CN103441276A - Preparation method of carbon-coated porous lithium iron phosphate powder - Google Patents
Preparation method of carbon-coated porous lithium iron phosphate powder Download PDFInfo
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- CN103441276A CN103441276A CN201310412832XA CN201310412832A CN103441276A CN 103441276 A CN103441276 A CN 103441276A CN 201310412832X A CN201310412832X A CN 201310412832XA CN 201310412832 A CN201310412832 A CN 201310412832A CN 103441276 A CN103441276 A CN 103441276A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000000843 powder Substances 0.000 title claims abstract description 31
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000008367 deionised water Substances 0.000 claims abstract description 42
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 42
- 239000000084 colloidal system Substances 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 33
- 239000002244 precipitate Substances 0.000 claims abstract description 24
- -1 ion compound Chemical class 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000001694 spray drying Methods 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 95
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 43
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 34
- 239000003153 chemical reaction reagent Substances 0.000 claims description 30
- 238000001556 precipitation Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000011268 mixed slurry Substances 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 10
- FVFJGQJXAWCHIE-UHFFFAOYSA-N [4-(bromomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CBr)C=C1 FVFJGQJXAWCHIE-UHFFFAOYSA-N 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 108010010803 Gelatin Proteins 0.000 claims description 6
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000008273 gelatin Substances 0.000 claims description 6
- 229920000159 gelatin Polymers 0.000 claims description 6
- 235000019322 gelatine Nutrition 0.000 claims description 6
- 235000011852 gelatine desserts Nutrition 0.000 claims description 6
- 235000013922 glutamic acid Nutrition 0.000 claims description 6
- 239000004220 glutamic acid Substances 0.000 claims description 6
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 5
- 239000002608 ionic liquid Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 4
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- XGBLLQBZRQMYNV-UHFFFAOYSA-N 1-butyl-3-methyl-2H-imidazole nitric acid Chemical compound [N+](=O)(O)[O-].C(CCC)N1CN(C=C1)C XGBLLQBZRQMYNV-UHFFFAOYSA-N 0.000 claims description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 2
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- QGKOZWJXEMFEOW-UHFFFAOYSA-N CN1CN(C=C1)CC.[N+](=O)(O)[O-] Chemical compound CN1CN(C=C1)CC.[N+](=O)(O)[O-] QGKOZWJXEMFEOW-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000010407 ammonium alginate Nutrition 0.000 claims description 2
- 239000000728 ammonium alginate Substances 0.000 claims description 2
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 229960002989 glutamic acid Drugs 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229960001367 tartaric acid Drugs 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000002019 doping agent Substances 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 238000000703 high-speed centrifugation Methods 0.000 description 8
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910052493 LiFePO4 Inorganic materials 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- KRILWIQWBHDGCQ-UHFFFAOYSA-K calcium;iron(2+);phosphate Chemical compound [Ca+2].[Fe+2].[O-]P([O-])([O-])=O KRILWIQWBHDGCQ-UHFFFAOYSA-K 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 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 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ZSWUXEDJKGRXQO-UHFFFAOYSA-N [P].[Fe].[Li].[C] Chemical compound [P].[Fe].[Li].[C] ZSWUXEDJKGRXQO-UHFFFAOYSA-N 0.000 description 1
- RMLHVYNAGVXKKC-UHFFFAOYSA-N [SH2]=N.C(F)(F)F Chemical compound [SH2]=N.C(F)(F)F RMLHVYNAGVXKKC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- 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 relates to a preparation method of carbon-coated porous lithium iron phosphate powder, which comprises the following steps: dissolving ferric iron salt in water to prepare a solution, regulating the pH value to 7.0-13.0 with a precipitating agent until Fe2O3.nH2O completely precipitates; separating the precipitate, washing, and acidifying to obtain electropositive Fe2O3.nH2O colloidal particles; adding deionized water into the colloidal particles, adding a surfactant, stirring intensely to obtain a Fe2O3.nH2O colloid; adding water-soluble lithium source, phosphorus source, carbon source and dopant ion compound into the Fe2O3.nH2O colloid, and stirring intensely to form a molecularly uniformly mixed colloid slurry mixture; carrying out spray drying on the slurry to obtain a spherical lithium iron phosphate precursor; and calcining the precursor in a microwave oven in an inert gas protective atmosphere to obtain the carbon-coated spherical porous lithium iron phosphate powder.
Description
Technical field
The present invention relates to the preparation method of anode material for lithium-ion batteries.
