CN108735997A - A kind of LiFePO4 based composites, preparation method and the usage more than LiFePO4 theoretical capacity - Google Patents
A kind of LiFePO4 based composites, preparation method and the usage more than LiFePO4 theoretical capacity Download PDFInfo
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- CN108735997A CN108735997A CN201810521839.8A CN201810521839A CN108735997A CN 108735997 A CN108735997 A CN 108735997A CN 201810521839 A CN201810521839 A CN 201810521839A CN 108735997 A CN108735997 A CN 108735997A
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- lithium
- inorganic carbon
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- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 229910052493 LiFePO4 Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 137
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910001868 water Inorganic materials 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 32
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 31
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 21
- 239000011574 phosphorus Substances 0.000 claims abstract description 21
- 239000011247 coating layer Substances 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims abstract description 8
- 238000005253 cladding Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229940116007 ferrous phosphate Drugs 0.000 claims abstract description 6
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 229910021389 graphene Inorganic materials 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 19
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 10
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 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
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004254 Ammonium phosphate Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- PYIDGJJWBIBVIA-UYTYNIKBSA-N lauryl glucoside Chemical compound CCCCCCCCCCCCO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O PYIDGJJWBIBVIA-UYTYNIKBSA-N 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 claims description 4
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 4
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 3
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000000467 phytic acid Substances 0.000 claims description 3
- 235000002949 phytic acid Nutrition 0.000 claims description 3
- 229940068041 phytic acid Drugs 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 3
- 229920001353 Dextrin Polymers 0.000 claims 1
- 239000004375 Dextrin Substances 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 235000019425 dextrin Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 description 39
- 238000012360 testing method Methods 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000003643 water by type Substances 0.000 description 10
- 239000011824 nuclear material Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000010079 rubber tapping Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 229910010710 LiFePO Inorganic materials 0.000 description 6
- 229910000901 LiFePO4/C Inorganic materials 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 239000002127 nanobelt Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910015078 LixV3O7 Inorganic materials 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000007581 slurry coating method Methods 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/62—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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of LiFePO4 based composites, preparation method and the usages more than LiFePO4 theoretical capacity.The LiFePO4 based composites include the compound coating layer of kernel and the cladding kernel, the kernel is made of inorganic carbon base body and the LiFePO4 being attached on the inorganic carbon base body, and the composition of the compound coating layer includes that a water seven aoxidizes three vanadium particles and inorganic carbon.The method includes:1) composite precursor being made of inorganic carbon base body and the ferrous phosphate being attached on the inorganic carbon base body is prepared;2) composite precursor is mixed with lithium source and phosphorus source, roasts, obtains kernel;3) kernel, vanadium source, dissolved organic carbon source, surfactant and solvent are mixed into obtain slurry, hydro-thermal reaction obtains LiFePO4 based composites.The tap density of the LiFePO4 based composites of the present invention is high, detains capacitance up to 170mAh/g or more, and high rate performance is good.
Description
Technical field
The invention belongs to field of lithium ion battery anode, it is related to that a kind of chemical property is good, compacted density is high
Anode material for lithium-ion batteries, preparation method and the usage, and in particular to a kind of phosphoric acid more than LiFePO4 theoretical capacity
Iron lithium based composites, preparation method and as positive electrode lithium ion battery purposes.
Background technology
As the power battery of latest generation, lithium ion battery have energy density is high, have extended cycle life, self discharge is low and
The advantages that memory-less effect and low stain, substantially meets the primary demand of portable device and energy automobile.Lithium-ion electric
One of the key component in pond is positive electrode, and commercialized positive electrode has cobalt acid lithium, LiMn2O4, ternary material, phosphorus
Sour iron lithium material etc..LiFePO 4 material as one of power battery anode material is because cheap, raw material sources are extensive, nothing
The advantages that pollution, is constantly subjected to pay close attention to.
LiFePO 4 material native electronic conductivity is low, low its practical application of influence of ion mobility, main modification
Means have two kinds of carbon coating and doping.But carbon coating can reduce the compacted density and tap density of material.Especially with having
When machine object is as carbon source, roasting process can discharge reducibility gas and so that material structure is loose porous, lead to material compacted density
Decline with tap density serious.
In order to solve these problems, have many workers to attempt to improve preparation process to overcome the above problem.CN
106252635 A disclose a kind of LiFePO4 of graphene coated and preparation method thereof, and method includes:S1, using go from
Sub- water is mixed to prepare graphene oxide dispersion with graphene oxide, and graphene oxide dispersion is mixed with nitrogen source, is mixed
Close object A;S2, lithium source dispersion liquid, phosphorus source dispersion liquid and source of iron dispersion are mixed to prepare using deionized water and lithium source, phosphorus source and source of iron
Liquid, then lithium source dispersion liquid obtained, phosphorus source dispersion liquid and source of iron dispersion liquid are sequentially added in mixture A, stir to get mixing
Object B;S3, mixture B is dried, obtains the ferric lithium phosphate precursor of nitrogen-doped graphene cladding;S4, by nitrogen-doped graphene packet
The ferric lithium phosphate precursor preheating covered, sintering obtain the lithium iron phosphate positive material of nitrogen-doped graphene cladding.However, simple
Carrying out surface cladding using nitrogen-doped graphene, there are of high cost, graphenes to be not easy to disperse, and is not easy to realize uniform cladding, to lead
The problem of causing covered effect undesirable, reduce the energy density per unit volume of product, finally influencing the chemical property of LiFePO4, this limit
Its application coated in electrode material is made.Moreover, when using ferric iron source, still unavoidable reduction process release gas
Problem.In addition, the above method cannot still solve the problems, such as that sheet electron conductivity is low.
Therefore, it is necessary to advanced optimized on current synthesis technology, to prepare a kind of high-tap density and have
The LiFePO4 based composites of excellent electrochemical performance.
