CN117401661A - Preparation method of carbon-coated sodium vanadium phosphate positive electrode material for sodium ion battery - Google Patents
Preparation method of carbon-coated sodium vanadium phosphate positive electrode material for sodium ion battery Download PDFInfo
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- CN117401661A CN117401661A CN202311194109.9A CN202311194109A CN117401661A CN 117401661 A CN117401661 A CN 117401661A CN 202311194109 A CN202311194109 A CN 202311194109A CN 117401661 A CN117401661 A CN 117401661A
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- Prior art keywords
- sodium
- vanadium
- carbon
- phosphate
- source
- Prior art date
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- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 title claims abstract description 142
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 126
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 37
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 150000003384 small molecules Chemical class 0.000 claims abstract description 13
- 125000003396 thiol group Chemical class [H]S* 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims description 76
- 239000007787 solid Substances 0.000 claims description 51
- 239000002131 composite material Substances 0.000 claims description 48
- 239000011734 sodium Substances 0.000 claims description 38
- 229910052593 corundum Inorganic materials 0.000 claims description 33
- 239000010431 corundum Substances 0.000 claims description 33
- 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 29
- 229910052708 sodium Inorganic materials 0.000 claims description 29
- 238000001354 calcination Methods 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 25
- 239000010405 anode material Substances 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 23
- 229910052720 vanadium Inorganic materials 0.000 claims description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 239000011574 phosphorus Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 238000001694 spray drying Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 claims description 11
- 238000001291 vacuum drying 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
- 238000000227 grinding Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 6
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 6
- 230000002572 peristaltic effect Effects 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 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
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- -1 vanadium phosphate monohydrate Chemical compound 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- CFPHMAVQAJGVPV-UHFFFAOYSA-N 2-sulfanylbutanoic acid Chemical compound CCC(S)C(O)=O CFPHMAVQAJGVPV-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229920002367 Polyisobutene Polymers 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 235000002639 sodium chloride Nutrition 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- KVJXEJFFQNSORF-UHFFFAOYSA-L disodium acetic acid diacetate Chemical compound [Na+].[Na+].CC(O)=O.CC(O)=O.CC([O-])=O.CC([O-])=O KVJXEJFFQNSORF-UHFFFAOYSA-L 0.000 claims description 3
- 229960003151 mercaptamine Drugs 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 108010094020 polyglycine Proteins 0.000 claims description 3
- 229920000232 polyglycine polymer Polymers 0.000 claims description 3
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 3
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 3
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 3
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 3
- HKAVADYDPYUPRD-UHFFFAOYSA-N 1h-pyrazine-2-thione Chemical compound SC1=CN=CC=N1 HKAVADYDPYUPRD-UHFFFAOYSA-N 0.000 claims description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 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
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 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
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000006012 monoammonium phosphate Substances 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
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 238000001556 precipitation 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
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims 1
- 238000003763 carbonization Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 description 17
- 239000002033 PVDF binder Substances 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 235000012431 wafers Nutrition 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical compound [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002226 superionic conductor Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
The invention provides a preparation method of a carbon-coated sodium vanadium phosphate positive electrode material for a sodium ion battery, which increases solubility in a heating and stirring mode to enable the material to be uniformly dispersed in a solution in an ionic state, and meanwhile, prevents crystallization of a carbon source by means of interaction between a small molecule A-class mercapto-containing carbon source and a high molecule B-class carbon source, forms a stable carbon-coated structure with uniform internal and external distribution after carbonization, and remarkably improves electronic conductivity of the sodium vanadium phosphate material. The carbon-coated sodium vanadium phosphate material prepared by the method has excellent electrochemical performance as a positive electrode of a sodium ion battery, the first discharge specific capacity is more than 110mAh/g at a rate of 1C, the discharge specific capacity is more than 105mAh/g at a rate of 5C, and the capacity retention rate is more than 99.2% after 1000 cycles at a rate of 5C, so that the double improvement of the carbon-coated sodium vanadium phosphate positive electrode material in the aspects of electronic conductivity and electrochemical performance is realized.
Description
Technical Field
The invention particularly relates to a preparation method of a carbon-coated sodium vanadium phosphate positive electrode material for a sodium ion battery. Belongs to the technical field of new energy battery materials, and relates to the positive electrode direction of a sodium ion battery.
