CN105655565B - A kind of sodium-ion battery composite positive pole and preparation method thereof - Google Patents
A kind of sodium-ion battery composite positive pole and preparation method thereof Download PDFInfo
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- CN105655565B CN105655565B CN201610217175.7A CN201610217175A CN105655565B CN 105655565 B CN105655565 B CN 105655565B CN 201610217175 A CN201610217175 A CN 201610217175A CN 105655565 B CN105655565 B CN 105655565B
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- Prior art keywords
- sodium
- vanadium
- ion battery
- amorphous carbon
- atmosphere
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 40
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title description 11
- CFVBFMMHFBHNPZ-UHFFFAOYSA-N [Na].[V] Chemical compound [Na].[V] CFVBFMMHFBHNPZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- RHFUXPCCELGMFC-UHFFFAOYSA-N n-(6-cyano-3-hydroxy-2,2-dimethyl-3,4-dihydrochromen-4-yl)-n-phenylmethoxyacetamide Chemical compound OC1C(C)(C)OC2=CC=C(C#N)C=C2C1N(C(=O)C)OCC1=CC=CC=C1 RHFUXPCCELGMFC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 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 claims abstract description 32
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 238000005253 cladding Methods 0.000 claims abstract description 12
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000002322 conducting polymer Substances 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- 238000011049 filling Methods 0.000 claims abstract 2
- 239000012298 atmosphere Substances 0.000 claims description 38
- 239000011734 sodium Substances 0.000 claims description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 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 12
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 12
- 229920000767 polyaniline Polymers 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229920000128 polypyrrole Polymers 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical class O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 3
- 239000007767 bonding agent Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 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
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 description 25
- 229910001373 Na3V2(PO4)2F3 Inorganic materials 0.000 description 24
- 229910020657 Na3V2(PO4)3 Inorganic materials 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 229920001690 polydopamine Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002228 NASICON Substances 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910017677 NH4H2 Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- -1 Amide hydrochloride Chemical class 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- ZVKRVGZVXQYLPZ-UHFFFAOYSA-N [Li].[V].P(O)(O)(O)=O Chemical compound [Li].[V].P(O)(O)(O)=O ZVKRVGZVXQYLPZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229960003638 dopamine Drugs 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 1
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- 229910003206 NH4VO3 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GWBWGPRZOYDADH-UHFFFAOYSA-N [C].[Na] Chemical compound [C].[Na] GWBWGPRZOYDADH-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 235000019593 adhesiveness Nutrition 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 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 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229960004502 levodopa Drugs 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000004137 mechanical activation Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 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
-
- 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
- H01M4/36—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
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Abstract
The invention discloses a kind of sodium-ion battery composite positive pole, for compound more caryogram core shell structures, the fluorophosphoric acid vanadium sodium that the vanadium phosphate sodium that its kernel is coated by multiple amorphous carbon layers coats with multiple amorphous carbon layers, which mixes, to be formed, and shell and the filling of kernel gap are conducting polymer；Respectively in nano level vanadium phosphate sodium and the external sheath amorphous carbon layer of fluorophosphoric acid vanadium sodium, conductive high polymer monomer is subjected to polymerisation, the vanadium phosphate sodium of amorphous carbon layer cladding made from adding thereto and the fluorophosphoric acid vanadium sodium of amorphous carbon layer cladding, it is well mixed, obtained mixture is spray-dried, obtains target product.The sodium-ion battery composite positive pole of the present invention, improve high rate performance, cycle performance, charging/discharging voltage and the heat endurance of sodium-ion battery positive material vanadium phosphate sodium, improve its energy density and power density, the tap density and processing characteristics of material can also be improved simultaneously, it is more suitable for the sodium-ion battery of high power and high-energy-density.
Description
Technical field
The invention belongs to cell art, is related to a kind of battery composite anode material and preparation method thereof, and in particular to
A kind of sodium-ion battery composite positive pole and preparation method thereof.
Background technology
Lithium ion battery has been widely used in various portable electric appts because of its excellent energy-storage property.But lithium
Reserves it is extremely limited, it is difficult to meet the needs of following long-run development, therefore, sight has been invested resourceful sodium by people
On.Sodium and lithium belong to same main group, and chemical property is similar, and electrode potential approaches, and resource reserve enriches.Na+Radius
(0.102nm) compares Li+Radius (0.076nm) it is big by 30%, standard electrode potential is -2.71V, only higher than the -3.04V of lithium
0.33V.If sodium ion secondary battery of good performance can be built, lithium ion battery will be compared in resource, environment and cost etc.