Invention content
It is more than that LiFePO4 is theoretical the purpose of the present invention is to provide one kind for the above-mentioned problems in the prior art
LiFePO4 based composites, the preparation method and the usage of capacity.
In order to achieve the above object, the present invention uses following technical scheme:
In a first aspect, the present invention provides a kind of LiFePO4 based composites, the composite material includes kernel and packet
The compound coating layer of the kernel is covered, the kernel is by inorganic carbon base body and the LiFePO4 being attached on the inorganic carbon base body
Particle is constituted, and the composition of the compound coating layer includes that a water seven aoxidizes three vanadium particles and inorganic carbon.
The preparation method that a water seven involved in the present invention aoxidizes three vanadium is the prior art, and chemical formula is represented by
V3O7·H2O, those skilled in the art can refer to method disclosed in the prior art and prepare, and foreign literature for example has:
Shaokang Gao,Zhanjun Chen,MingdengWei,Single crystal nanobelts of V3O7·H2O:A
lithium intercalation host with a large capacity,Electrochimica Acta 54(2009)
1115–1118.Domestic literature for example has:Yellow Wonder, Gao Shaokang, Wei's bright lamp, hydrothermal synthesis V3O7·H2O nanobelts and its electrification
Learn performance study, South China Normal University's journal, in November, 2009.
In the present invention, seven three vanadium height ratio capacities of oxidation of a hydration, high platform voltage, and with kernel of the present invention and inorganic
The good compatibility of carbon cannot be replaced by other covering materials.
In the LiFePO4 based composites of the present invention, including two kinds of carbon, one is the nothings as matrix in kernel
Machine carbon, the purpose is to be used to load lithium iron phosphate particles;Another kind is the inorganic carbon being located in compound coating layer as conductive layer,
The inorganic carbon be by organic carbon source through carbonated transition from, it is closely multiple to be formed that one water seven of connection aoxidizes three vanadium particles
Close clad.Above two carbon aoxidizes the cooperation of three vanadium particles with lithium iron phosphate particles and a water seven, forms stable structure, shakes
The LiFePO4 based composites of real density height and electrochemical performance.
As the optimal technical scheme of LiFePO4 based composites of the present invention, the compound coating layer is by a water seven
It aoxidizes three vanadium particles and inorganic carbon is constituted, three vanadium particles are preferably aoxidized by a water seven and agraphitic carbon is constituted.
Preferably, the compound coating layer aoxidizes three vanadium particles by a water seven, and bonds a water seven and aoxidize three vanadium
The inorganic carbon of grain constitutes (referred to as V3O7·H2O/C clads), the inorganic carbon is by dissolved organic carbon source through carbonated transition
And come.
Preferably, in the compound coating layer, it is 1 that a water seven, which aoxidizes three vanadium particles and the mass ratio of inorganic carbon,:30~1:
2, such as 1:30,1:28,1:25,1:20,1:15,1:12,1:10,1:8,1:6,1:5,1:4,1:3 or 1:2 etc., preferably 1:
30~1:20.
As the optimal technical scheme of composite material of the present invention, in the kernel, inorganic carbon base body includes carbon nanometer
Pipe, carbon nanocoils, graphene, nitrogen-doped graphene, carbosphere or super carbon black any one or at least two combination, it is excellent
Be selected as in carbon nanotube, carbon nanocoils, graphene or nitrogen-doped graphene any one or at least two combination, above-mentioned
Under optimum condition, the tap density and chemical property of material can be preferably promoted.
Preferably, in the kernel, the mass ratio of inorganic carbon base body and lithium iron phosphate particles is 0.001:1~0.005:1,
Such as 0.001:1,0.002:1,0.003:1,0.004:1 or 0.005:1 etc..
As the optimal technical scheme of composite material of the present invention, the grain size of the composite material at 0.5 μm~20 μm,
Such as 0.5 μm, 1 μm, 2 μm, 5 μm, 10 μm, 12.5 μm, 15 μm, 17 μm, 18 μm or 20 μm etc..
Preferably, the grain size of the lithium iron phosphate particles is at 0.4 μm~19 μm, for example, 0.4 μm, 0.8 μm, 1.5 μm, 2 μm,
3 μm, 5 μm, 7.5 μm, 10 μm, 12 μm, 14 μm, 15 μm, 17 μm or 19 μm etc..
Preferably, the water seven aoxidizes the grain sizes of three vanadium in 50nm~200nm, for example, 50nm, 60nm, 70nm, 80nm,
100nm, 120nm, 135nm, 150nm, 160nm, 175nm, 185nm or 200nm etc..
Second aspect, the present invention provides the preparation method of LiFePO4 based composites as described in relation to the first aspect, described
Method includes the following steps:
(1) compound precursor being made of inorganic carbon base body and the ferrous phosphate being attached on the inorganic carbon base body is prepared
Body;
(2) composite precursor is mixed with lithium source and phosphorus source, is roasted, obtained by inorganic carbon base body and be attached to described
The kernel that lithium iron phosphate particles on inorganic carbon base body are constituted;
(3) gained kernel, vanadium source, dissolved organic carbon source, surfactant and solvent are mixed to get slurry, hydro-thermal is anti-
It answers, obtains LiFePO4 based composites.
As the optimal technical scheme of the method for the invention, the preparation method of step (1) is:
(A) surfactant and inorganic carbon base body are scattered in solvent;
(B) divalent source of iron and phosphorus source are added in step (A) acquired solution;
(C) adjust pH value, be then transferred to reaction kettle and react in confined conditions, obtain composite precursor, it is described it is compound before
It drives body to be made of inorganic carbon base body and the ferrous phosphate being attached on the inorganic carbon base body, may be simply referred to as Fe3(PO4)2/ C is compound
Presoma.