Background
The positive electrode material is used as one of key materials in a sodium ion battery system, and largely determines the performance index, the cycle life and the manufacturing cost of the battery. Wherein the sodium super ion conductor (Na + Super Ionic Conductor sodium vanadium phosphate (Na) of NASICON structure 3 V 2 (PO 4 ) 3 NVP) positive electrode material belongs to a hexagonal system, has the dual advantages of high rate performance and cycle performance, has two types of unique sodium ion migration channels (Na 1 site and Na2 site), and has the Na2 site with reversible deintercalation at a 3.3V voltage platform corresponding to V 3+ /V 4+ Can provide a theoretical capacity of about 117mAh/g, but extremely low electron conductivity also severely limits the performance of the capacity. At present, the common preparation methods of the sodium vanadium phosphate include a high-temperature solid phase method, a sol-gel method, an electrostatic spinning method and a hydrothermal method. Wherein, the high-temperature solid phase method has simple process and easy industrialization, and adopts the high-temperature solid phase method in the work of CN115954456A to make the vanadium source (V) 2 O 5 、VO 2 Or NH 4 VO 3 ) Sodium source (Na) 2 CO 3 、CH 3 COONa or NaCl), phosphorus source (NH) 4 H 2 PO 4 、(NH 4 ) 2 HPO 4 Or H 3 PO 4 ) And a carbon source (citric acid, oxalic acid or grape acid) are ball-milled according to a certain proportion and then are subjected to segmented high-temperature calcination, however, the obtained vanadium sodium phosphate product is easy to agglomerate, so that the particle size of the particles is larger and the distribution is uneven. Preparation of stoichiometric ratio by sol-gel methodThe method is characterized in that the product particles are uniform and controllable in morphology, a soluble sodium source, a vanadium source and a phosphorus source are adopted to form sol through polycondensation and hydrolysis under the action of a complexing agent, the dried gel is subjected to heat treatment to obtain a vanadium sodium phosphate product, the sol-gel method and the glycine combustion method are adopted to couple in the work of CN115872383A, and sodium nitrate is used as a sodium source and is used as an oxidant to promote the combustion of glycine, so that the reaction time is shortened, however, the sol-gel method is complex in process and long in treatment period, and industrial production is not easy to realize. In the work of CN115275140, ammonium metavanadate, oxalic acid and sodium dihydrogen phosphate are adopted as raw materials, boric acid and polyvinylpyrrolidone are respectively used as a doping agent and a bonding agent, and the nanofiber-shaped boron-doped sodium vanadium phosphate is successfully prepared by an electrostatic spinning technology and a high-temperature annealing process. The hydrothermal method is a common liquid phase chemical method, the reaction condition is mild, the operation is convenient, the prepared product has smaller particle size and uniform distribution, but the reaction is carried out in a sealed reaction kettle, the growth process of the crystal cannot be observed and regulated, and meanwhile, the method has strong equipment dependence, high cost and great potential safety hazard in industrial production.
Therefore, a simple and effective preparation method is urgently needed, on one hand, a large amount of pure-phase sodium vanadium phosphate materials can be generated in situ, the industrial application requirements are met, and on the other hand, the inherent defects (low electronic conductivity) of the materials are improved, and the high capacity and high stability characteristics are exerted.
Disclosure of Invention
Based on the related technical means, the solubility of a vanadium source, a sodium source, a phosphorus source and a carbon source is increased by heating and high-speed stirring, and the mixed carbon coating is realized on a pure-phase sodium vanadium phosphate material by a small molecular A-type sulfhydryl-containing carbon source and a high molecular B-type carbon source after high-temperature calcination, wherein the high molecular B-type carbon source can enhance the viscosity and adsorptivity of a precursor solution, effectively prevent crystallization of the A-type sulfhydryl-containing carbon source, and in addition, a large-size carbon layer formed after high-temperature calcination phase inversion can well coat an in-situ generated sodium vanadium phosphate material, simultaneously promote small-particle-size sulfur-doped carbon (sulfur and carbon are coupled to generate a synergistic effect through d-p orbits to adjust fermi energy level, improve electron conductivity) particles to extend the inner core of the sodium vanadium phosphate material through internal holes, form an internal and external uniform carbon coating structure, improve the electron conductivity of the sodium vanadium phosphate material, further have excellent battery performance, the initial discharge specific capacity of > 110 h/g at a rate of 1C multiplying power, the specific capacity of > 105 h/g at a cycle rate of 5C and the cycle rate of > 1000.1000% after the cycle rate is maintained.
The preparation method of the vanadium sodium phosphate composite sodium ion battery anode material provided by the invention is innovative based on the traditional high-temperature solid phase method, improves the solubility in a solvent by heating and stirring, realizes the high electron conductivity of the material by uniformly coating the inner-outer carbon of the vanadium sodium phosphate material with a small molecular A-type mercapto-containing carbon source and a high molecular B-type carbon source after high-temperature carbonization, has simple integral operation and simple and convenient process, has low dependence on experimental equipment, is easy to realize large-scale commercial production, provides a new thought for preparing pure-phase and high-conductivity vanadium sodium phosphate materials and other lithium/sodium electrode materials, and has high specific capacity and long cycle life when being applied to the field of sodium ion battery anode materials, and is favorable for promoting the development of sodium-electricity industry and even new energy plate blocks.
Aiming at the problems, the aim of the patent is to provide a preparation method of a carbon-coated sodium vanadium phosphate positive electrode material for a sodium ion battery, which specifically comprises the following steps:
(1) Preparing a vanadium sodium phosphate composite precursor dispersion liquid: weighing a certain amount of sodium source, vanadium source, phosphorus source and carbon source, and completely dispersing the sodium source, the vanadium source, the phosphorus source and the carbon source in a solvent in a heating and stirring mode to obtain uniform vanadium sodium phosphate composite precursor dispersion liquid;
(2) Preparing a vanadium sodium phosphate composite solid precursor: the sodium vanadium phosphate composite precursor dispersion liquid enables sodium source, vanadium source, phosphoric acid and carbon source solid materials to be fully and uniformly mixed, and the solvent is gasified in a drying mode to obtain a sodium vanadium phosphate composite solid precursor;
(3) Preparing a carbon-coated sodium vanadium phosphate anode material: and weighing a certain amount of vanadium sodium phosphate composite solid precursor, placing the precursor into corundum, placing the corundum into a tubular furnace for calcination, heating the corundum under a protective atmosphere, taking the corundum out after the vanadium sodium phosphate composite solid precursor is naturally cooled to room temperature, crushing the vanadium sodium phosphate composite solid precursor by a powder grinding machine, fully and uniformly mixing the crushed vanadium sodium phosphate composite solid precursor, and then pouring the crushed powdery solid into a screen for sieving to obtain the high-performance carbon-coated vanadium sodium phosphate anode material with uniform particle size distribution.
