CN114864929A - Preparation method of modified micro-nano structure sodium ion battery positive electrode material - Google Patents
Preparation method of modified micro-nano structure sodium ion battery positive electrode material Download PDFInfo
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- CN114864929A CN114864929A CN202210643603.8A CN202210643603A CN114864929A CN 114864929 A CN114864929 A CN 114864929A CN 202210643603 A CN202210643603 A CN 202210643603A CN 114864929 A CN114864929 A CN 114864929A
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- Prior art keywords
- sodium
- nano
- ion battery
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- modified micro
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 38
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 38
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010405 anode material Substances 0.000 claims abstract description 42
- 238000000498 ball milling Methods 0.000 claims abstract description 26
- 239000011164 primary particle Substances 0.000 claims abstract description 25
- 238000001694 spray drying Methods 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000011163 secondary particle Substances 0.000 claims abstract description 19
- 239000012530 fluid Substances 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000004321 preservation Methods 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 239000011734 sodium Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 15
- 235000015165 citric acid Nutrition 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 14
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- 239000011261 inert gas Substances 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 4
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 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
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 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 2
- 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 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 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
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 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
- 229930006000 Sucrose Natural products 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 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
- 239000012298 atmosphere Substances 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
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 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
- 239000008103 glucose Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052704 radon Inorganic materials 0.000 claims description 2
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 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
- 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
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 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
- 235000010288 sodium nitrite 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
- 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
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011247 coating layer Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 description 24
- 238000001816 cooling Methods 0.000 description 13
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- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
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- 239000002994 raw material Substances 0.000 description 3
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- 239000004332 silver Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000004277 Ferrous carbonate Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
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- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 2
- 235000019268 ferrous carbonate Nutrition 0.000 description 2
- 229960004652 ferrous carbonate Drugs 0.000 description 2
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- 230000003179 granulation Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 2
- 229910001958 silver carbonate Inorganic materials 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
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- 239000003365 glass fiber Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- OVMJVEMNBCGDGM-UHFFFAOYSA-N iron silver Chemical group [Fe].[Ag] OVMJVEMNBCGDGM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
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- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
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- 235000009518 sodium iodide Nutrition 0.000 description 1
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- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
-
- 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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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of a modified micro-nano structure sodium ion battery anode material, which is characterized in that two-fluid spray drying is adopted to obtain smaller primary particles, the stability of product batches is easy to control, 30-100nm primary particles with more lattice defects are formed at the initial stage of sintering, then sintering and heat preservation are carried out to obtain 50-200nm primary particles with better crystal forms, and the average particle size of secondary particles is 2-5 mu m. The coating layer is uniformly distributed on the surface of the positive electrode material and tightly combined, so that sodium ions can be transmitted conveniently, and the obtained aluminum-coated modified micro-nano structure sodium ion battery positive electrode material has higher conductivity, larger specific capacity, good rate capability and cycle performance. The method does not need long-time ball milling or high-pressure resistant equipment, and has the advantages of simple process, environmental friendliness, low cost and easy industrialization.
Description
Technical Field
The invention belongs to the field of sodium ion battery anode materials, and particularly relates to a preparation method of a modified micro-nano structure sodium ion battery anode material.
Background
Lithium ion batteries are also the most widely studied energy storage batteries, but because of the limited storage capacity of metallic lithium, the price is rising year by year and the requirement of large-scale energy storage technology, sodium ion batteries become the research and development hot spots of battery technology in recent years due to the characteristics of abundant raw materials, low cost, high safety and the like. Since the radius of sodium ions is larger than that of lithium ions, the current research is critical to develop an electrode material capable of stably and rapidly extracting and intercalating sodium ions. Among many sodium ion battery positive electrode materials, polyanion-type compounds are considered as the most promising electrode materials due to their excellent structural stability, safety and suitable voltage platform. The sodium iron phosphate material has the advantages of abundant raw materials, low price, three-dimensional ion diffusion channels, good safety performance and wide attention. But the problems of poor electronic conductivity, slow ion diffusion rate and the like still influence the further application of the material.