In this optimal technical scheme, step (B) the divalent source of iron and phosphorus source stoichiometrically mix, to form phosphoric acid
Ferrous lithium.
Preferably, the method for preparing composite precursor further includes:Precipitation filtering is carried out after the completion of step (C) reaction, is washed
The step washed and dried.
Preferably, step (A) described surfactant is cetyl trimethylammonium bromide, polyoxyethylene ether, polyethylene
In alcohol, polyethylene glycol, hydroxyethyl cellulose or Dodecyl Glucoside any one or at least two combination.
Preferably, step (A) the inorganic carbon base body includes carbon nanotube, carbon nanocoils, graphene, N doping graphite
Alkene, carbosphere or super carbon black any one or at least two combination, preferably carbon nanotube, carbon nanocoils, graphene
In nitrogen-doped graphene any one or at least two combination.
Preferably, the solvent of step (A) described reaction is water and/or ethyl alcohol, and the water is preferably deionized water or pure water.
Preferably, step (A) is described is separated into:Mixing in solvent first is added in surfactant, then in the item of stirring
Inorganic carbon base body is continuously added under part, the stirring is is vigorously stirred, and speed of agitator is preferably in 200r/min~800r/min, example
As 200r/min, 300r/min, 350r/min, 400r/min, 450r/min, 500r/min, 550r/min, 600r/min,
650r/min, 700r/min or 800r/min etc..
Preferably, in the solution of step (A), the content of surfactant is 0.5g/L~5g/L, such as 0.5g/L, 1g/
L, 2g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L or 5g/L etc..
Preferably, step (B) the divalent source of iron includes in ferrous sulfate, frerrous chloride, ferrous acetate or ferrous oxalate
Any one or at least two combination.
Preferably, step (B) phosphorus source includes arbitrary in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate
It is a kind of or at least two combination.
Preferably, in step (B), the molar ratio of the divalent source of iron, phosphorus source and inorganic carbon base body is Fe:P:C=1:(1
~1.03):(0.001~0.01), such as 1:1:0.005,1:1.01:0.006,1:1.03:0.01,1:1:0.005 or 1:
1.03:0.008 etc..
Preferably, in the solution of step (B), Fe2+A concentration of 0.01mol/L~0.1mol/L, such as 0.01mol/L,
0.03mol/L, 0.05mol/L, 0.08mol/L or 0.1mol/L etc..
Preferably, step (C) adjusts pH value to 3~7, preferably 6~7;
Preferably, step (C) adjusts pH value using ammonium hydroxide, and the ammonium hydroxide is weak aqua ammonia.
Preferably, step (C) adjusts pH value under stirring conditions.
Preferably, the temperature of step (C) described reaction be 100 DEG C~300 DEG C, such as 100 DEG C, 125 DEG C, 150 DEG C, 180
DEG C, 220 DEG C, 260 DEG C, 280 DEG C or 300 DEG C etc..
Preferably, the time of step (C) described reaction is 1h~for 24 hours, for example, 1h, 3h, 5h, 8h, 10h, 12h, 15h,
18h, 20h, 22h or for 24 hours etc., preferably 1h~12h.
As the optimal technical scheme of the method for the invention, step (2) described lithium source includes lithium carbonate, lithium acetate, hydrogen
In lithia, lithium chloride or lithium nitrate any one or at least two combination.
Preferably, step (2) phosphorus source includes arbitrary in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate
It is a kind of or at least two combination.
Preferably, in step (2), the molar ratio of the lithium source, composite precursor and phosphorus source is Li:Fe:P=(3~
3.15):3:(1~1.03), such as 3:3:1,3.12:3:1,3.15:3:1,3:3:1.01 or 3:3:1.03 waiting.
Preferably, step (2) is described is mixed into dry mixed.
Preferably, the time of step (2) described mixing is 2h~12h, such as 2h, 4h, 6.5h, 8h, 10h or 12h etc. is excellent
It is selected as 4h~12h.
Preferably, step (2) roasting carries out under an inert atmosphere, and the inert atmosphere includes nitrogen atmosphere, argon gas
In atmosphere, helium atmosphere, neon atmosphere, Krypton atmosphere or xenon atmosphere any one or at least two combination atmosphere.
Preferably, the temperature of step (2) described roasting be 600 DEG C~750 DEG C, such as 600 DEG C, 625 DEG C, 650 DEG C, 675
DEG C, 700 DEG C, 720 DEG C, 740 DEG C or 750 DEG C etc..
Preferably, the time of step (2) described roasting is 2h~for 24 hours, preferably 4~12h.
As the optimal technical scheme of the method for the invention, step (3) the vanadium source is vanadic anhydride, metavanadic acid
In ammonium, vanadium tetrachloride or vanadic sulfate any one or at least two combination.
Preferably, step (3) the dissolved organic carbon source is citric acid, glucose, sucrose, phytic acid, soluble starch
In cyclodextrin any one or at least two combination.
Preferably, step (3) described surfactant is cetyl trimethylammonium bromide, polyoxyethylene ether, polyethylene
In alcohol, polyethylene glycol, hydroxyethyl cellulose or Dodecyl Glucoside any one or at least two combination.
Preferably, step (3) kernel, vanadium source and the molar ratio in dissolved organic carbon source are Fe:V:C=1:(0.001
~0.1):(0.001~0.1), such as 1:0.001:0.001,1:0.01:0.001,1:0.05:0.001,1:0.01:0.005
Or 1:0.008:0.005 etc..
Preferably, step (3) is described is mixed into:First dissolved organic carbon source and vanadium source are dissolved in solvent, stirred evenly, then is added
Enter surfactant and kernel.
Preferably, the solvent of step (3) described hydro-thermal reaction be water and/or ethyl alcohol, the water be preferably deionized water or
Pure water.