The introduction of the ionic form in the technical process of the invention is beneficial to better realizing the uniform compounding of the precursor materials, improves the bonding strength among all raw material components under the action of high temperature, enhances the structural stability of the material, is beneficial to generating the high-purity and high-crystallinity sodium vanadium phosphate material, and improves the specific capacity and the cycle performance of the carbon-coated sodium vanadium phosphate anode material.
Preferably, the sodium source in step (1) comprises one or more of sodium acetate, sodium carbonate, disodium tetraacetate, sodium nitrate, sodium sulfate, sodium chloride, sodium bicarbonate, sodium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate.
Preferably, the vanadium source in step (1) comprises one or more of ammonium metavanadate, vanadium pentoxide, vanadium oxide, vanadium trioxide, vanadium phosphate monohydrate, vanadium sulfate, vanadyl sulfate, sodium orthovanadate and vanadyl oxalate.
Preferably, the phosphorus source in the step (1) comprises one or more of sodium hypophosphite, disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate, phosphoric acid, ammonium dihydrogen phosphate and diammonium hydrogen phosphate;
preferably, the carbon source in the step (1) comprises a small molecule class a thiol-containing carbon source and a high molecule class B carbon source, wherein the molar ratio of the small molecule class a thiol-containing carbon source to the high molecule class B carbon source is 1:1-3:1, and the small molecule class a thiol-containing carbon source comprises one or more of 2-mercaptobutyric acid, 3-mercaptopropionic acid, 2-mercaptoethylamine, 2-mercaptopyridine, 2-mercaptopyrazine and 1, 5-dimercaptonaphthyl; the polymer B carbon source comprises one or more of polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyvinyl alcohol, polyisobutylene, polyglycine, polyaniline, polyacrylonitrile and polypyrrole.
Preferably, in the step (1), the molar ratio of the sodium source to the vanadium source is 1:1-3:1, the molar ratio of the sodium source to the phosphorus source is 1:3-1:1, and the mass ratio of the vanadium sodium phosphate positive electrode active material precursor (including the sodium source, the vanadium source and the phosphorus source) to the carbon source is 5:1-15:1. Particularly, the vanadium sodium phosphate precursor material can be further added with a series of doping elements capable of improving the performance of the vanadium sodium phosphate, such as a manganese source, a boron source, a chromium source, a cobalt source and the like.
Preferably, the solvent in the step (1) comprises one or more of deionized water, absolute ethyl alcohol, absolute ethyl ether and absolute methyl alcohol, and the mass of the precursor of the sodium vanadium phosphate positive electrode active material (comprising a sodium source, a vanadium source and a phosphorus source) and the mass of the carbon source account for 10-30% of the total mass of the solution.
Preferably, in the step (1), the temperature of the heating solvent is 60-80 ℃, the stirring speed is 300-2000rpm, the heating and stirring time is 0.5-10h, and the heating and stirring are required until the solution is completely clear and has no solid precipitation state.
Preferably, the drying mode in the step (2) can be one or more of spray drying, forced air drying and vacuum drying. Wherein, the spray drying fan is set at 75-95, the temperature is set at 160-250 ℃, the peristaltic pump is set at 10-50mL/min, the needle is set at 5-15s, the particle size of the outlet particles can be precisely regulated and controlled by regulating the solid content of the solution and the spray drying parameters, the particle size range is 2-10 mu m, and the time required by spray drying is determined according to the sample amount; the blast drying temperature is set to 80-180 ℃ and the drying time is 10-30h; the pressure in the vacuum drying box body is required to be less than-30 MPa, the drying temperature is set to be 80-180 ℃, and the drying time is 10-30h.
Preferably, the vanadium sodium phosphate composite solid precursor material obtained in the step (2) may be ground into powder by a solid phase grinding method.
Preferably, the protective atmosphere in the step (3) can be nitrogen, helium, argon, neon and other inert gases, and the airflow speed is 2-50mL/min.
Preferably, in the step (3), the temperature rising rate is 2-10 ℃/min, the calcination temperature is 600-1000 ℃, the calcination time is 5-20h, and particularly, the carbonization time can be fully increased in a sectional calcination mode, the primary calcination temperature rising rate is 2-10 ℃/min, the primary calcination temperature is 300-500 ℃, the primary calcination time is 2-5h, the secondary calcination temperature rising rate is 2-10 ℃/min, the secondary calcination temperature is 600-1000 ℃, and the calcination time is 5-20h.
Preferably, the power of the powdering machine in the step (3) is 200-2000W, the working time is not more than 30s, the discharge particle size is less than 0.5mm, and the sieving number is 200-350 meshes.
The invention relates to a battery assembled by carbon-coated sodium vanadium phosphate anode materials obtained by the preparation method.
The composite positive electrode material is applied to a sodium ion battery system with high rate performance and long-cycle stability.