It is advantageous, by as a kind of new green environment protection energy-storage battery of great development prospect.
In recent years, the material with NASICON (Fast ion conductor) type frame structure is increasingly becoming study hotspot.
NASICON refers to a kind of solid electrolyte under moderate temperature conditions with fabulous ionic conductance performance.Wherein sodium ion
In cell positive material, vanadium phosphate sodium (Na3V2(PO4)3) there is NASICON type open three dimensional frame structures, this structure tool
Have and supply Na+The three-dimensional channel of fast transferring diffusion；Na+In abjection/telescopiny, caving in for three-dimensional frame structure will not be caused
Destroy, can only cause the minor variations of lattice parameter；In charge and discharge process, Na3V2(PO4)3Electrode reaction be a typical case
Two phase reaction, i.e.,And in whole electrode process, the abjection of sodium/embedding
Volume Changes caused by entering are very small (8.26%), and this is favorably improved its cycle performance.Na3V2(PO4)3As sodium ion
During cell positive material, storage sodium average voltage is higher, based on V4+/V3+The charging/discharging voltage platform of oxidation-reduction pair be about
3.4V(vs.Na/Na+), theoretical specific capacity 118mAh/g, heat endurance is also very well (450 DEG C), therefore Na3V2(PO4)3It is very suitable
The positive electrode of high-performance room-temperature sodium ion energy-storage battery is synthesized, novel Room Temperature can be built together with the negative material such as hard carbon
Sodium ion energy-storage battery.
However, due to the presence of phosphate radical polyanion, Na3V2(PO4)3Electronic conductivity it is relatively low.Researcher at present
Adulterated using carbon coating, metal ion is bulk phase-doped, reduce material granule, changes the means such as material morphology to improve the material
Electronic conductivity, so that it obtains preferable high rate performance and cycle performance.But in current study on the modification method, substantially
On be all monistic to be directed to Na3V2(PO4)3The problem of electronic conductivity is low, in fact, to make Na3V2(PO4)3As one kind
The sodium-ion battery positive material of high-energy-density and high power density with excellent high rate performance, it should also find more comprehensive
Close effective modified method.
Nearest fluorophosphoric acid vanadium sodium is reported is used for sodium-ion battery as a kind of novel battery material.Fluorophosphoric acid vanadium sodium has
NASICON structures, ionic conductivity is high, has two charging/discharging voltage platforms, respectively 3.7V (vs.Na/Na+) and 4.2V
(vs.Na/Na+), in V4+/V3+Oxidation-reduction pair all positive electrodes in, fluorophosphoric acid vanadium sodium has highest average voltage
3.95V(vs.Na/Na+), theoretical specific capacity 128mAh/g, heat endurance is also very good (510 DEG C), in charge and discharge process,
The electrode reaction of fluorophosphoric acid vanadium sodium is also a typical two phase reaction, i.e.,
In whole electrode process, Volume Changes caused by abjection/insertion of sodium are very small (about 1.79%), than vanadium phosphate sodium
Cycle performance is more preferably.But fluorophosphoric acid vanadium sodium has fluorine element, in preparation process, fluorine more or less understands etching apparatus, therefore
Only large-scale production can not possibly be realized by the use of fluorophosphoric acid vanadium sodium as positive electrode.
The content of the invention
In view of this, an object of the present invention is to provide a kind of sodium-ion battery composite positive pole, to improve sodium
Ion battery positive electrode Na3V2(PO4)3High rate performance, cycle performance, charging/discharging voltage and heat endurance, improve its energy
Density and power density, while can also improve the tap density and processing characteristics of material, it is more suitable for high power and high energy
The sodium-ion battery of metric density.
Specifically, the present invention provides following technical scheme：
The sodium-ion battery composite positive pole of the present invention, is compound more caryogram core shell structures, its kernel is determined by multiple nothings
The vanadium phosphate sodium of shape carbon-coating cladding and the fluorophosphoric acid vanadium sodium of multiple amorphous carbon layers cladding mix composition, and shell and kernel gap are filled out
It is conducting polymer to fill.