Preferably, the solid content of the slurry of step (3) described hydro-thermal reaction be 10%~40%, such as 10%, 12%,
15%, 20%, 22%, 24%, 25%, 28%, 30%, 35% or 40% etc..
Preferably, in step (3), the mass volume ratio of surfactant and solvent is 0.5g/L~5g/L, such as 0.5g/
L, 1g/L, 1.5g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L or 5g/L etc..
Preferably, the temperature of step (3) described hydro-thermal reaction be 100 DEG C~300 DEG C, such as 100 DEG C, 120 DEG C, 150 DEG C,
175 DEG C, 200 DEG C, 220 DEG C, 240 DEG C, 260 DEG C, 280 DEG C or 300 DEG C etc..
Preferably, the time of step (C) described reaction is 1h~12h, such as 1h, 3h, 5h, 6h, 8h, 10h or 12h etc..
As the further preferred technical solution of the method for the invention, the described method comprises the following steps:
(1) compound precursor being made of inorganic carbon base body and the ferrous phosphate being attached on the inorganic carbon base body is prepared
Body specifically includes:
(A) mixing in solvent first is added in surfactant, then continuously adds inorganic carbon base body under stirring conditions,
It is uniformly dispersed;
(B) divalent source of iron and phosphorus source are added in step (A) acquired solution, are stirred evenly;
(C) weak aqua ammonia is added under agitation and adjusts pH value to 6~7, be then transferred to reaction kettle in confined conditions 100
DEG C~300 DEG C of reaction 1h~12h, precipitation is filtered, washed and dried, and obtains composite precursor (referred to as Fe3(PO4)2/C);
(2) by the composite precursor and lithium source and phosphorus source dry mixed 2h~12h, under an inert atmosphere 600 DEG C~750
DEG C roasting 4h~12h, obtain being made of inorganic carbon base body and the lithium iron phosphate particles being attached on the inorganic carbon base body in
Core;
(3) first dissolved organic carbon source and vanadium source are dissolved in solvent, are stirred evenly, added surfactant and kernel obtains
The solid content of slurry, slurry is 10%~40%, and in 100 DEG C~300 DEG C hydro-thermal reaction 1h~12h, precipitation is filtered, washed and does
It is dry, obtain LiFePO4 based composites (referred to as LiFePO4/C@V3O7·H2O/C is compound).
The third aspect, the present invention provide a kind of positive plate, include the LiFePO4 described in first aspect in the positive plate
Based composites are as positive electrode.
Preferably, the positive plate further includes foil, binder and conductive agent.
Fourth aspect, the present invention provide a kind of lithium ion battery, the lithium ion battery include described in the third aspect just
Pole piece.
Lithium ion battery of the present invention further includes negative plate, diaphragm and electrolyte.
Compared with the prior art, the present invention has the advantages that:
(1) the present invention provides a kind of new structural LiFePO4 based composites, including described in kernel and cladding
The compound coating layer of kernel, the kernel is by inorganic carbon base body and the lithium iron phosphate particles structure being attached on the inorganic carbon base body
At the composition of the compound coating layer includes that a water seven aoxidizes three vanadium particles and inorganic carbon.
LiFePO4 little particle is embedded on inorganic carbon base body in the structure, is reduced material internal pore structure, is improved
The compacted density of material.V3O7·H2O/C clads discharge platform is high, and the good compatibility with LiFePO4, the compound coating layer is again
2.5~3.7V voltage ranges inner capacities is up to 200mAh/g or more, and discharge platform voltage is up to 2.75V, stable cycle performance,
This is other vanadium oxide series positive electrodes (such as VO2、V2O3Deng) do not have;The compound coating layer and the present invention are specific
Kernel coordinates, and is coated on the surface of kernel, can not only promote the chemical property of material, but also can reduce clad to ferric phosphate
The influence of lithium material discharge platform voltage;In addition, V3O7·H2O/C materials can provide new Li+Site, the Li in discharge process+
Insertion can form LixV3O7·H2O structures provide additional capacity so that the button of finally obtained LiFePO4 based composites
Capacitance can reach 170mAh/g or more, and high rate performance is good.
(2) method of the invention prepares LiFePO 4 using divalent source of iron and is formed on inorganic carbon base body, adds lithium
Source and phosphorus source roasting on inorganic carbon base body so that form LiFePO4, last covered composite yarn clad.During this, ferro element
It is always divalent, avoids in roasting process ferric iron and restored that release gas leads to the problem of hole and conventional method disappears by carbon
The problem of consuming the inorganic carbon base body of ball interior and influencing material internal electric conductivity.The present invention not only improves and avoids aerogenesis from structure
Two aspect improve material tap density, the electrification of material is also improved using kernel inorganic carbon and shell compound coating layer
Learn performance.
The reagent and equipment that method of the present invention uses are available commercially, without special customized.
Description of the drawings
Fig. 1 (a) and Fig. 1 (b) is LiFePO made from embodiment 1 respectively4/C@V3O7·H2O/C composite materials are put in difference
SEM figures under big multiple.
Fig. 2 (a) is using LiFePO made from embodiment 14/C@V3O7·H2Button cell made of O/C composite materials
0.5C charging and discharging capacity curve graphs.
Fig. 2 (b) is using LiFePO made from embodiment 14/C@V3O7·H2Button cell made of O/C composite materials
High rate performance figure, in figure, from left to right respectively 10C, 5C, 3C, 2C, 1C, 0.5C, 0.2C and 0.1C.
Specific implementation mode
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
(1) 1g cetyl trimethylammonium bromides are added into 1L deionized waters to stir evenly, in stirring for 400r/min
It mixes and 0.001mol carbon nanocoils is added under speed into above-mentioned solution, after carbon nanocoils are uniformly dispersed, amount compares Fe by mol:
P=1:1.03 ratio sequentially adds frerrous chloride, ammonium dihydrogen phosphate thereto so that the whole molar concentration of final solution
With Fe2+It is calculated as 0.1mol/L.