The invention improves the solubility of raw materials in a solvent in a heating and stirring mode to realize full and uniform mixing, and simultaneously adopts a micromolecular A-class sulfhydryl-containing carbon source and a macromolecule B-class carbon source to calcine and phase-change and then jointly coat an in-situ generated vanadium sodium phosphate material, thereby obviously improving the ion/electron conductivity and electrochemical performance of the vanadium sodium phosphate material.
Drawings
Fig. 1 is an XRD pattern of the carbon-coated sodium vanadium phosphate cathode material prepared in example 1.
Fig. 2 is an SEM image of the carbon-coated sodium vanadium phosphate positive electrode material precursor prepared in example 1.
Fig. 3 is an SEM image of the carbon-coated sodium vanadium phosphate cathode material prepared in example 1.
Fig. 4 is a graph showing the particle size distribution of the carbon-coated sodium vanadium phosphate cathode material prepared in example 1.
Fig. 5 is a graph showing the cycle performance of the carbon-coated sodium vanadium phosphate cathode material prepared in example 1 at a 5C rate.
Fig. 6 is an SEM image of the carbon-coated sodium vanadium phosphate cathode material prepared in example 2.
Fig. 7 is an SEM image of the cobalt-doped carbon coated sodium vanadium phosphate cathode material prepared in example 3.
Fig. 8 is an SEM image of the boron-doped carbon-coated sodium vanadium phosphate cathode material prepared in example 4.
Detailed Description
Specific embodiments of the present invention will be described in more detail below. While specific embodiments of the invention are described below, it should be noted that the invention can be practiced in various ways within the scope of the claims and is not limited by the specific embodiments. Furthermore, it should be noted that, in the specific embodiments, the specific technical solutions or means are not noted, and all the methods need to be performed according to the conditions limited by the claims, and the medicines and the reagents mentioned in the specific embodiments are conventional products which are commercially available in market channels.
Example 1
Preparing a vanadium sodium phosphate composite precursor dispersion liquid: adding ammonium metavanadate, anhydrous sodium carbonate and monoammonium phosphate into deionized water according to a molar ratio of V to Na to P of 2 to 3, adding small molecule class A mercapto carbon source-containing 2-mercapto butyric acid and macromolecule class B carbon source polyisobutene according to a mass ratio of 3 to 1, wherein the mass ratio of vanadium sodium phosphate positive electrode active material precursor (comprising sodium source, vanadium source and phosphorus source) to carbon source is 5 to 1, regulating the solid content of the solution to 20%, magnetically stirring at 400rpm, heating the solution to 70 ℃, and then continuing stirring for 0.5h until the solution is completely changed into a clear state, thereby obtaining uniform precursor dispersion.
Preparing a vanadium sodium phosphate composite solid precursor: and (3) spray drying the precursor dispersion, adjusting the set value of a spray drying fan to be 95, setting the temperature to be 180 ℃, setting the set value of a peristaltic pump to be 20, setting the set value of a through needle to be 10s, starting an air pump when the outlet temperature is increased to be more than 80 ℃, closing the peristaltic pump (about 5 min) after the materials are completely sprayed by the inlet water, and closing the fan when the inlet air temperature is reduced to be below 90 ℃, so as to collect the green vanadium sodium phosphate composite solid precursor in a collector.
Preparing a carbon-coated sodium vanadium phosphate anode material: weighing 2g of the vanadium sodium phosphate composite solid precursor, placing the precursor into corundum, placing the corundum into a tube furnace for calcination, heating the corundum under the nitrogen atmosphere, adjusting the airflow flow rate to be 10mL/min, firstly heating the corundum to 500 ℃ at the heating rate of 3 ℃/min, heating the corundum to 850 ℃ at the heating rate of 5 ℃/min after heat preservation for 2 hours, taking the vanadium sodium phosphate composite solid precursor out after waiting for naturally cooling to room temperature after heat preservation for 10 hours, crushing the vanadium sodium phosphate composite solid precursor by a powdering machine with the power of 200W, continuously crushing the vanadium sodium phosphate composite solid precursor for 20s to fully and uniformly mix the vanadium sodium phosphate composite solid precursor, then pouring the crushed powdery solid into a 325-mesh screen for sieving, and finally obtaining the high-performance carbon-coated vanadium sodium phosphate anode material with uniform particle size distribution, wherein the discharging particle size is lower than 0.045 mm.
High rate performance and long cycling stability sodium ion battery assembly: weighing NVP/C (0.35 g) prepared above, PVDF and SP according to the mass ratio of 7:2:1, preparing a PVDF solution with NMP as a solvent to 5wt.%, using the PVDF solution, controlling the solid content of the slurry to be 22% -25%, coating the slurry on an aluminum foil through a coating machine, drying the slurry for 1-3 hours at 120 ℃ by blowing, then cutting into wafers with the diameter of 12mm by a manual sheet punching machine and taking the wafers as working electrodes for standby, weighing the mass of the pole pieces after vacuum drying at 150 ℃ overnight, adopting a metal sodium sheet as a counter electrode, adopting a glass fiber diaphragm to form a sodium ion transmission channel, adopting 1.0M NaClO 4 inEC: pc=1:1 vol% with 5.0% FEC (NC-004) for experimental electrolyte system assembled button cell (half cell) and charge-discharge rate and stability tests were performed.