Researchers have made a lot of efforts to improve the electrochemical properties and structural stability of sodium iron phosphate, for example, CN114368736A discloses a preparation method of a sodium iron phosphate positive electrode material, which comprises the steps of preserving heat of lithium iron phosphate at a certain temperature, quenching, mixing with sodium salt, ball milling, molten salt ion exchange sintering, and cooling to obtain a bulk material; and cleaning, solid-liquid separation and drying the obtained bulk material to obtain the required material. The discharge capacity of a battery assembled by electrodes prepared from the olivine type sodium iron phosphate cathode material at 0.1C multiplying power is 148mAh g within the voltage range of 2.1-3.6V -1 The discharge capacity at 2C rate was 110mAh g -1 The capacity retention after 300 cycles at 0.5C was 95.6%. The iron phosphate sodium is prepared by adopting lithium iron phosphate and sodium salt as raw materials and performing molten salt ion exchange, and the discovery shows that the required amount of the sodium salt is large, the consumed time is long, complete replacement is difficult to realize, and the obtained product has impure phases. CN114249311A discloses a preparation method of porous sodium-ion battery anode material sodium iron phosphate, which comprises the steps of preparing a mixture of silver carbonate and ferrous carbonate by a coprecipitation method to obtain silver-iron atom-level doped eutectic, and then co-sintering the eutectic with sodium dihydrogen phosphate and sodium iodide to obtain sodium iron phosphate, wherein when the sodium dihydrogen phosphate and the ferrous carbonate are subjected to solid-phase mixed sintering, silver carbonate is decomposed into carbon dioxide and silver oxide, the silver oxide is decomposed into silver simple substance and oxygen, and the silver single substance is decomposed into silver simple substance and oxygenThe material has appropriate conductivity, the electrochemical performance of the sodium iron phosphate is improved to a certain extent, but the operation process is complex and high in cost, and the conductivity, specific capacity and rate capability of the sodium iron phosphate still have a space for further improving.
Disclosure of Invention
The invention aims to provide a preparation method of a modified micro-nano structure sodium ion battery anode material, which is simple in process and low in cost, and the obtained micro-nano structure sodium iron phosphate anode material has high conductivity, high specific capacity and good rate performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a modified micro-nano structure sodium ion battery anode material comprises the following steps:
(1) adding a sodium source, a carbon source, iron phosphate, a dispersing agent and a solvent into a ball milling tank, and uniformly ball-milling;
(2) carrying out two-fluid spray drying on the slurry obtained in the step (1), controlling the feeding frequency to be 9-11Hz and the air inlet speed to be 3.5-4.5m 3 /h；
(3) Uniformly mixing the material obtained in the step (2) and the nano oxide in a mixer;
(4) sintering the mixed material obtained in the step (3) in an inert gas atmosphere, and screening to obtain a positive electrode material; the sintering is carried out at the temperature rise rate of 3 ℃/min and the temperature preservation time is 8-10 h; primary particles with the particle size of 30-100nm are formed in the initial sintering stage, primary particles with the particle size of 50-200nm and the crystal form is better are obtained through sintering and heat preservation, the average particle size of the secondary particles is 2-5 mu m, and the largest secondary particle size is less than 20 mu m.
In the step (1), the sodium source is any one or a combination of at least two of sodium hydroxide, sodium carbonate, sodium oxalate, sodium nitrite, disodium hydrogen phosphate, sodium bicarbonate, sodium citrate, anhydrous sodium sulfate, sodium stearate, sodium oleate, sodium tartrate, sodium alginate, sodium carboxymethylcellulose or sodium lactate.
In the step (1), the carbon source is any one or a combination of at least two of glucose, sucrose, fructose, starch, citric acid, ascorbic acid, tartaric acid or oxalic acid.
In the step (1), the dispersant is one or more than two of polyethylene glycol, polyvinyl alcohol, tween-80, tween-60, span-80 or triton x-100.
In the step (1), the solvent is one or more than two of pure water, ethanol, propanol or acetone.
The molar ratio of the P/Fe element to the Na element in the step (1) is 1: 1-1.05.
The content of the carbon source in the step (1) is 1-10% of the mass of the anode material; the content of the dispersing agent is 1-20% of the mass of the positive electrode material; the content of the solvent is 20-80% of the mass of the positive electrode material.
In the step (2), the feeding frequency is controlled to be 10Hz, and the air inlet speed is controlled to be 4.0m 3 /h。
In the step (3), the nano oxide is at least one of nano vanadium pentoxide, nano titanium dioxide, nano zirconium oxide, nano cerium oxide, nano zinc oxide, nano aluminum oxide, nano manganese dioxide or nano tungsten oxide, and the coating amount is 0.1-0.8%.
In the step (4), the inert gas is one or more than two of nitrogen, helium, neon, argon, krypton, xenon or radon.