(2) pH for stirring evenly acquired solution, and ammonia spirit being added to solution thereto under agitation is 7 left
It is right.Acquired solution is transferred in reaction kettle, for 24 hours in 100 DEG C of confined reactions, gained precipitation is filtered, washed, is dried, is answered
Close persursor material.
(3) amount compares Li by mol:Fe:P=3:3:1 ratio sequentially adds lithium carbonate, compound precursor into batch mixer
Simultaneously 12h is mixed in body material, ammonium dihydrogen phosphate, gained batch mixing is roasted to 12h under nitrogen atmosphere at 700 DEG C, you can obtain
The kernel being made of nano wire and lithium iron phosphate particles attached thereto.
(4) amount compares Fe by mol:V:C=1:0.01:0.001 ratio dispensing kernel, ammonium metavanadate, glucose, are pressed
The solid deionized water containing proportioning of 20% slurry matches cetyl trimethylammonium bromide by the dosage of 1g/L deionized waters.
Deionized water, ammonium metavanadate and glucose are added into reaction kettle and stirs evenly, adds inner nuclear material and ten
Six alkyl trimethyl ammonium bromides are uniformly dispersed.Above-mentioned suspension is transferred in reaction kettle, the confined reaction 1h at 240 DEG C, by institute
It must precipitate and be filtered, washed, dry, you can obtain material requested, i.e. LiFePO4/C@V3O7·H2O/C composite materials.
Fig. 1 (a) and Fig. 1 (b) is LiFePO made from embodiment 1 respectively4/C@V3O7·H2O/C composite materials are put in difference
SEM figures under big multiple.By sphere regular appearance it can be seen from Fig. 1 (a) and Fig. 1 (b) and closely knit.
Reached as can be seen from Table 1 with the 0.1C specific discharge capacities of the button cell prepared by prepared composite material
170.035mAh/g, 5C specific discharge capacity are 141.03mAh/g, and 10C specific discharge capacities are 126.10mAh/g, and powder tapping
Density is up to 1.66g/cm3。
Battery is prepared using the composite material of this implementation, is as follows:By assembling CR2016 type button cells
Mode to carry out prepared composite positive pole the assessment of charge-discharge performance, the CT3008 produced using Shenzhen Xin Wei companies
8 lane testing cabinet of type charge and discharge carries out battery performance test.Using PVDF as binder, superconductive carbon black is conductive agent.When sizing mixing,
According to active material, the mass ratio of Ketjen black and PVDF are 93:3:4 ratio allocates slurry, the slurry coating machine that will be mixed well
On aluminium foil coated in 20um thickness, 12h is dried in vacuo at 120 DEG C.Gained aluminium foil is cut to 16mm diameters with slitter
Then sequin is assembled into button cell in Lab2000 type glove boxes.During electrochemical property test, charge and discharge electrical measurement
Examination voltage range is 2.5-3.7V.The capacity for the positive electrode tested is the capacity deducted after carbon, and all tests all exist
It carries out at room temperature.
Fig. 2 (a) is using LiFePO made from embodiment 14/C@V3O7·H2Battery 0.5C made of O/C composite materials fills
Specific discharge capacity curve graph.
Fig. 2 (b) is using LiFePO made from embodiment 14/C@V3O7·H2The multiplying power of battery made of O/C composite materials
Performance map, in figure, from left to right respectively 10C, 5C, 3C, 2C, 1C, 0.5C, 0.2C and 0.1C.
From Fig. 2 (a) and Fig. 2 (b) as can be seen that material 0.1C specific discharge capacities can reach 170.035mAh/g, it is more than
LiFePO4 theoretical capacity, and high rate performance is good.
Embodiment 2
(1) 2g polyvinyl alcohol is added into 1L deionized waters to stir evenly, under the mixing speed of 400r/min upwards
Addition 0.005mol carbon nanotubes in solution are stated, after carbon nanotube is uniformly dispersed, amount compares Fe by mol:P=1:1.01
Ratio sequentially adds ferrous oxalate, diammonium hydrogen phosphate thereto so that the whole molar concentration of final solution is with Fe2+It is calculated as
0.2mol/L.
(2) pH for stirring evenly acquired solution, and ammonia spirit being added to solution thereto under agitation is 7 left
It is right;Acquired solution is transferred in reaction kettle, in 180 DEG C of confined reaction 18h;Gained precipitation is filtered, washed, is dried, is answered
Close persursor material.
(3) amount compares Li by mol:Fe:P=3.15:3:1.03 ratio sequentially adds lithium acetate into batch mixer, answers
It closes persursor material, diammonium hydrogen phosphate and 4h is mixed, gained batch mixing is roasted under nitrogen atmosphere at 670 DEG C to 10h, you can
Obtain the kernel being made of carbon nanotube and lithium iron phosphate particles attached thereto.
(4) amount compares Fe by mol:V:C=1:0.02:0.005 ratio dispensing inner nuclear material, vanadic anhydride, plant
Acid matches polyvinyl alcohol by the solid deionized water containing proportioning of 40% slurry by the dosage of 5g/L deionized waters.
Deionized water, vanadic anhydride and phytic acid are added into reaction kettle and stirs evenly, add inner nuclear material and gathers
Vinyl alcohol is uniformly dispersed.Above-mentioned suspension is transferred in reaction kettle, the confined reaction 10h at 180 DEG C, gained precipitation is filtered,
Washing, drying, you can obtain material requested, i.e. LiFePO4/C@V3O7·H2O/C composite materials.