Preferably, the mass ratio of described vanadium phosphate sodium, fluorophosphoric acid vanadium sodium, conducting polymer and amorphous carbon be 50~
80：8~40：3~18：5~20.
Preferably, described conducting polymer is polyaniline (PANI), polypyrrole (PPY), poly- 3,4-ethylene dioxythiophene
(PEDOT) one or more in.
The second object of the present invention is to provide a kind of preparation method of above-mentioned sodium-ion battery composite positive pole, specifically
, comprise the steps：
A. respectively in nano level vanadium phosphate sodium and the external sheath amorphous carbon layer of fluorophosphoric acid vanadium sodium；
Preferably, described vanadium phosphate sodium and fluorophosphoric acid vanadium sodium are made respectively by mechanical activation-solid phase reduction method.
Specifically, mechanical activation-solid phase reduction method prepares vanadium phosphate sodium or fluorophosphoric acid vanadium sodium, it is by sodium source, phosphorus source, vanadium
Source, Fluorine source (do not need) ball milling mixing when preparing vanadium phosphate sodium, then 550~800 DEG C of 1~24h of calcining under reducing atmosphere,
It is final to obtain vanadium phosphate sodium or fluorophosphoric acid vanadium sodium.
Preferably, described sodium source be sodium fluoride, sodium dihydrogen phosphate, sodium carbonate, sodium hydroxide, one kind in sodium acetate or
It is several；Described Fluorine source is sodium fluoride and/or ammonium fluoride；Described vanadium source is in vanadic anhydride, vanadium dioxide, metavanadic acid ammonia
One or more；Described phosphorus source is the one or more in ammonium dihydrogen phosphate, sodium dihydrogen phosphate, triammonium phosphate, phosphoric acid.
Preferably, described reducing atmosphere be argon hydrogen mixed atmosphere, nitrogen and hydrogen mixture atmosphere, acetylene/argon gas mixed atmosphere,
Any one in acetylene/nitrogen mixture atmosphere.
Specifically, described amorphous carbon layer is pyrolyzed to be formed with poly-dopamine (PDA) for carbon source, i.e., in vanadium phosphate sodium
It is that vanadium phosphate sodium or fluorophosphoric acid vanadium sodium are added into dopamine hydrochloride with the method for fluorophosphoric acid vanadium sodium external sheath amorphous carbon layer
(DAHCl) in solution, at least 4h is stirred at room temperature, filters, wash, dry, then under reducing atmosphere, 450~650 DEG C are forged
Burn 0.5~5h and obtain.
Preferably, described carbon source can also be glucose, citric acid, oxalic acid, polyethylene glycol, salicylic acid, tartaric acid, poly-
One or more in vinyl alcohol and cinnamic acid.
Preferably, described reducing atmosphere be argon hydrogen mixed atmosphere, nitrogen and hydrogen mixture atmosphere, acetylene/argon gas mixed atmosphere,
Any one in acetylene/nitrogen mixture atmosphere.
B. conductive high polymer monomer is subjected to polymerisation, adds amorphous carbon layer cladding made from step a thereto
The fluorophosphoric acid vanadium sodium of vanadium phosphate sodium and amorphous carbon layer cladding, is well mixed；
Preferably, described conductive high polymer monomer is in aniline monomer, pyrrole monomer, 3,4-ethylene dioxythiophene monomer
One or more.
C. step b mixture is spray-dried, obtains target product.
Specifically, described spray drying be under protective atmosphere 100~220 DEG C be dried.
Preferably, described protective atmosphere is the one or more in nitrogen, argon gas, neon.
Spraying is prepared usually micron-sized, is combined with the nanoscale of above mechanical activation, can be formed nano-micro structure.
Further, the present invention also provides a kind of sodium-ion battery anode composite, including matrix and is placed in matrix surface
Coating material, the coating material include above-mentioned sodium-ion battery composite positive pole, conductive material and bonding agent.
Further, the present invention also provides a kind of sodium-ion battery, including above-mentioned sodium-ion battery anode composite, negative pole,
Barrier film and electrolyte between a positive electrode and a negative electrode is set.
Compared with prior art, sodium-ion battery composite positive pole of the invention tool has the advantage that：
(1) using vanadium phosphate sodium as main body active positive electrode material, fluorophosphoric acid vanadium sodium is as the second phase active positive electrode material, system
Standby composite positive pole, specific capacity, charging/discharging voltage platform, cycle performance and the heat endurance of vanadium phosphate sodium can obtain simultaneously
Improve, while can also solve the problems, such as that fluorophosphoric acid vanadium sodium is unable to large-scale practical application.