Background technology
Lithium ion battery anode material lithium iron phosphate (LiFePO
4) theoretical capacity is 170mAh/g, reversible charge ratio capacity is higher, have again simultaneously raw material sources extensively, pollute the advantages such as low, that fail safe good, have extended cycle life, be comparatively desirable power type and accumulation energy type anode material for lithium-ion batteries at present.But the ionic conductance of LiFePO4 and electron conductivity are all lower, be only suitable for being discharged and recharged under low current density, during high power charging-discharging, specific capacity reduces, and this has limited the application of this material.LiFePO4 has been carried out to the electric conductivity that a large amount of study on the modification improves LiFePO4 both at home and abroad, mainly comprised and prepare nanoscale LiFePO
4, preparation porous LiFePO
4, the modes such as carbon coating, metal ion mixing, wherein coated modified carbon research mainly concentrates on the carbon that adopts different carbon sources and coating technology to realize various forms and coats.
At present, the preparation method of LiFePO 4 powder mainly contains solid phase method, carbothermic method, sol-gal process, hydro thermal method and microwave method etc.Sol-gel process is preparation high-performance LiFePO
4the effective ways of material, particularly the addition as the doping ion is few, and the employing accurately sol-gal process of control composition is an important technological means.Chinese patent (CN102005564A) discloses a kind of method that adopts ferric hydroxide colloid to prepare nanocrystalline LiFePO 4 powder, adopts Fe (OH)
3colloid is raw material; add ,Lin source, lithium source and organic carbon source in colloid; the even also low-temperature vacuum drying of strong stirring; form uniform, as to contain lithium iron phosphorus carbon nanoscale presoma; put into crucible and be warmed up to 500-800 ℃ at the Muffle furnace of inert atmosphere protection; insulation 2-24 hour; organic carbon source is cracked into carbon under inert atmosphere; ferric iron is reduced to ferrous iron by carbon; form the LiFePO4 that carbon coats, naturally cool to room temperature and obtain nanocrystalline LiFePO 4 powder by grinding or pulverizing.Chinese patent (CN102881903A) discloses a kind of method of porous calcium phosphate iron powder for lithium, by the water-soluble wiring solution-forming of trivalent iron salt, under fluidized state, adds alkali lye to obtain Fe (OH)
3nano particle, Fe (OH)
3nano particle is dispersed in water after washing, forms the di-iron trioxide colloid under strong agitation; Add ,Lin source, water-soluble lithium source, carbon source and doping ionic compound in the di-iron trioxide colloid, strong agitation forms the mixed uniformly colloidal mixed slurry of molecular level; Slurry is spray-dried obtains even-grained ferric lithium phosphate precursor; Presoma obtains the spherical porous LiFePO 4 powder that carbon coats in Muffle furnace under inert atmosphere.
But the glucose etc. of all usining in above-mentioned patent prepares carbon-coated LiFePO 4 for lithium ion batteries as carbon source, often need to destroy polymer chain in these traditional carbon source carbonisations and decompose producing H
2o, CO
2deng gas and little molecular organic compound, cause the inner defects such as crack, pore that form of carbon film.Document J. Mater. Chem, 2012,22 (11): in 4611-4614, the author adopts the two fluoroform sulfimide salt (EMIm-TFSI) of ionic liquid 1-ethyl-3-methyl-imidazoles as carbon source, after Pintsch process at electrode material LiFePO
4particle surface has formed the nitrating carbon film of the even compact that about 15nm is thick, and he thinks that the nitrating carbon film of this even compact has obviously reduced the polarization of electrode interior, so its high rate performance and cycle performance carry out the LiFePO of carbon coating as carbon source than glucose
4material all is significantly improved.On the other hand, above-mentioned patent all adopts traditional mode of heating, by radiation, convection current, conduct these three kinds of modes and from outward appearance to inner essence heated, this mode of heating easily causes lithium iron phosphate particles, and from outward appearance to inner essence carbon content is inhomogeneous.Inhomogeneous and unsettled carbon film easily causes the polarization in charge and discharge process, causes LiFePO 4 material high rate performance and cycle performance variation.
Summary of the invention
the purpose of this invention is to providethe preparation method of the coated porous LiFePO 4 powder of a kind of carbon.