Using method test tap density same as Example 1 and it is assembled into battery testing charging and discharging capacity and again
Rate performance, the results show that the powder tapping density of prepared composite positive pole is 1.64g/cm3, 0.1C specific discharge capacities are
171.12mAh/g, 5C specific discharge capacity are 142.11mAh/g, and 10C specific discharge capacities are 126.34mAh/g.
Embodiment 3
(1) 5g polyethylene glycol is added into 1L deionized waters to stir evenly, under the mixing speed of 400r/min upwards
Addition 0.04mol graphenes in solution are stated, after carbon nanocoils are uniformly dispersed, amount compares Fe by mol:P=1:1.02 ratio
Ferrous sulfate, ammonium phosphate are sequentially added thereto so that the whole molar concentration of final solution is with Fe2+It is calculated as 0.5mol/L.
(2) acquired solution is stirred evenly, and is slowly added to ammonia spirit thereto under agitation to the pH of solution
It is 4 or so.Acquired solution is transferred in reaction kettle, in 150 DEG C of confined reaction 20h, gained precipitation is filtered, washed, is dried, is obtained
To composite precursor material.
(3) amount compares Li by mol:Fe:P=3.13:3:1 ratio sequentially added into batch mixer lithium chloride, it is compound before
It drives body material, phosphoric acid and 6h is mixed, gained batch mixing is roasted to 18h under nitrogen atmosphere at 620 DEG C, you can obtain by graphite
The kernel that alkene and lithium iron phosphate particles attached thereto are constituted.
(4) amount compares Fe by mol:V:C=1:0.01:0.01 ratio dispensing inner nuclear material, vanadic sulfate, citric acid,
By the solid deionized water containing proportioning of 10% slurry, cetyl trimethylammonium bromide is matched by the dosage of 0.5g/L deionized waters.
Deionized water, vanadic sulfate and citric acid are added into reaction kettle and stirs evenly, adds inner nuclear material and ten
Six alkyl trimethyl ammonium bromides are uniformly dispersed.Above-mentioned suspension is transferred in reaction kettle, the confined reaction 4h at 220 DEG C, by institute
It must precipitate and be filtered, washed, dry, you can obtain material requested, i.e. LiFePO4/C@V3O7·H2O/C composite materials.
Using method test tap density same as Example 1 and it is assembled into battery testing charging and discharging capacity and again
Rate performance, the results show that the powder tapping density of prepared composite positive pole is 1.66g/cm3, 0.1C specific discharge capacities are
169.03mAh/g, 5C specific discharge capacity are 139.41mAh/g, and 10C specific discharge capacities are 125.44mAh/g.
Embodiment 4
(1) into 1L deionized waters be added 4g polyoxyethylene ether stir evenly, under the mixing speed of 800r/min to
0.002mol nitrogen-doped graphenes are added in above-mentioned solution, after carbon nanotube is uniformly dispersed, amount compares Fe by mol:P=1:
1.03 ratio sequentially adds ferrous acetate, diammonium hydrogen phosphate thereto so that the whole molar concentration of final solution is with Fe2+
It is calculated as 0.3mol/L.
(2) acquired solution is stirred evenly, and is slowly added to ammonia spirit thereto under agitation to the pH of solution
It is 5 or so;Acquired solution is transferred in reaction kettle, in 200 DEG C of confined reaction 5h;Gained precipitation is filtered, washed, is dried, is obtained
To composite precursor material.
(3) amount compares Li by mol:Fe:P=3.11:3:1.03 ratio sequentially adds lithium nitrate into batch mixer, answers
It closes persursor material, diammonium hydrogen phosphate and 9h is mixed, gained batch mixing is roasted under helium atmosphere at 750 DEG C to 3h, you can
Obtain the kernel being made of nitrogen-doped graphene and lithium iron phosphate particles attached thereto.
(4) amount compares Fe by mol:V:C=1:0.05:0.003 ratio dispensing inner nuclear material, vanadium tetrachloride, sucrose,
By the solid deionized water containing proportioning of 30% slurry, polyoxyethylene ether is matched by the dosage of 3g/L deionized waters.
Deionized water, vanadium tetrachloride and sucrose are added into reaction kettle and stirs evenly, adds inner nuclear material and polyoxy
Vinethene is uniformly dispersed.Above-mentioned suspension is transferred in reaction kettle, the confined reaction 12h at 200 DEG C, gained precipitation is filtered,
Washing, drying, you can obtain material requested, i.e. LiFePO4/C@V3O7·H2O/C composite materials.
Using method test tap density same as Example 1 and it is assembled into battery testing charging and discharging capacity and again
Rate performance, the results show that the powder tapping density of prepared composite positive pole is 1.65g/cm3, 0.1C specific discharge capacities are
170.99mAh/g, 5C specific discharge capacity are 141.94mAh/g, and 10C specific discharge capacities are 126.00mAh/g.
Embodiment 5
(1) 3g polyvinyl alcohol is added into 1L deionized waters to stir evenly, under the mixing speed of 400r/min upwards
Addition 0.012mol carbon nanocoils in solution are stated, after carbon nanotube is uniformly dispersed, amount compares Fe by mol:P=1:1.03
Ratio sequentially adds frerrous chloride, diammonium hydrogen phosphate thereto so that the whole molar concentration of final solution is with Fe2+It is calculated as
0.25mol/L.
(2) acquired solution is stirred evenly, and is slowly added to ammonia spirit thereto under agitation to the pH of solution
It is 4 or so;Acquired solution is transferred in reaction kettle, in 175 DEG C of confined reaction 6.5h;Gained precipitation is filtered, washed, is dried,
Obtain composite precursor material.