(2) in vanadium phosphate sodium and fluorophosphoric acid vanadium sodium external sheath amorphous carbon, vanadium phosphate sodium and fluorophosphoric acid can not only be improved
The electronic conductivity of vanadium sodium, while growing up for crystal grain can also be suppressed, strengthen the electronics contact between adjacent particle, so as to improve
The high rate performance and cycle performance of composite positive pole and battery.
Especially using poly-dopamine as carbon source, poly-dopamine synthesis condition is simple, mainly by dopamine in alkaline water
Autohemagglutination is aoxidized in solution to form, and utilizes the strong adhesion characteristics of dopamine in the course of the polymerization process, using it as carbon source, poly-dopamine meeting
Strength is attached to the particle surface of phosphoric acid vanadium lithium and fluorophosphoric acid vanadium sodium, then by being sintered into carbon to form one layer complete amorphous
Carbon coating layer, and the extremely strong adhesivenesses of PDA cause the conductive network structure that " carbon bridge " is formd between particle, considerably increase
Transmission of the electronics in active material.
(3) conducting polymer not only has high electronic conduction characteristic, and itself also has electro-chemical activity, as outer
Shell clad composite material, dual-use function can be played.In addition, the material being prepared by the method for the present invention, can form nano-micro structure
Compound multinuclear core shell structure composite positive pole, conducting polymer coats multiple amorphous carbon layers as outer shell
Vanadium phosphate sodium and fluorophosphoric acid vanadium sodium be wrapped in a spherical conductive polymer subshell, composite positive pole can not only be improved
Electric conductivity, and this nano-micro structure can make uniformly to divide in nano level interior nuclear active material phosphoric acid vanadium lithium and fluorophosphoric acid vanadium
Dissipate in conductive polymer sub-network, can further accelerate the transmission speed of electronics and ion between each particle, so as to
Improve composite positive pole overall high rate performance and cycle performance.In addition, the processing characteristics and tap density of material can obtain
To being obviously improved.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, make required in being described below to embodiment
Accompanying drawing is briefly described, it should be apparent that, the accompanying drawing for the present invention in describing below is only the one of the present invention
A little embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to these
Accompanying drawing obtains other accompanying drawings.
Fig. 1 is the structural representation of sodium-ion battery composite positive pole of the present invention；
Fig. 2 is Na prepared by embodiment 13V2(PO4)3X-ray diffraction (XRD) collection of illustrative plates；
Fig. 3 is Na prepared by embodiment 13V2(PO4)2F3XRD spectrum；
Fig. 4 is Na prepared by embodiment 13V2(PO4)3/C·Na3V2(PO4)2F3/ C@PANI XRD spectrum；
Fig. 5 is Na prepared by embodiment 13V2(PO4)3First charge-discharge curve map under 0.1C multiplying powers；
Fig. 6 is Na prepared by comparative example 13V2(PO4)3The first charge-discharge curve maps of/C@PANI under 0.1C multiplying powers；
Fig. 7 is Na prepared by embodiment 13V2(PO4)3/C·Na3V2(PO4)2F3/ C@PANI under 0.1C multiplying powers first
Charging and discharging curve figure.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, detailed retouch is carried out to the technical scheme in the embodiment of the present invention
State.