The present invention is the preparation method of the coated porous LiFePO 4 powder of a kind of carbon, the steps include:
(1) Fe
2o
3colloid preparation: take source of iron, be dissolved in deionized water and be mixed with Fe
3+in the solution of concentration 0.1～1mol/L, adopt the ammoniacal liquor of mass concentration 10% or urea liquid as precipitation reagent, the organic molecule dispersant is dissolved in deionized water as end liquid, mol ratio is: dispersant: Fe
3+=1:10, pH=6.8-7.0;
(2) by Fe
3+solution and precipitation reagent add end liquid simultaneously, control pH=7.0-13.0 to Fe
2o
3.nH
2o precipitates fully; By after precipitate and separate, washing, under stirring, with mol ratio HCl:Fe
2o
3=1:100-1:500 adds the watery hydrochloric acid of 0.01mol/L to carry out acidifying, obtains electropositive Fe
2o
3.nH
2the O colloidal particle; Colloidal particle by centrifugation after, add deionized water, add surfactant simultaneously, mass ratio is: surfactant: Fe
2o
3=1:10-1:100 stirs under 30-100 ℃, and mixing time continues 1-10h, obtains Fe
2o
3the Fe that mass ratio is 5-30%
2o
3.nH
2the O colloid;
(3) slurry preparation: according to stoichiometric proportion Li
xfe
ypO
4: M
z, wherein M is the doping ion, x=0.8-1.2, and y=0.8-1.2, z=0.01-0.1, take ,Lin source, lithium source and doping metals compound, and the addition of carbon source is Li
xfe
ypO
4: M
zmass ratio 5-20%; ,Lin source, lithium source, carbon source and doping metals compound are joined to Fe
2o
3.nH
2in the O colloid, continue to be stirred, form homodisperse gluey mixed slurry;
(4) presoma preparation: adopt the spray drying mode to carry out drying to slurry, inlet temperature is 110-130 ℃, obtain composition evenly, the spherical LiFePO 4 presoma of even particle size distribution;
(5) calcining: spray drying gained presoma is put into to crucible, be warming up to 500～800 ℃ under inert atmosphere protection, naturally cooling after insulation 10-40 min, obtain the spherical porous LiFePO 4 powder that carbon coats.
The present invention is with Fe
2o
3.nH
2the O colloid is dispersion, can make each raw material components reach molecular level and evenly mix, the even coating that the ion that is conducive to adulterate enters lattice and carbon film; Using ionic liquid as carbon source, utilize ionic liquid cracking under microwave field to carry out carbon film coated.The carbon-coated LiFePO 4 for lithium ion batteries of preparation is spherical, porous particle, and the carbon film evenly coated in the particle micropore is conducive to the infiltration of electrolyte and the transmission of electronics, therefore has good chemical property and high rate performance.
The accompanying drawing explanation
The process chart that Fig. 1 is the synthetic coated porous LiFePO4 of carbon of the present invention, the scanning electron microscope (SEM) photograph that Fig. 2 is the synthetic coated porous LiFePO4 of carbon of the present invention, the specific discharge capacity curve chart that Fig. 3 is the synthetic coated porous LiFePO4 of carbon of the present invention.
Embodiment
as shown in Figure 1,the present invention is the preparation method of the coated porous LiFePO 4 powder of a kind of carbon, the steps include:
(1) Fe
2o
3colloid preparation: take source of iron, be dissolved in deionized water and be mixed with Fe
3+in the solution of concentration 0.1～1mol/L, adopt the ammoniacal liquor of mass concentration 10% or urea liquid as precipitation reagent, the organic molecule dispersant is dissolved in deionized water as end liquid, mol ratio is: dispersant: Fe
3+=1:10, pH=6.8-7.0;
(2) by Fe
3+solution and precipitation reagent add end liquid simultaneously, control pH=7.0-13.0 to Fe
2o
3.nH
2o precipitates fully; By after precipitate and separate, washing, under stirring, with mol ratio HCl:Fe
2o
3=1:100-1:500 adds the watery hydrochloric acid of 0.01mol/L to carry out acidifying, obtains electropositive Fe
2o
3.nH
2the O colloidal particle; Colloidal particle by centrifugation after, add deionized water, add surfactant simultaneously, mass ratio is: surfactant: Fe
2o
3=1:10-1:100 stirs under 30-100 ℃, and mixing time continues 1-10h, obtains Fe
2o
3the Fe that mass ratio is 5-30%
2o
3.nH
2the O colloid;
(3) slurry preparation: according to stoichiometric proportion Li
xfe
ypO
4: M
z, wherein M is the doping ion, x=0.8-1.2, and y=0.8-1.2, z=0.01-0.1, take ,Lin source, lithium source and doping metals compound, and the addition of carbon source is Li
xfe
ypO
4: M
zmass ratio 5-20%; ,Lin source, lithium source, carbon source and doping metals compound are joined to Fe
2o
3.nH
2in the O colloid, continue to be stirred, form homodisperse gluey mixed slurry;
(4) presoma preparation: adopt the spray drying mode to carry out drying to slurry, inlet temperature is 110-130 ℃, obtain composition evenly, the spherical LiFePO 4 presoma of even particle size distribution;
(5) calcining: spray drying gained presoma is put into to crucible, be warming up to 500～800 ℃ under inert atmosphere protection, naturally cooling after insulation 10-40 min, obtain the spherical porous LiFePO 4 powder that carbon coats.