(3) amount compares Li by mol:Fe:P=3.10:3:1.02 ratio sequentially adds lithium nitrate into batch mixer, answers
It closes persursor material, diammonium hydrogen phosphate and 8h is mixed, gained batch mixing is roasted to 4.5h under argon gas atmosphere at 725 DEG C, i.e.,
The available kernel being made of carbon nanocoils and lithium iron phosphate particles attached thereto.
(4) amount compares Fe by mol:V:C=1:0.1:0.06 ratio dispensing inner nuclear material, ammonium metavanadate, glucose,
By the solid deionized water containing proportioning of 25% slurry, polyvinyl alcohol is matched by the dosage of 4g/L deionized waters.
Deionized water, ammonium metavanadate and glucose are added into reaction kettle and stirs evenly, add inner nuclear material and gathers
Vinyl alcohol is uniformly dispersed.Above-mentioned suspension is transferred in reaction kettle, the confined reaction 6.5h at 225 DEG C, gained precipitation is filtered,
Washing, drying, you can obtain material requested, i.e. LiFePO4/C@V3O7·H2O/C composite materials.
Using method test tap density same as Example 1 and it is assembled into battery testing charging and discharging capacity and again
Rate performance, the results show that the powder tapping density of prepared composite positive pole is 1.65g/cm3, 0.1C specific discharge capacities are
170.83mAh/g, 5C specific discharge capacity are 140.89mAh/g, and 10C specific discharge capacities are 126.01mAh/g.
Comparative example 1
In addition to step (1) is added without carbon nanocoils, other preparation methods and condition are same as Example 1.
Using method test tap density same as Example 1 and it is assembled into battery testing charging and discharging capacity and again
Rate performance, the results show that the powder tapping density of prepared composite positive pole is 1.70g/cm3, 0.1C specific discharge capacities are
162.47mAh/g, 5C specific discharge capacity are 120.44mAh/g, and 10C specific discharge capacities are 101.44mAh/g.
If being added without carbon nanocoils in preparation process as carrier, the spherical LiFePO 4 material internal of synthesis is excessively closely knit
And poorly conductive so that material tap density increases and capacity is relatively low.
Comparative example 2
In addition to step (1) the divalent source of iron frerrous chloride is replaced with ferric iron source iron chloride, other preparation methods and
Condition is same as Example 1.
Using method test tap density same as Example 1 and it is assembled into battery testing charging and discharging capacity and again
Rate performance, the results show that the powder tapping density of prepared composite positive pole is 1.60g/cm3, 0.1C specific discharge capacities are
163.75mAh/g, 5C specific discharge capacity are 122.84mAh/g, and 10C specific discharge capacities are 108.24mAh/g.
If using ferric iron source as raw material in preparation process, Fe3+Inner inorganic carbon base body is consumed in carbothermic reduction process
And release reducibility gas so that material internal electric conductivity is low, loose porous, reduces chemical property and the jolt ramming of material
Density.
Comparative example 3
In addition to step (3) is added without ammonium metavanadate, other preparation methods and condition are same as Example 1.
Using method test tap density same as Example 1 and it is assembled into battery testing charging and discharging capacity and again
Rate performance, the results show that the powder tapping density of prepared composite positive pole is 1.66g/cm3, 0.1C specific discharge capacities are
165.66mAh/g, 5C specific discharge capacity are 135.47mAh/g, and 10C specific discharge capacities are 120.79mAh/g.
If being added without vanadium source in preparation process, V is not present in the composite layer of synthesis3O7·H2O can not be provided additional
Embedding lithium site, specific discharge capacity of the material in 0.1C be unable to reach 170mAh/g or more.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, the selection etc. of concrete mode, all fall within protection scope of the present invention and the open scope.
Table 1 is the powder tapping density of different embodiment and comparative examples and buckles the comparison diagram of electrical testing specific discharge capacity.
Table 1
Claims (10)
1. a kind of LiFePO4 based composites, which is characterized in that the composite material includes kernel and the cladding kernel
Compound coating layer, the kernel is made of inorganic carbon base body and the lithium iron phosphate particles being attached on the inorganic carbon base body,
The composition of the compound coating layer includes that a water seven aoxidizes three vanadium particles and inorganic carbon.
2. composite material according to claim 1, which is characterized in that the compound coating layer aoxidizes three vanadium by a water seven
Grain and inorganic carbon are constituted, and preferably aoxidize three vanadium particles by a water seven and agraphitic carbon is constituted;
Preferably, the compound coating layer aoxidizes three vanadium particles by a water seven, and bonds a water seven and aoxidize three vanadium particles
Inorganic carbon constitute, the inorganic carbon be by dissolved organic carbon source through carbonated transition from;
Preferably, in the compound coating layer, it is 1 that a water seven, which aoxidizes three vanadium particles and the mass ratio of inorganic carbon,:30~1:2, it is excellent
It is selected as 1:30~1:20.
3. composite material according to claim 1 or 2, which is characterized in that in the kernel, inorganic carbon base body includes that carbon is received
Mitron, carbon nanocoils, graphene, nitrogen-doped graphene, carbosphere or super carbon black any one or at least two combination,
Preferably in carbon nanotube, carbon nanocoils, graphene or nitrogen-doped graphene any one or at least two combination;
Preferably, in the kernel, the mass ratio of inorganic carbon base body and lithium iron phosphate particles is 0.001:1~0.005:1.
4. according to claim 1-3 any one of them methods, which is characterized in that the grain size of the composite material 0.5 μm~
20μm;
Preferably, the grain size of the lithium iron phosphate particles is at 0.4 μm~19 μm;
Preferably, a water seven aoxidizes the grain size of three vanadium in 50nm~200nm.
