和9.3 g VOC2O4加入250mL去离子水中均匀混合。同时加入碳源,为葡萄糖、一水柠檬酸和聚乙二醇的一种或几种,碳源占总重量的20 wt%。粗混/粗磨制备过程在蓝氏研磨机中进行,转速为30 Hz,时间为2h;粗混/粗磨均匀后的浆料转至纳米研磨机中进行细磨,转速2200 r/min,时间为4 h;随后,将浆料在250 ℃下喷雾干燥得到前驱体粉末,并放置石墨坩埚中,在高纯氮气保护下,在管式炉中进行烧结:升温速率为3 ℃/min,烧结温度为565 ℃,恒温烧结10 h。最后,将冷却获得的粉体材料置于气流粉碎机中进行粉碎、筛分、除磁,即可获得Na4Fe2Mn0.1V0.6(PO4)2P2O7/C复合正极材料。
Na4Fe2Mn0.1V0.6(PO4)2P2O7/C复合正极材料即在Mn掺杂量大幅减少下,该复合正极材料在充放电循环时仍保持较高的工作电压,如图5所示。
需要强调的是,公布实例的目的在于进一步帮助理解本发明的内涵和外延,但是本领域的技术人员可以理解,在不脱离本发明及所附权利要求的范围内,各种替换和修改都是可能的。因此,本发明不应局限于实例中所公开的内容,本发明要求保护的范围以权利要求书界定的范围为准。
Claims (10)
1.一种钠离子电池正极材料,其特征是碳包覆的Mn2+和V3+共掺杂改性的磷酸/焦磷酸铁钠聚阴离子型复合材料,其化学式为Na4Fe2MnxV(2-2x)/3(PO4)2P2O7/C,其中0<x<1,Mn2+和V3+掺杂到晶体材料的晶胞中部分取代Fe2+晶格位置,原位碳层均匀包覆在Na4Fe2MnxV(2-2x)/3(PO4)2P2O7表面,碳含量为1~5 wt%。
2.如权利要求1所述的钠离子电池正极材料,其特征在于,所述复合材料为亚微米或微米级颗粒,通过将钠源、铁源、锰源、钒源、磷源和碳源在分散介质中均匀混合后,经研磨、喷雾干燥得到均一混合的颗粒粉末,然后在400~600 ℃烧结,最后气流粉碎得到。
3.如权利要求1所述的钠离子电池正极材料,其特征在于,0.2<x<0.8。
4.如权利要求1所述的钠离子电池正极材料,其特征在于,Na4Fe2MnxV(2-2x)/3(PO4)2P2O7/C复合材料的粒径D50为0.2~5 μm。
5.权利要求1~4任一所述的钠离子电池正极材料的制备方法,包括以下步骤:
1)按照化学计量,将钠源、铁源、锰源、钒源、磷源和碳源在分散介质中均匀混合;
2)将步骤1)混合均匀的浆料置于纳米砂磨机中研磨,调控混合原料粒径在0.2~5 μm;
3)将研磨后的浆料喷雾干燥,获得均一混合的颗粒粉末;
4)将步骤3)获得的混合颗粒粉末在惰性气氛或还原气氛中于400~600 ℃烧结;
5)冷却至室温后,将粉体置于气流粉碎机中进行粉碎、筛分、除磁,获得Na4Fe2MnxV(2-2x)/3(PO4)2P2O7/C复合材料。
6.如权利要求5所述的制备方法,其特征在于,步骤1)中所述分散介质为醇或水,碳源的加入量占所有原料的5~30 wt%。
7.如权利要求5所述的制备方法,其特征在于,所述钠源选自碳酸钠、焦磷酸钠、草酸钠、醋酸钠、磷酸钠、磷酸二氢钠、磷酸氢二钠、焦磷酸二氢二钠、焦磷酸一氢三钠、柠檬酸钠、甲酸钠、硫酸钠中的一种或多种;所述铁源选自硝酸铁、硝酸亚铁、硫酸铁、硫酸亚铁、草酸铁、草酸亚铁、乙酸铁、磷酸铁、焦磷酸铁、氯化铁、氯化亚铁、四氧化三铁、三氧化二铁、铁粉中的一种或多种;所述锰源选自硝酸锰、硫酸锰、碳酸锰、乙酸锰、柠檬酸锰、草酸锰、氯化锰、焦磷酸锰、磷酸锰、磷酸二氢锰中的一种或多种;所述钒源选自偏钒酸铵、草酸氧钒、五氧化二钒中的一种或多种;所述磷源选自磷酸二氢铵、磷酸氢二铵、焦磷酸钠、磷酸钠、磷酸二氢钠、磷酸氢二钠、磷酸铁、焦磷酸铁、磷酸、焦磷酸、焦磷酸二氢二钠、焦磷酸一氢三钠、焦磷酸锰、磷酸锰、磷酸二氢锰中的一种或多种;所述碳源选自环氧树脂、酚醛树脂、蔗糖、葡萄糖、可溶性淀粉、草酸、柠檬酸、苹果酸、甲醛、乙醛、正丁醛、乳酸、聚乙二醇、环糊精中的一种或多种。
8.如权利要求5所述的制备方法,其特征在于,步骤3)喷雾进风口温度为200~280 ℃,进料速率为10~50 mL/min。
9.如权利要求5所述的制备方法,其特征在于,步骤4)在管式炉中进行,烧结时升温速率为2~10 ℃/min,烧结气氛是氮气、氩气、氮氢混合气、氩氢混合气中的一种。
10.一种钠离子电池,其特征在于,其正极采用权利要求1~4任一所述的钠离子电池正极材料。
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