According to above-described preparation method, source of iron is ironic citrate (FeC specifically
6h
5o
7), or iron chloride (FeCl
3.6H
2or ferric nitrate [Fe (NO O),
3)
39H
2o], or ferric sulfate [Fe
2(SO
4)
3], or the combination of above source of iron material.
According to above-described preparation method, the organic molecule dispersant is citric acid specifically, or glutamic acid, or ascorbic acid, or tartaric acid, or salicylic acid, or above several combination.
According to above-described preparation method, surfactant is gelatin specifically, or polyethylene glycol, or polyvinyl alcohol, or ammonium polymethacrylate, or ammonium oleate, or ammonium alginate, or the combination of the above surfactant materials.
According to above-described preparation method, the lithium source is lithium carbonate (Li specifically
2cO
3), or lithium hydroxide (LiOH), or lithium dihydrogen phosphate (LiH
2pO
4), or the combination of the above lithium source substance.
According to above-described preparation method, the phosphorus source is diammonium hydrogen phosphate [(NH specifically
4)
2hPO
4], or ammonium dihydrogen phosphate (NH
4h
2pO
4), or lithium dihydrogen phosphate (LiH
2pO
4), or phosphoric acid (H
3pO
4), or the combination of the above phosphorus source material.
According to above-described preparation method, carbon source is 1-ethyl-3-methylimidazole nitrate [EMIm] NO specifically
3, or 1-butyl-3-methylimidazole nitrate [BMIm] NO
3, or 1-methyl imidazolium tetrafluoroborate [MIm] BF
4, or 1-ethyl imidazol(e) tetrafluoroborate [EIm] BF
4, or 1-methylimidazole dihydric phosphate [MIm] H
2pO
4, or 1-butyl imidazole dihydric phosphate [BIm] H
2pO
4, or 1-ethyl-3-methylimidazole dintrile amine [EMIm] N (CN)
2, or 1-butyl-3-methylimidazole dintrile amine [BMIm] N (CN)
2deng, or the combination of the above ionic liquid.
According to above-described preparation method, the doping metals compound is magnesium nitrate [Mg (NO specifically
3)
2.2H
2o], or magnesium oxalate [MgC
2o
4.2H
2o], or nickel nitrate [Ni (NO
3)
26H
2o], or nickel acetate [C
2h
3niO
2], or cobalt nitrate [Co (NO
3)
26H
2o], or cobalt acetate [C
4h
6o
4co4H
2o], or aluminum nitrate [Al (NO
3)
39H
2o], or the combination of the above doping metals compound.
Below in conjunction with the drawings and specific embodiments, the present invention is described further.
Embodiment 1:
According to stoichiometric proportion Li
0.99mg
0.01fePO
4at first take 27.03g iron chloride (FeCl
3.6H
2o), be dissolved in deionized water and be made into Fe
3+the solution of concentration 0.1mol/L, adopt the ammoniacal liquor of mass concentration 10% as precipitation reagent, and the 1.92g citric acid is dissolved in the 100mL deionized water as end liquid; By Fe
3+solution and precipitation reagent add end liquid simultaneously, regulate the addition of precipitation reagent and control pH=8.0 to Fe
2o
3.3H
2o precipitates fully; By after precipitate and separate, washing, under stirring, add the 0.01mol/L watery hydrochloric acid of 50mL to carry out acidifying, high speed centrifugation (4000r/min) adds in the 100mL deionized water after separating, add 0.08g ammonium oleate and 0.08g gelatin in deionized water, under 30 ℃, 600 rpm strong stirring 4h obtain Fe again
2o
3.3H
2the O colloid.Take 1.57g1-ethyl-3-methylimidazole nitrate, 2.37g lithium hydroxide and 0.26g magnesium nitrate.These materials are added to Fe
2o
3.3H
2in the O colloid, continue to stir 2h with 600rpm and obtain uniform gluey mixed slurry.Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma.Presoma is put into crucible and is warming up to 500 ℃ at the microwave oven of nitrogen protection, is incubated after 20 min naturally coolingly, obtains the spherical porous LiFePO 4 powder that carbon coats, and granule-morphology as shown in Figure 2.