And (3) making the buckle electric: respectively assembling the obtained modified sodium iron phosphate composite materials into button cells, mixing the obtained positive electrode material of the sodium ion battery with conductive carbon black and a binder PVDF according to the mass ratio of 7:2:1, adding an N-methyl pyrrolidone solution, and uniformly mixing to prepare the positive electrode slurry of the battery. Coating the slurry on an aluminum foil, vacuum drying and rolling to prepare a positive pole piece, taking a sodium metal piece as a negative pole, and taking 1mol/L NaPF 6 The button cell was assembled in a glove box filled with argon gas using Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (volume ratio 1:1) solution as electrolyte and glass fiber as separator.
Compared with the prior art, the preparation method for preparing the aluminum-coated micro-nano structure sodium ion battery anode material has the following advantages:
(1) the conventional centrifugal spray drying and static drying granulation has larger granularity, the product performance consistency is difficult to control through the working procedures of crushing, screening and the like after the conventional centrifugal spray drying and static drying granulation are carried out, the material capacity is low, the multiplying power and the cycle performance are poor, and if small primary particles are obtained, the primary particles need to be prepared by adopting a long-time ball milling or liquid phase method, the cost is higher; the preparation method of the invention uses two-fluid spray drying to obtain smaller primary particles by controlling the feeding frequency and the air inlet rate, can be directly applied, has less working procedures and easier control of the stability of product batches, forms 30-100nm primary particles with more lattice defects at the initial stage of sintering, and then obtains 50-200nm primary particles with better crystal forms through sintering and heat preservation, wherein the average particle size of the secondary particles is 2-5 mu m, and the maximum secondary particle size is less than 20 mu m, so that the prepared anode material has the performances of high conductivity, high specific capacity and the like.
(2) The coating layer is uniformly distributed on the surface of the positive electrode material and tightly combined, so that sodium ions can be transmitted conveniently, the circulating stability of the positive electrode material of the sodium ion battery is improved, good stability can be realized in electrolyte and air, and the obtained modified micro-nano ferric sodium phosphate positive electrode material has high conductivity, large specific capacity, good rate capability and good circulating performance.
The method does not need long-time ball milling or high-pressure resistant equipment, and has the advantages of simple process, environmental friendliness, low cost and easy industrialization.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the modified micro-nano structure sodium ion battery cathode material prepared in example 1;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the modified micro-nano structure sodium ion battery cathode material prepared in example 1;
FIG. 3 is an XRD diffraction spectrum of the modified micro-nano structure sodium ion battery anode material prepared in example 1;
FIG. 4 is a graph comparing the 1C cycle performance of example 1 and comparative example 2;
fig. 5 is a graph comparing the rate performance of example 1 and comparative example 1.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. For a further understanding of the invention, reference is made to the following description and specific preferred examples, which are not intended to limit the scope of the invention as claimed.
Example 1
The embodiment provides a modified micro-nano structure sodium ion battery anode material, and a preparation method of the anode material comprises the following steps:
weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and performing ball milling at the feeding frequency of 10Hz and the air inlet rate of 4.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 600 ℃ at 3 ℃/min in the nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate cathode material, wherein the primary particles of the material are 50-200nm, and the average particle size of the secondary particles is 2.0 mu m.
Wherein, fig. 1 is a Scanning Electron Microscope (SEM) image of the modified micro-nano structure sodium ion battery cathode material prepared in example 1; FIG. 2 is a Transmission Electron Microscope (TEM) image of the modified micro-nano structure sodium ion battery cathode material prepared in example 1; FIG. 3 is an XRD diffraction spectrum of the modified micro-nano structure sodium ion battery anode material prepared in example 1;
example 2
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and performing ball milling at the feeding frequency of 10Hz and the air inlet rate of 4.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 600 ℃ at 3 ℃/min in the nitrogen atmosphere, calcining for 8h, naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate cathode material,the material has primary particle of 50-100nm and secondary particle of average size of 1.8 micron.
Example 3
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and performing ball milling at the feeding frequency of 15Hz and the air inlet rate of 5.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 600 ℃ at 3 ℃/min in the nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate anode material, wherein the primary particles of the material are 100-200nm, and the average particle size of the secondary particles is 2.3 mu m.
Example 4
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10% of Tween-60, 6% of citric acid and 50% of pure water in the total weight of the positive electrode material respectively, ball-milling for 8 hours in a ball mill, taking out slurry, and feeding at the frequency of 10Hz and the air inlet rate of 3.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano alumina according to the mass ratio of 1:0.006, heating to 600 ℃ at 3 ℃/min under the nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate cathode material, wherein the material has the primary particle size of 100 plus materials of 200nm, and the average particle size of the secondary particles of 4.6 mu m.