Embodiment 1
Na3V2(PO4)3/C·Na3V2(PO4)2F3/ C@PANI preparation
A. 0.2mol Na is prepared3V2(PO4)3：By Na2CO3、V2O5、NH4H2PO4According to stoichiometric proportion dispensing, with ethanol
For solvent, pulpous state compound is obtained in 6 hours with 400 revs/min of speed ball milling in planetary ball mill, then at 80 DEG C
Forced air drying, by the presoma being dried to obtain under argon hydrogen mixed atmosphere (5vol.% hydrogen), calcined 6 hours in 650 DEG C,
Furnace cooling obtains product Na3V2(PO4)3, tap density 1.12g/cm3。
Prepare 0.1mol Na3V2(PO4)2F3：By NaF, V2O5、NH4H2PO4According to stoichiometric proportion dispensing, using ethanol as
Solvent, pulpous state compound is obtained in 6 hours with 400 revs/min of speed ball milling in planetary ball mill, then the drum at 80 DEG C
It is air-dried dry, by the presoma being dried to obtain under argon hydrogen mixed atmosphere (5vol.% hydrogen), calcined 6 hours in 650 DEG C, with
Stove cools down to obtain product Na3V2(PO4)2F3。
B. using 0.002mol/L tri methylol amino methane (Tris) solution as solvent, 0.5mgmL is prepared-1DOPA
Amide hydrochloride, pH=8.5, Na prepared by a steps is weighed respectively3V2(PO4)3And Na3V2(PO4)2F3Add 100mL DOPA
In amide hydrochloride, after room temperature magnetic agitation 12h, filter, washing, dry powder-mixed presoma.Body before mixing
Body is calcined 2 hours under 550 DEG C of argon hydrogen mixed atmospheres (5vol.% hydrogen) in tube furnace, after keeping atmosphere furnace cooling
Obtain the vanadium phosphate sodium and fluorophosphoric acid vanadium sodium Na of product amorphous carbon cladding3V2(PO4)3/C·Na3V2(PO4)2F3/C。
C. take 0.2mL aniline monomer to be dissolved in 0.1mol/L 100mL hydrochloric acid solutions, it is made that step b is added in stirring
Standby product, ultrasonic disperse is uniform, and it is 1.2 to weigh with aniline mol ratio:1 ammonium persulfate is dissolved in 0.1mol/L 50mL hydrochloric acid
In solution, under conditions of ice-water bath, ammonium persulfate solution is added dropwise to the phosphoric acid of aniline-hydrochloric acid-amorphous carbon cladding
In vanadium sodium and fluorophosphoric acid vanadium sodium, stirring reaction obtains suspension in 5 hours.
D. the suspension prepared by step c is spray-dried in 150 DEG C in a nitrogen atmosphere, finally gives anode composite
Material Na3V2(PO4)3/C·Na3V2(PO4)2F3/ C@PANI, its tap density reach 1.85g/cm3。
Embodiment 2
Na3V2(PO4)3/C·Na3V2(PO4)2F3/ C@PPY preparation
A. 0.2mol Na is prepared3V2(PO4)3：By NaH2PO4、V2O3According to stoichiometric proportion dispensing, using ethanol as solvent,
Pulpous state compound is obtained in 8 hours with 350 revs/min of speed ball milling in planetary ball mill, then air blast is done at 80 DEG C
It is dry, by the presoma being dried to obtain under nitrogen and hydrogen mixture atmosphere (8vol.% hydrogen), calcined 8 hours in 600 DEG C, it is cold with stove
But product Na is obtained3V2(PO4)3, tap density 1.10g/cm3。
Prepare 0.17mol Na3V2(PO4)2F3：By NaF, V2O5、H3PO4According to stoichiometric proportion dispensing, in planetary ball
Pulpous state compound is obtained in 5 hours with 450 revs/min of speed ball milling in grinding machine, the then forced air drying at 80 DEG C will be dry
The presoma arrived is calcined 8 hours, furnace cooling obtains product under nitrogen and hydrogen mixture atmosphere (8vol.% hydrogen) in 600 DEG C
Na3V2(PO4)2F3。
B. a certain amount of citric acid is weighed, deionized water is added, weighs Na prepared by a steps respectively3V2(PO4)3And Na3V2
(PO4)2F3Add in above-mentioned citric acid solution, after room temperature magnetic agitation 4h, filter, washing, dry powder-mixed forerunner
Body.Mixing precursor is calcined 3 hours under 500 DEG C of nitrogen in tube furnace, product is obtained without fixed after keeping atmosphere furnace cooling
The vanadium phosphate sodium and fluorophosphoric acid vanadium sodium Na of shape carbon coating3V2(PO4)3/C·Na3V2(PO4)2F3/C。
C. the Na prepared by b step3V2(PO4)3/C·Na3V2(PO4)2F3/ C is dispersed in the iron of p-methyl benzenesulfonic acid containing 25wt%
Ethanol solution, suspension stirs 0.5 hour under ice-water bath, adds a certain amount of pyrroles (having been distilled before using), then
Reacted 1 hour under being stirred under ice-water bath and obtain suspension.