Fig. 1 is an XRD pattern of the prepared carbon-coated sodium vanadium phosphate positive electrode material. XRD spectrum of carbon-coated sodium vanadium phosphate anode material and sodium vanadium phosphate Na with NASICON structure 3 V 2 (PO 4 ) 3 The standard database card 00-062-0345 completely corresponds to the standard database card, and no other miscellaneous peaks exist, which shows that the pure-phase and high-crystallinity sodium vanadium phosphate material can be successfully prepared by adopting the method disclosed by the invention.
Fig. 2 is an SEM image of the prepared carbon-coated sodium vanadium phosphate positive electrode material precursor. After spray drying, the solid precursor has a micron-sized spherical structure, and has smooth surface and compact structure.
Fig. 3 is an SEM image of the prepared carbon-coated sodium vanadium phosphate cathode material. The vanadium sodium phosphate anode material formed after high-temperature calcination integrally maintains the compact microsphere structure of the precursor, and simultaneously the surface of the microsphere becomes rough under the high-temperature effect, which is more beneficial to electrolyte infiltration.
Fig. 4 is a graph showing the particle size distribution of the prepared carbon-coated sodium vanadium phosphate cathode material. The particle size distribution of the carbon-coated sodium vanadium phosphate positive electrode material is in the range of 0.4-40 mu m, wherein the D10 particle size is 2.610 mu m, the D50 particle size is 7.721 mu m, and the D90 particle size is 16.817 mu m.
Fig. 5 is a graph showing the cycle performance of the prepared carbon-coated sodium vanadium phosphate positive electrode material at 5C rate. In the 1000-cycle process, the coulombic efficiency of the prepared carbon-coated sodium vanadium phosphate anode material is basically maintained at 100%, and meanwhile, the capacity retention rate is as high as 99.99%, and basically no attenuation exists.
Example 2
Preparing a vanadium sodium phosphate composite precursor dispersion liquid: adding vanadyl sulfate, sodium dihydrogen phosphate and carbon nano tubes into absolute ethyl alcohol according to the molar ratio of V to Na to P of 2 to 3, adding small molecule A-class mercapto-containing carbon source 1, 5-dimercaptonaphthyl and macromolecule B-class carbon source polyvinyl alcohol according to the mass ratio of 3 to 1, wherein the mass ratio of a precursor of a vanadium sodium phosphate positive electrode active material (comprising a sodium source, a vanadium source and a phosphorus source) to the carbon source is 15 to 1, regulating the solid content of the solution to be 10%, magnetically stirring at the rotating speed of 2000rpm, heating the solution to 60 ℃, continuing stirring for 2 hours until the solution is completely changed into a completely uniformly mixed suspension state, and dissolving other substances except the carbon nano tubes to obtain a uniform precursor dispersion.
Preparing a vanadium sodium phosphate composite solid precursor: and (3) carrying out forced air drying on the precursor dispersion liquid, wherein the forced air drying temperature is 120 ℃, the time is 20 hours, until the precursor dispersion liquid is completely dried, and obtaining the vanadium sodium phosphate composite solid precursor powder after solid-phase grinding.
Preparing a carbon-coated sodium vanadium phosphate anode material: weighing 3g of the vanadium sodium phosphate composite solid precursor, placing the precursor into corundum, placing the corundum into a tube furnace for calcination, heating the corundum under the argon atmosphere, adjusting the airflow flow rate to be 20mL/min, heating the corundum to 700 ℃ at the heating rate of 5 ℃/min, preserving heat for 20 hours, taking the corundum out after waiting for naturally cooling to room temperature, crushing the corundum by using a powder crusher with the power of 2000W, continuously crushing the corundum for 10s to fully and uniformly mix the dried vanadium sodium phosphate composite solid, and then pouring the crushed powdery solid into a 350-mesh screen for sieving, so that the discharging grain size is lower than 0.045mm, and finally obtaining the high-performance carbon-coated vanadium sodium phosphate anode material with uniform grain size distribution.
High rate performance and long cycle stabilityAssembling a sodium ion battery: weighing NVP/C (0.35 g) prepared above, PVDF and SP according to the mass ratio of 7:2:1, preparing a PVDF solution with NMP as a solvent to 5wt.%, using the PVDF solution, controlling the solid content of the slurry to be 22% -25%, coating the slurry on an aluminum foil through a coating machine, drying the slurry for 1-3 hours at 120 ℃ by blowing, then cutting into wafers with the diameter of 12mm by a manual sheet punching machine and taking the wafers as working electrodes for standby, weighing the mass of the pole pieces after vacuum drying at 150 ℃ overnight, adopting a metal sodium sheet as a counter electrode, adopting a glass fiber diaphragm to form a sodium ion transmission channel, adopting 1.0M NaClO 4 inEC: pc=1:1 vol% with 5.0% FEC (NC-004) for experimental electrolyte system assembled button cell (half cell) and charge-discharge rate and stability tests were performed.
Fig. 6 is an SEM image of the prepared carbon-coated sodium vanadium phosphate cathode material. The carbon-coated sodium vanadium phosphate anode material has a fluffy porous structure as a whole.