Example 5
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and feeding at the frequency of 2Hz and the air inlet rate of 3.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 600 ℃ at 3 ℃/min in the nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate anode material, wherein the primary particles of the material are 100-300nm, and the average particle size of the secondary particles is 3.8 mu m.
Example 6
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and feeding at the frequency of 5Hz and the air inlet rate of 3.6m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 600 ℃ at 3 ℃/min in the nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate anode material, wherein the primary particles of the material are 100-300nm, and the average particle size of the secondary particles is 4.1 mu m.
Example 7
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and performing ball milling at the feeding frequency of 10Hz and the air inlet rate of 4.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 850 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, calcining for 8h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate cathode material, wherein the primary particles of the material are 50-250nm, and the average particle size of the secondary particles is 3.0 mu m.
Example 8
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and performing ball milling at the feeding frequency of 10Hz and the air inlet rate of 4.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 900 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate anode material, wherein the primary particles of the material are 100-250nm, and the average particle size of the secondary particles is 3.2 mu m.
Example 9
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and performing ball milling at the feeding frequency of 10Hz and the air inlet rate of 4.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 280 ℃ at 3 ℃/min in a nitrogen atmosphere, calcining for 15h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate cathode material, wherein the primary particles of the material are 50-150nm, and the average particle size of the secondary particles is 1.9 mu m.
Example 10
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and performing ball milling at the feeding frequency of 10Hz and the air inlet rate of 4.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 250 ℃ at 6 ℃/min in a nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate cathode material, wherein the primary particles of the material are 50-100nm, and the average particle size of the secondary particles is 1.7 mu m.
Comparative example 1
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10% triton x-100, 6% citric acid and 50% pure water of the total weight of the positive electrode material respectively, ball-milling for 8 hours in a ball mill, taking out slurry, and carrying out centrifugal drying. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 600 ℃ at 3 ℃/min in the nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate anode material, wherein the primary particles of the material are 300-700nm, and the average particle size of the secondary particles is 18.7 mu m.
Comparative example 2
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, and respectively adding 10 percent of the total weight of the positive electrode materialBall milling Triton x-100, 6% citric acid and 50% pure water in a ball mill for 8h, taking out slurry, and feeding at a feeding frequency of 10Hz and an air inlet rate of 4.0m 3 Two-fluid spray drying was carried out. And heating the obtained dried material to 600 ℃ at a speed of 3 ℃/min under the nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate cathode material, wherein the primary particles of the material are 50-200nm, and the average particle size of the secondary particles is 2.0 mu m.
And (3) performance testing:
1) testing the first discharge capacity and the coulombic efficiency: the button cells prepared from the positive electrode materials in examples 1-6 and comparative examples 1-2 were tested by a blue tester, the voltage range was 2.0-4.5V, the charge and discharge were activated for one turn at 0.1C, the first charge and discharge specific capacity and the first coulombic efficiency were obtained, and the test results are shown in table 1.
2)1C cycle performance: the button cell prepared by the anode materials in the embodiments 1-6 and the comparative examples 1-2 is tested by using a blue tester, the voltage range is 2.0-4.5V, the button cell is charged and discharged for one circle at 0.1C, then the button cell is charged at constant current and constant voltage at 0.5C, the cut-off current is 0.05C, constant current discharge is carried out at 1C, and 200 circles are circulated, so that relevant data of parameters such as the 100 th circle discharge capacity and the 100 th circle capacity retention ratio, the 200 th circle discharge capacity and the 200 th circle capacity retention ratio are respectively obtained. The test results are shown in table 2 and fig. 4.
3) Rate capability: the button cells prepared by the positive electrode materials in the examples 1-6 and the comparative examples 1-2 were tested by a blue tester, the voltage range was 2.0-4.5V, constant current and constant voltage charging was performed at a current of 0.5C, and the charge cutoff current was 0.05C; constant current discharge was performed at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, and 0.1C currents, respectively, with a discharge cutoff voltage of 2V.
The test results are shown in table 3 and fig. 5.