D. the suspension prepared by step c is spray-dried in 140 DEG C in a nitrogen atmosphere, finally gives anode composite
Material Na3V2(PO4)3/C·Na3V2(PO4)2F3/ C@PPY, its tap density reach 1.74g/cm3。
Embodiment 3
Na3V2(PO4)3/C·Na3V2(PO4)2F3/ C@PEDOT preparation
A. 0.2mol Na is prepared3V2(PO4)3：By NaOH, V2O5、NH4H2PO4According to stoichiometric proportion dispensing, with ethanol
For solvent, pulpous state compound is obtained in 5 hours with 450 revs/min of speed ball milling in planetary ball mill, then at 80 DEG C
Forced air drying, by the presoma being dried to obtain under acetylene and argon gas mixed atmosphere (10vol.% acetylene), in 700 DEG C of calcinings
5 hours, furnace cooling obtained product Na3V2(PO4)3, tap density 1.09g/cm3。
Prepare 0.03mol Na3V2(PO4)2F3：By NH4F、NH4VO3、NaH2PO4According to stoichiometric proportion dispensing, with second
Alcohol is solvent, pulpous state compound is obtained within 5 hours in planetary ball mill with 450 revs/min of speed ball milling, then at 80 DEG C
Lower forced air drying, by the presoma being dried to obtain under acetylene and argon gas mixed atmosphere (10vol.% acetylene), forged in 700 DEG C
Burn 5 hours, furnace cooling obtains product Na3V2(PO4)2F3。
B. a certain amount of glucose is weighed, deionized water is added, weighs Na prepared by a steps respectively3V2(PO4)3And Na3V2
(PO4)2F3Add in above-mentioned glucose solution, after room temperature magnetic agitation 5h, filter, washing, dry powder-mixed forerunner
Body.Mixing precursor is calcined 5 hours under 450 DEG C of nitrogen in tube furnace, product is obtained without fixed after keeping atmosphere furnace cooling
The vanadium phosphate sodium and fluorophosphoric acid vanadium sodium Na of shape carbon coating3V2(PO4)3/C·Na3V2(PO4)2F3/C。
C. a certain amount of double trifluoromethanesulfonimide lithiums (LiTFSI) are weighed, are dissolved in methanol, add 3,4-
Na prepared by ethylenedioxy thiophene monomer and step b3V2(PO4)3/C·Na3V2(PO4)2F3/ C, suspended after stirring
Liquid.
D. the suspension prepared by step c is spray-dried in 120 DEG C in a nitrogen atmosphere, finally gives anode composite
Material Na3V2(PO4)3/C·Na3V2(PO4)2F3/ C@PEDOT, its tap density reach 1.82g/cm3。
Comparative example 1
Na3V2(PO4)3/ C@PANI preparation
Prepare Na3V2(PO4)3/ C@PANI method prepares Na with embodiment 13V2(PO4)3/C·Na3V2(PO4)2F3/C@
PANI's is similar, and difference is that Na need not be prepared3V2(PO4)2F3/ C, remaining step prepare gained with embodiment 1
Na3V2(PO4)3/ C@PANI tap density is 1.65g/cm3。
Embodiment 4
The preparation of battery：
The composite prepared using embodiment 1 is (poly- inclined with acetylene black (conductive agent), PVDF by it as positive electrode active materials
Difluoroethylene, bonding agent) according to 80:10:After 10 mass ratio weighs, a period of time is ground in mortar, is allowed to well mixed,
1-METHYLPYRROLIDONE (NMP) is added, incessantly grinding a period of time, finally gives uniform dark thick slurry like material.
The uniform sizing material obtained after grinding is placed on aluminium foil, film in uniform thickness is uniformly coated into scraper.With metallic sodium
Piece is to electrode, and all-glass paper (Whatman, GF/A) is barrier film, 1mol/L NaClO4/ PC (propene carbonate) is electrolysis
Liquid, CR2032 type button cells are assembled into the argon gas atmosphere glove box of anhydrous and oxygen-free.
Comparative example 2
Using the material prepared in comparative example 1 as positive electrode active materials, remaining step is the same as embodiment 4.
The high rate performance and cycle performance of the sample of table 1 compare
* note：NVP=Na3V2(PO4)3, NVPF=Na3V2(PO4)2F3。
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each embodiment is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that those skilled in the art should for clarity
Using specification as an entirety, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
It is appreciated that other embodiment.