Example 3
Preparing a cobalt doped sodium vanadium phosphate composite precursor dispersion liquid: adding vanadium trioxide, sodium chloride, cobalt acetate tetrahydrate and phosphoric acid into absolute ethyl alcohol according to the mass ratio of V to Co to Na to P of 1.8 to 0.3 to 3, adding small molecule class A mercapto carbon source-containing 2-mercaptoethylamine and macromolecule class B carbon source polyglycine to the absolute ethyl alcohol according to the mass ratio of 2 to 1, wherein the mass ratio of a vanadium sodium phosphate positive electrode active material precursor (comprising a sodium source, a vanadium source and a phosphorus source) to the carbon source is 10 to 1, adding the vanadium sodium phosphate positive electrode active material precursor into absolute ethyl ether, regulating the solid content of the solution to 15%, magnetically stirring the solution at a rotating speed of 1000rpm, heating the solution to 80 ℃, and continuing stirring for 5 hours until the solution is completely changed into a suspension state which is completely and uniformly mixed, and dissolving other substances except vanadium pentoxide to obtain a uniform precursor dispersion.
Preparing a cobalt doped sodium vanadium phosphate composite solid precursor: and (3) carrying out vacuum drying on the precursor dispersion liquid, wherein the pressure in a vacuum drying box is less than-30 MPa, the vacuum drying temperature is set to 180 ℃, the drying time is 10 hours, and the cobalt-doped sodium vanadium phosphate composite solid precursor powder is obtained after solid-phase grinding until the precursor dispersion liquid is completely dried.
Preparing a cobalt-doped carbon-coated sodium vanadium phosphate positive electrode material: weighing 5g of the vanadium sodium phosphate composite solid precursor, placing the precursor into corundum, placing the corundum into a tube furnace for calcination, heating the corundum under helium atmosphere, adjusting the airflow flow rate to 40mL/min, heating the corundum to 300 ℃ at a heating rate of 6 ℃/min, heating the corundum to 1000 ℃ at a temperature of 10 ℃/min after heat preservation for 5h, crushing the corundum by a powder crusher with power of 1000W, continuously crushing the corundum for 5s to fully and uniformly mix the corundum, and pouring the crushed powdery solid into a 200-mesh screen for sieving, so that the discharging grain diameter is lower than 0.074mm, and finally obtaining the high-performance cobalt-doped carbon-coated vanadium sodium phosphate anode material with uniform grain diameter distribution.
High rate performance and long cycling stability sodium ion battery assembly: weighing NVP/C (0.35 g) prepared above, PVDF and SP according to the mass ratio of 7:2:1, preparing a PVDF solution with NMP as a solvent to 5wt.%, using the PVDF solution, controlling the solid content of the slurry to be 22% -25%, coating the slurry on an aluminum foil through a coating machine, drying the slurry for 1-3 hours at 120 ℃ by blowing, then cutting into wafers with the diameter of 12mm by a manual sheet punching machine and taking the wafers as working electrodes for standby, weighing the mass of the pole pieces after vacuum drying at 150 ℃ overnight, adopting a metal sodium sheet as a counter electrode, adopting a glass fiber diaphragm to form a sodium ion transmission channel, adopting 1.0M NaClO 4 inEC: pc=1:1 vol% with 5.0% FEC (NC-004) for experimental electrolyte system assembled button cell (half cell) and charge-discharge rate and stability tests were performed.
Fig. 7 is an SEM image of the prepared cobalt-doped carbon-coated sodium vanadium phosphate cathode material. The carbon-coated sodium vanadium phosphate anode material has a block structure with uniform distribution.
Example 4
Preparing a boron doped sodium vanadium phosphate composite precursor dispersion liquid: vanadium pentoxide, sodium borohydride, disodium hydrogen phosphate and fructose are added into absolute ethyl alcohol according to the mass ratio of V to Na to P to B of 2 to 3 to 2.8 to 0.2, small molecule A-class sulfhydryl-containing carbon source 2-sulfhydryl pyridine and macromolecule B-class carbon source polyaniline according to the mass ratio of 3 to 1, wherein the mass ratio of vanadium sodium phosphate positive electrode active material precursor (comprising sodium source, vanadium source and phosphorus source) to carbon source is 5 to 1, the solution is added into absolute ethyl ether, the solid content is regulated to 20 percent, magnetic stirring is carried out at the rotating speed of 500rpm, and the solution is continuously stirred for 2 hours after the temperature is heated to 80 ℃ until the solution becomes completely clear, so that uniform precursor dispersion is obtained.
Preparing a boron doped sodium vanadium phosphate composite solid precursor: and (3) spray drying the precursor dispersion, adjusting the set value of a spray drying fan to 90, setting the temperature to 230 ℃, setting the set value of a peristaltic pump to 30, setting the set value of a needle to 6s, starting an air pump when the outlet temperature is increased to more than 80 ℃, closing the peristaltic pump (about 5 min) after the materials are completely sprayed by water, and closing the fan when the inlet air temperature is reduced to below 90 ℃, so as to collect the boron-doped sodium vanadium phosphate composite solid precursor in a collector.
Preparing a boron-doped carbon-coated sodium vanadium phosphate positive electrode material: weighing 3g of the vanadium sodium phosphate composite solid precursor, placing the precursor into corundum, placing the corundum into a tube furnace for calcination, heating the corundum under helium atmosphere, adjusting the airflow flow rate to 15mL/min, heating the corundum to 500 ℃ at a heating rate of 2 ℃/min, heating the corundum to 900 ℃ at a heating rate of 5 ℃/min after heat preservation for 3 hours, carrying out crushing by a powder grinding machine with power of 500W, continuously crushing for 25s to fully and uniformly mix the powder, and then pouring the crushed powder solid into a 300-mesh screen for sieving to ensure that the discharge grain diameter is lower than 0.048mm, thereby finally obtaining the high-performance boron-doped carbon-coated vanadium sodium phosphate anode material with uniform grain diameter distribution.