Evaluation of
TABLE 1
As can be seen from table 1, the conventional centrifugal spray drying employed in comparative example 1 has a low material capacity and a low first discharge efficiency. In the examples 1 to 6, smaller primary particles are obtained by two-fluid spray drying, the initial charge specific capacity is increased from 89.5mAh/g to 151.3mAh/g after sintering, the discharge specific capacity is increased from 75.2mAh/g to 149.7mAh/g, and the initial charge-discharge efficiency is 98.94%, while the initial charge specific capacity, the discharge specific capacity and the initial charge-discharge efficiency are reduced to different degrees after sintering at different temperatures in the examples 7 to 10.
TABLE 2
Table 2 is data on cycle performance of examples 1 to 6 and comparative examples 1 to 2, and it can be seen from the table that the capacity retention of the sodium ion positive electrode material prepared in example 1 is improved from 71.54% to 98.10% after 100 cycles, and the capacity retention is improved from 67.4% to 95.30% after 200 cycles.
TABLE 3
Table 3 is data on rate performance of examples 1 to 6 and comparative examples 1 to 2, and it can be seen from the table that the capacity retention rate of the positive electrode material for sodium ion battery prepared in example 1 at 5C rate is increased from 70.84% to 89.94%, and the 0.1C capacity retention rate after testing over-rate is still 97.64%.
The comparison between the examples and the comparative examples shows that the positive electrode material prepared by two-fluid spray drying has the performances of high conductivity, high specific capacity and the like. The coating layer is uniformly distributed on the surface of the anode material and tightly combined, so that sodium ions can be transmitted conveniently, and the obtained modified micro-nano iron sodium phosphate anode material has high conductivity, large specific capacity, good rate performance and good cycle performance.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a modified micro-nano structure sodium ion battery anode material is characterized in that,
the preparation method comprises the following steps:
(1) adding a sodium source, a carbon source, iron phosphate, a dispersing agent and a solvent into a ball milling tank, and uniformly ball-milling;
(2) carrying out two-fluid spray drying on the slurry obtained in the step (1), controlling the feeding frequency to be 9-11Hz and the air inlet speed to be 3.5-4.5m 3 /h；
(3) Uniformly mixing the material obtained in the step (2) and the nano oxide in a mixer;
(4) sintering the mixed material obtained in the step (3) in an inert gas atmosphere, and screening to obtain a positive electrode material; the sintering is carried out at the temperature rise rate of 3 ℃/min and the temperature preservation time is 8-10 h; primary particles with the particle size of 30-100nm are formed in the initial sintering stage, primary particles with the particle size of 50-200nm and the crystal form is better are obtained through sintering and heat preservation, the average particle size of the secondary particles is 2-5 mu m, and the largest secondary particle size is less than 20 mu m.
2. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: in the step (1), the sodium source is any one or a combination of at least two of sodium hydroxide, sodium carbonate, sodium oxalate, sodium nitrite, disodium hydrogen phosphate, sodium bicarbonate, sodium citrate, anhydrous sodium sulfate, sodium stearate, sodium oleate, sodium tartrate, sodium alginate, sodium carboxymethylcellulose or sodium lactate.
3. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: in the step (1), the carbon source is any one or a combination of at least two of glucose, sucrose, fructose, starch, citric acid, ascorbic acid, tartaric acid or oxalic acid.
4. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: in the step (1), the dispersant is one or more than two of polyethylene glycol, polyvinyl alcohol, tween-80, tween-60, span-80 or triton x-100.
5. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: in the step (1), the solvent is one or more than two of pure water, ethanol, propanol or acetone.
6. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: the molar ratio of the P/Fe element to the Na element in the step (1) is 1: 1-1.05.
7. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: the content of the carbon source in the step (1) is 1-10% of the mass of the anode material; the content of the dispersing agent is 1-20% of the mass of the positive electrode material; the content of the solvent is 20-80% of the mass of the positive electrode material.
8. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: in the step (2), the feeding frequency is controlled to be 10Hz, and the air inlet speed is controlled to be 4.0m 3 /h。
9. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: in the step (3), the nano oxide is at least one of nano vanadium pentoxide, nano titanium dioxide, nano zirconium oxide, nano cerium oxide, nano zinc oxide, nano aluminum oxide, nano manganese dioxide or nano tungsten oxide, and the coating amount is 0.1-0.8%.
10. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: in the step (4), the inert gas is one or more than two of nitrogen, helium, neon, argon, krypton, xenon or radon.
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| CN112490427A (en) * | 2020-11-30 | 2021-03-12 | 湖北亿纬动力有限公司 | Cathode material and preparation method and application thereof |
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