The battery performance test of gained lithium iron phosphate positive material all adopts the CR2025 button cell, in being full of the glove box of inert atmosphere, is assembled.Negative pole adopts metal lithium sheet, and electrolyte adopts 1mol.L
-liPF6/EC:DMC (1:1), wherein EC is ethylene carbonate, DMC is dimethyl carbonate.Positive plate preparation technology is as follows: by positive electrode and conductive agent acetylene black, the binding agent PVDF(polyvinylidene fluoride prepared) by 85:8:7, mix, add appropriate NMP(N-methyl pyrrolidone) in agate mortar, grind evenly, form the colloidal mixture of thickness, then be uniformly coated on the aluminium foil that 0.02mm is thick, be placed in 120 ℃ of vacuumize 20h, the battery assembled carries out charge-discharge performance and cycle performance test with blue electric battery test system.As shown in Figure 3, charge-discharge magnification is under the 2C condition, and material initial discharge specific capacity is 143.2mAh/g, through 50 circulation volume conservation rates 99.8%
Embodiment 2:
According to stoichiometric proportion Li
0.99mg
0.01fePO
4at first take 27.03g iron chloride (FeCl
3.6H
2o), be dissolved in deionized water and be made into Fe
3+the solution of concentration 0.1mol/L, adopt the ammoniacal liquor of mass concentration 10% as precipitation reagent, and the 1.92g citric acid is dissolved in the 100mL deionized water as end liquid; By Fe
3+solution and precipitation reagent add end liquid simultaneously, regulate the addition of precipitation reagent and control pH=8.0 to Fe
2o
3.3H
2o precipitates fully; By after precipitate and separate, washing, under stirring, add the 0.01mol/L watery hydrochloric acid of 50mL to carry out acidifying, high speed centrifugation (4000r/min) adds in the 100mL deionized water after separating, add 0.08g ammonium oleate and 0.08g polyethylene glycol in deionized water, under 30 ℃, 600 rpm strong stirring 4h obtain Fe again
2o
3.3H
2the O colloid.Take 1.57g1-ethyl-3-methylimidazole nitrate, 2.37g lithium hydroxide and 0.26g magnesium nitrate.These materials are added to Fe
2o
3.3H
2in the O colloid, continue to stir 2h with 600rpm and obtain uniform gluey mixed slurry.Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma.Presoma is put into crucible and is warming up to 500 ℃ at the microwave oven of nitrogen protection, is incubated after 20 min naturally coolingly, obtains carbon and coats spherical porous calcium phosphate iron powder for lithium.
According to the method assembled battery of embodiment 1, to be tested, charge-discharge magnification is under the 2C condition, the material initial discharge capacity reaches 140.0mAh/g, through 50 circulation volume conservation rates 100%.
Embodiment 3:
According to stoichiometric proportion Li
0.99mg
0.01fePO
4at first take 27.03g iron chloride (FeCl
3.6H
2o), be dissolved in deionized water and be made into Fe
3+the solution of concentration 0.1mol/L, adopt the ammoniacal liquor of mass concentration 10% as precipitation reagent, and the 1.92g citric acid is dissolved in the 100mL deionized water as end liquid; By Fe
3+solution and precipitation reagent add end liquid simultaneously, regulate the addition of precipitation reagent and control pH=8.0 to Fe
2o
3.3H
2o precipitates fully; By after precipitate and separate, washing, under stirring, add the 0.01mol/L watery hydrochloric acid of 50mL to carry out acidifying, high speed centrifugation (4000r/min) adds in the 100mL deionized water after separating, add 0.08g ammonium oleate and 0.08g gelatin in deionized water, under 30 ℃, 600 rpm strong stirring 4h obtain Fe again
2o
3.3H
2the O colloid.Take 1.57g1-ethyl imidazol(e) tetrafluoroborate, 2.37g lithium hydroxide and 0.26g magnesium nitrate.These materials are added to Fe
2o
3.3H
2in the O colloid, continue to stir 2h with 600rpm and obtain uniform gluey mixed slurry.Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma.Presoma is put into crucible and is warming up to 500 ℃ at the microwave oven of nitrogen protection, is incubated after 20 min naturally coolingly, obtains the spherical porous LiFePO 4 powder that carbon coats.