High rate performance and long cycling stability sodium ion battery assembly: weighing NVP/C (0.35 g) prepared above, PVDF and SP according to the mass ratio of 7:2:1, preparing a PVDF solution with NMP as a solvent to 5wt.%, using the PVDF solution, controlling the solid content of the slurry to be 22% -25%, coating the slurry on an aluminum foil through a coating machine, drying the slurry for 1-3 hours at 120 ℃ by blowing, then cutting into wafers with the diameter of 12mm by a manual sheet punching machine and taking the wafers as working electrodes for standby, weighing the mass of the pole pieces after vacuum drying at 150 ℃ overnight, adopting a metal sodium sheet as a counter electrode, adopting a glass fiber diaphragm to form a sodium ion transmission channel, adopting 1.0M NaClO 4 inEC: pc=1:1 vol% with 5.0% FEC (NC-004) for experimental electrolyte system assembled button cell (half cell) and charge-discharge rate and stability tests were performed.
Fig. 8 is an SEM image of the prepared boron-doped carbon-coated sodium vanadium phosphate cathode material. The carbon-coated sodium vanadium phosphate anode material integrally presents a microsphere/block structure.
Example 5
The steps are the same as those in example 1, only the sodium source is disodium tetraacetate, the vanadium sodium phosphate composite precursor dispersion liquid is obtained in step 5.1, and the other steps are the same as those in example 1, so that the carbon-coated vanadium sodium phosphate anode material is obtained.
Example 6
The steps are the same as those in the embodiment 1, only the phosphorus source is trisodium phosphate, the vanadium sodium phosphate composite precursor dispersion liquid is obtained in the step 6.1, and the other steps are the same as those in the embodiment 1, so that the carbon-coated vanadium sodium phosphate cathode material is obtained.
Example 7
The steps are the same as those in example 1, only the small molecule A-class sulfhydryl-containing carbon source is 3-mercaptopropionic acid, the vanadium sodium phosphate composite precursor dispersion liquid is obtained in step 7.1, and the other steps are the same as those in example 1, so as to obtain the carbon-coated vanadium sodium phosphate positive electrode material.
Example 8
The steps are the same as those in the embodiment 1, only the high polymer B-type carbon source is polyacrylonitrile, so as to obtain a vanadium sodium phosphate composite solid precursor, and the other steps are the same as those in the embodiment 1, so as to obtain the carbon-coated vanadium sodium phosphate anode material.
Example 9
The procedure was carried out in the same manner as in example 1, the spray-drying temperature in step 9.2 was adjusted to 200℃and the other procedures were carried out in the same manner as in example 1, to obtain a carbon-coated sodium vanadium phosphate cathode material.
Example 10
The procedure was carried out in the same manner as in example 1, the secondary calcination time in step 10.3 was adjusted to 20 hours, and the other procedures were carried out in the same manner as in example 1, to obtain a carbon-coated sodium vanadium phosphate cathode material.
Comparative example 1
The steps are the same as those in example 1, no small molecule A-class mercapto carbon source 2-mercaptobutyric acid is added, and the other steps are the same as those in example 1, so as to obtain the carbon-coated sodium vanadium phosphate anode material.
Comparative example 2
The procedure is the same as in example 4, polymer B carbon source polyisobutene is not added, and the other procedures are the same as in example 1, so as to obtain the carbon-coated sodium vanadium phosphate anode material.
Table 1: the main physical and chemical parameters and sodium ion battery performance of examples 1-10 and comparative examples 1-2:
as can be seen from the contents of table 1, the pure-phase high-crystallinity carbon-coated sodium vanadium phosphate cathode material with good sodium ion battery performance can be successfully prepared according to the invention, which comprises a plurality of types of metal/nonmetal-doped carbon-coated sodium vanadium phosphate cathode materials.
According to the contents of table 1, the D50 particle size of the carbon-coated sodium vanadium phosphate positive electrode material is in the range of 4-10 mu m, the particle size and the battery performance of the carbon-coated sodium vanadium phosphate positive electrode material can be regulated by precisely regulating experimental parameters in the preparation process, and the introduction of the small molecular A-class mercapto-containing carbon source or the high molecular B-class carbon source is beneficial to improving the electronic conductivity, specific capacity and cycling stability of the sodium vanadium phosphate.
It should be understood that the above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention, not to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the carbon-coated sodium vanadium phosphate positive electrode material for the sodium ion battery is characterized by comprising the following steps of:
(1) Preparing a vanadium sodium phosphate composite precursor dispersion liquid: weighing a certain amount of sodium source, vanadium source, phosphorus source and carbon source, and completely dispersing the sodium source, the vanadium source, the phosphorus source and the carbon source in a solvent in a heating and stirring mode to obtain uniform vanadium sodium phosphate composite precursor dispersion liquid;
(2) Preparing a vanadium sodium phosphate composite solid precursor: the sodium vanadium phosphate composite precursor dispersion liquid enables sodium source, vanadium source, phosphoric acid and carbon source solid materials to be fully and uniformly mixed, and the solvent is gasified in a drying mode to obtain a sodium vanadium phosphate composite solid precursor;
(3) Preparing a carbon-coated sodium vanadium phosphate anode material: and weighing a certain amount of vanadium sodium phosphate composite solid precursor, placing the precursor into corundum, placing the corundum into a tubular furnace for calcination, heating the corundum under a protective atmosphere, taking the corundum out after the vanadium sodium phosphate composite solid precursor is naturally cooled to room temperature, crushing the vanadium sodium phosphate composite solid precursor by a powder grinding machine, fully and uniformly mixing the crushed vanadium sodium phosphate composite solid precursor, and then pouring the crushed powdery solid into a screen for sieving to obtain the high-performance carbon-coated vanadium sodium phosphate anode material with uniform particle size distribution.