Claims (10)
- A kind of 1. sodium-ion battery composite positive pole, it is characterised in that：It is compound more caryogram core shell structures, and kernel is by multiple The fluorophosphoric acid vanadium sodium of vanadium phosphate sodium and multiple amorphous carbon layers cladding of amorphous carbon layer cladding mixes composition, shell and interior internuclear Gap filling is conducting polymer.
- 2. sodium-ion battery composite positive pole according to claim 1, it is characterised in that：Described vanadium phosphate sodium, fluorine The mass ratio of vanadium phosphate sodium, conducting polymer and amorphous carbon is 50~80：8~40：3~18：5~20.
- 3. sodium-ion battery composite positive pole according to claim 1 or 2, it is characterised in that：Described conductive polymer Son is polyaniline, the one or more in polypyrrole, poly- 3,4- ethylenedioxy thiophenes.
- A kind of 4. method for preparing the sodium-ion battery composite positive pole described in claim any one of 1-3, it is characterised in that Comprise the steps：A. respectively in nano level vanadium phosphate sodium and the external sheath amorphous carbon layer of fluorophosphoric acid vanadium sodium；B. conductive high polymer monomer is subjected to polymerisation, adds the phosphoric acid of amorphous carbon layer cladding made from step a thereto The fluorophosphoric acid vanadium sodium of vanadium sodium and amorphous carbon layer cladding, is well mixed；C. step b mixture is spray-dried, obtains target product.
- 5. according to the method for claim 4, it is characterised in that：Described nano level vanadium phosphate sodium and fluorophosphoric acid vanadium sodium by Mechanical activation-solid phase reduction method is made respectively, respectively by sodium source, phosphorus source and vanadium source, or sodium source, phosphorus source, vanadium source and Fluorine source ball milling Mixing, then 550~800 DEG C of 1~24h of calcining under reducing atmosphere, finally obtain vanadium phosphate sodium or fluorophosphoric acid vanadium sodium；It is described Sodium source be sodium fluoride, sodium dihydrogen phosphate, sodium carbonate, sodium hydroxide, the one or more in sodium acetate；Described Fluorine source is fluorine Change sodium and/or ammonium fluoride；Described vanadium source is the one or more in vanadic anhydride, vanadium dioxide, metavanadic acid ammonia；Described Phosphorus source is the one or more in ammonium dihydrogen phosphate, sodium dihydrogen phosphate, triammonium phosphate, phosphoric acid；Described reducing atmosphere is argon Any one in hydrogen mixed atmosphere, nitrogen and hydrogen mixture atmosphere, acetylene/argon gas mixed atmosphere, acetylene/nitrogen mixture atmosphere.
- 6. according to the method for claim 4, it is characterised in that：It is amorphous in vanadium phosphate sodium and fluorophosphoric acid vanadium sodium external sheath The method of carbon-coating, it is to add vanadium phosphate sodium or fluorophosphoric acid vanadium sodium in dopamine hydrochloride solution, at least 4h is stirred at room temperature, takes out Filter, washing, dry, then under reducing atmosphere, 450~650 DEG C are calcined 0.5~5h and obtained；Described reducing atmosphere is Any one in argon hydrogen mixed atmosphere, nitrogen and hydrogen mixture atmosphere, acetylene/argon gas mixed atmosphere, acetylene/nitrogen mixture atmosphere.
- 7. according to the method for claim 4, it is characterised in that：Described conductive high polymer monomer is aniline monomer, pyrroles One or more in monomer, 3,4- ethylenedioxy thiophene monomers.
- 8. according to the method for claim 4, it is characterised in that：Described spray drying be 100 under protective atmosphere~ 220 DEG C are dried；Described protective atmosphere is the one or more in nitrogen, argon gas, neon.
- A kind of 9. sodium-ion battery anode composite, it is characterised in that：It is described including matrix and the coating material for being placed in matrix surface Coating material includes sodium-ion battery composite positive pole, conductive material and the bonding agent described in claim any one of 1-3.
- A kind of 10. sodium-ion battery, it is characterised in that：Including the sodium-ion battery anode composite described in claim 9, negative pole, Barrier film and electrolyte between a positive electrode and a negative electrode is set.
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| FR3062384B1 (en) * | 2017-02-01 | 2021-02-12 | Centre Nat Rech Scient | PROCESS FOR THE PREPARATION OF A VANADIUM-CARBON PHOSPHATE COMPOSITE MATERIAL BY THE LIQUID ROUTE |
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