5. the preparation method of LiFePO4 based composites according to any one of claims 1-4, which is characterized in that the side
Method includes the following steps:
(1) composite precursor being made of inorganic carbon base body and the ferrous phosphate being attached on the inorganic carbon base body is prepared;
(2) composite precursor is mixed with lithium source and phosphorus source, roasts, obtains by inorganic carbon base body and be attached to described inorganic
The kernel that lithium iron phosphate particles on carbon base body are constituted;
(3) gained kernel, vanadium source, dissolved organic carbon source, surfactant and solvent are mixed to get slurry, hydro-thermal reaction,
Obtain LiFePO4 based composites.
6. according to the method described in claim 5, it is characterized in that, the preparation method of step (1) is:
(A) surfactant and inorganic carbon base body are scattered in solvent;
(B) divalent source of iron and phosphorus source are added in step (A) acquired solution;
(C) pH value is adjusted, reaction kettle is then transferred to and reacts in confined conditions, obtain composite precursor, the composite precursor
It is made of inorganic carbon base body and the ferrous phosphate being attached on the inorganic carbon base body;
Preferably, the method for preparing composite precursor further includes:Step (C) reaction after the completion of carry out precipitation be filtered, washed and
Dry step;
Preferably, step (A) described surfactant is cetyl trimethylammonium bromide, polyoxyethylene ether, polyvinyl alcohol, gathers
In ethylene glycol, hydroxyethyl cellulose or Dodecyl Glucoside any one or at least two combination;
Preferably, step (A) the inorganic carbon base body includes carbon nanotube, carbon nanocoils, graphene, nitrogen-doped graphene, carbon
Microballoon or super carbon black any one or at least two combination, preferably carbon nanotube, carbon nanocoils, graphene or nitrogen mixes
In miscellaneous graphene any one or at least two combination;
Preferably, the solvent of step (A) described reaction is water and/or ethyl alcohol, and the water is preferably deionized water or pure water;
Preferably, step (A) is described is separated into:Mixing in solvent first is added in surfactant, then under stirring conditions
Inorganic carbon base body is continuously added, the rotating speed of the stirring is preferably in 200r/min~800r/min;
Preferably, in the solution of step (A), the content of surfactant is 0.5g/L~5g/L;
Preferably, step (B) the divalent source of iron includes appointing in ferrous sulfate, frerrous chloride, ferrous acetate or ferrous oxalate
It anticipates a kind of or at least two combinations;
Preferably, step (B) phosphorus source includes any one in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate
Or at least two combination;
Preferably, in step (B), the molar ratio of the divalent source of iron, phosphorus source and inorganic carbon base body is Fe:P:C=1:(1~
1.03):(0.001~0.01);
Preferably, in the solution of step (B), Fe2+A concentration of 0.01mol/L~0.1mol/L;
Preferably, step (C) adjusts pH value to 3~7, preferably 6~7;
Preferably, step (C) adjusts pH value using ammonium hydroxide;
Preferably, step (C) adjusts pH value under stirring conditions;
Preferably, the temperature of step (C) described reaction is 100 DEG C~300 DEG C;
Preferably, the time of step (C) described reaction is 1h~for 24 hours, preferably 1h~12h.
7. method according to claim 5 or 6, which is characterized in that step (2) described lithium source include lithium carbonate, lithium acetate,
In lithium hydroxide, lithium chloride or lithium nitrate any one or at least two combination;
Preferably, step (2) phosphorus source includes any one in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate
Or at least two combination;
Preferably, in step (2), the molar ratio of the lithium source, composite precursor and phosphorus source is Li:Fe:P=(3~3.15):
3:(1~1.03);
Preferably, step (2) is described is mixed into dry mixed;
Preferably, the time of step (2) described mixing is 2h~12h;
Preferably, step (2) it is described roasting carry out under an inert atmosphere, the inert atmosphere include nitrogen atmosphere, argon gas atmosphere,
In helium atmosphere, neon atmosphere, Krypton atmosphere or xenon atmosphere any one or at least two combination atmosphere;
Preferably, the temperature of step (2) described roasting is 600 DEG C~750 DEG C;
Preferably, the time of step (2) described roasting is 2h~for 24 hours, preferably 4h~12h.
8. according to claim 5-7 any one of them methods, which is characterized in that step (3) the vanadium source be vanadic anhydride,
In ammonium metavanadate, vanadium tetrachloride or vanadic sulfate any one or at least two combination;
Preferably, step (3) the dissolved organic carbon source is citric acid, glucose, sucrose, phytic acid, soluble starch or ring
In dextrin any one or at least two combination;
Preferably, step (3) described surfactant is cetyl trimethylammonium bromide, polyoxyethylene ether, polyvinyl alcohol, gathers
In ethylene glycol, hydroxyethyl cellulose or Dodecyl Glucoside any one or at least two combination;
Preferably, step (3) kernel, vanadium source and the molar ratio in dissolved organic carbon source are Fe:V:C=1:(0.001~
0.1):(0.001~0.1);
Preferably, step (3) is described is mixed into:First dissolved organic carbon source and vanadium source are dissolved in solvent, stirred evenly, table is added
Face activating agent and kernel;
Preferably, the solvent of step (3) described hydro-thermal reaction is water and/or ethyl alcohol, and the water is preferably deionized water or pure water;
Preferably, the solid content of the slurry of step (3) described hydro-thermal reaction is 10%~40%;
Preferably, in step (3), the mass volume ratio of surfactant and solvent is 0.5g/L~5g/L;
Preferably, the temperature of step (3) described hydro-thermal reaction is 100 DEG C~300 DEG C;
Preferably, the time of step (C) described hydro-thermal reaction is 1h~12h.
9. a kind of positive plate, which is characterized in that iron phosphate lithium-based comprising claim 1-4 any one of them in the positive plate
Composite material is as positive electrode;
Preferably, the positive plate further includes foil, binder and conductive agent.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes the positive plate described in claim 9;
Preferably, the lithium ion battery further includes negative plate, diaphragm and electrolyte.
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