2. The method for preparing a carbon-coated sodium vanadium phosphate positive electrode material for sodium ion batteries according to claim 1, wherein the sodium source in the step (1) comprises one or more of sodium acetate, sodium carbonate, disodium tetraacetate, sodium nitrate, sodium sulfate, sodium chloride, sodium bicarbonate, sodium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate;
the vanadium source comprises one or more of ammonium metavanadate, vanadium pentoxide, vanadium oxide, vanadium trioxide, vanadium phosphate monohydrate, vanadium sulfate, vanadyl sulfate, sodium orthovanadate and vanadyl oxalate;
the phosphorus source comprises one or more of sodium hypophosphite, disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate, phosphoric acid, monoammonium phosphate and diammonium hydrogen phosphate.
3. The method for preparing the carbon-coated sodium vanadium phosphate positive electrode material for the sodium ion battery according to claim 1, wherein the carbon source in the step (1) comprises a small molecule A-type mercapto-containing carbon source and a high molecule B-type carbon source, and the molar ratio of the small molecule A-type mercapto-containing carbon source to the high molecule B-type carbon source is 1:1-3:1, wherein the small molecule A-type mercapto-containing carbon source comprises one or more of 2-mercaptobutyric acid, 3-mercaptopropionic acid, 2-mercaptoethylamine, 2-mercaptopyridine, 2-mercaptopyrazine and 1, 5-dimercaptonaphthyl; the polymer B carbon source comprises one or more of polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyvinyl alcohol, polyisobutylene, polyglycine, polyaniline, polyacrylonitrile and polypyrrole.
4. The method for preparing the carbon-coated sodium vanadium phosphate positive electrode material for the sodium ion battery according to claim 1, wherein in the step (1), the molar ratio of the sodium source to the vanadium source is 1:1-3:1, the molar ratio of the sodium source to the phosphorus source is 1:3-1:1, and the mass ratio of the precursor of the sodium vanadium phosphate positive electrode material to the carbon source is 5:1-15:1.
5. The preparation method of the carbon-coated sodium vanadium phosphate positive electrode material for the sodium ion battery, which is disclosed in claim 1, is characterized in that the solvent in the step (1) comprises one or more of deionized water, absolute ethyl alcohol, absolute ethyl ether and absolute methanol, and the mass of the precursor of the sodium vanadium phosphate positive electrode active material and the mass of a carbon source account for 10% -30% of the total mass of the solution.
6. The method for preparing the carbon-coated sodium vanadium phosphate positive electrode material for the sodium ion battery according to claim 1, wherein the heating solvent temperature in the step (1) is 60-80 ℃, the stirring speed is 300-2000rpm, and the heating and stirring time is 1-10 h; heating and stirring are needed until the solution is completely clear and has no solid precipitation.
7. The method for preparing the carbon-coated sodium vanadium phosphate positive electrode material for the sodium ion battery according to claim 1, wherein the drying mode in the step (2) can be one or more of spray drying, air blast drying and vacuum drying; the spray drying fan is set to 75-95, the temperature is set to 160-250 ℃, the peristaltic pump is set to 10-50mL/min, the needle is set to 5-15s, the particle size of the outlet particles can be precisely regulated and controlled by regulating the solid content of the solution and the spray drying parameters, the particle size range is 2-10 mu m, and the time required by spray drying is determined according to the sample amount; the blast drying temperature is set to 80-180 ℃ and the drying time is set to 10-30h; the pressure in the vacuum drying box body is required to be less than-30 MPa, the drying temperature is set to be 80-180 ℃, and the drying time is set to be 10-30h; the obtained vanadium sodium phosphate composite solid precursor material is ground into powder by a solid phase grinding mode.
8. The method for preparing the carbon-coated sodium vanadium phosphate positive electrode material for the sodium ion battery according to claim 1, wherein the protective atmosphere in the step (3) can be nitrogen, helium, argon, neon and other inert gases, and the airflow speed is 2-50 mL/min; the temperature rising rate is 2-10 ℃/min, the calcining temperature is 600-1000 ℃, the calcining time is 5-20h, and particularly, the carbonizing time can be fully increased by adopting a sectional calcining mode, the primary calcining temperature rising rate is 2-10 ℃/min, the primary calcining temperature is 300-500 ℃, the primary calcining time is 2-5h, the secondary calcining temperature rising rate is 2-10 ℃/min, the secondary calcining temperature is 600-1000 ℃, and the calcining time is 5-20h.
9. The method for preparing the carbon-coated sodium vanadium phosphate positive electrode material for the sodium ion battery according to claim 1, wherein the power of the powdering machine in the step (3) is 200-2000W, the working time is not more than 30s, the discharge particle size is less than 0.5mm, and the sieving number is 200-350 meshes.
10. A sodium vanadium phosphate composite material prepared according to the method of any one of claims 1-12.
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