According to the method assembled battery of embodiment 1, to be tested, charge-discharge magnification is under the 2C condition, the material initial discharge capacity reaches 141.3mAh/g, through 50 circulation volume conservation rates 98.6%.
Embodiment 4:
According to stoichiometric proportion Li
0.99mg
0.01fePO
4at first take 27.03g iron chloride (FeCl
3.6H
2o), be dissolved in deionized water and be made into Fe
3+the solution of concentration 0.1mol/L, adopt the ammoniacal liquor of mass concentration 10% as precipitation reagent, and the 1.92g citric acid is dissolved in the 100mL deionized water as end liquid; By Fe
3+solution and precipitation reagent add end liquid simultaneously, regulate the addition of precipitation reagent and control pH=8.0 to Fe
2o
3.3H
2o precipitates fully; By after precipitate and separate, washing, under stirring, add the 0.01mol/L watery hydrochloric acid of 50mL to carry out acidifying, high speed centrifugation (4000r/min) adds in the 100mL deionized water after separating, add 0.08g ammonium oleate and 0.08g polyethylene glycol in deionized water, under 30 ℃, 600 rpm strong stirring 4h obtain Fe again
2o
3.3H
2the O colloid.Take 1.57g1-ethyl imidazol(e) tetrafluoroborate, 2.37g lithium hydroxide and 0.26g magnesium nitrate.These materials are added to Fe
2o
3.3H
2in the O colloid, continue to stir 2h with 600rpm and obtain uniform gluey mixed slurry.Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma.Presoma is put into crucible and is warming up to 500 ℃ at the microwave oven of nitrogen protection, naturally cooling after insulation 20min, obtains carbon and coats spherical porous calcium phosphate iron powder for lithium.
According to the method assembled battery of embodiment 1, to be tested, charge-discharge magnification is under the 2C condition, the material initial discharge capacity reaches 138.3mAh/g, through 50 circulation volume conservation rates 99.2%.
Embodiment 5:
According to stoichiometric proportion Li
0.99mg
0.01fePO
4at first take 24.33g iron chloride (FeCl
3.6H
2o) and 2.45g ironic citrate (FeC
6h
5o
7) (mol ratio iron chloride: ironic citrate=9:1), be dissolved in deionized water and be made into Fe
3+the solution of concentration 0.1mol/L, adopt the ammoniacal liquor of mass concentration 10% as precipitation reagent, and 1.92g glutamic acid is dissolved in the 100mL deionized water as end liquid; By Fe
3+solution and precipitation reagent add end liquid simultaneously, regulate the addition of precipitation reagent and control pH=8.0 to Fe
2o
3.3H
2o precipitates fully; By after precipitate and separate, washing, under stirring, add the 0.01mol/L watery hydrochloric acid of 50mL to carry out acidifying, high speed centrifugation (4000r/min) adds in the 100mL deionized water after separating, add 0.08g ammonium oleate and 0.08g gelatin in deionized water, under 30 ℃, 600 rpm strong stirring 4h obtain Fe again
2o
3.3H
2the O colloid.Take 1.57g1-ethyl-3-methylimidazole nitrate, 2.37g lithium hydroxide and 0.26g magnesium nitrate.These materials are added to Fe
2o
3.3H
2in the O colloid, continue to stir 2h with 600rpm and obtain uniform gluey mixed slurry.Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma.Presoma is put into crucible and is warming up to 500 ℃ at the microwave oven of nitrogen protection, is incubated after 20 min naturally coolingly, obtains the spherical porous LiFePO 4 powder that carbon coats.
According to the method assembled battery of embodiment 1, to be tested, charge-discharge magnification is under the 2C condition, the material initial discharge capacity reaches 138.3mAh/g, through 50 circulation volume conservation rates 99.8%.
Embodiment 6:
According to stoichiometric proportion Li
0.99mg
0.01fePO
4at first take 24.33g iron chloride (FeCl
3.6H
2o) and 2.45g ironic citrate (FeC
6h
5o
7) (mol ratio iron chloride: ironic citrate=9:1), be dissolved in deionized water and be made into Fe
3+the solution of concentration 0.1mol/L, adopt the ammoniacal liquor of mass concentration 10% as precipitation reagent, and 1.92g glutamic acid is dissolved in the 100mL deionized water as end liquid; By Fe
3+solution and precipitation reagent add end liquid simultaneously, regulate the addition of precipitation reagent and control pH=8.0 to Fe
2o
3.3H
2o precipitates fully; By after precipitate and separate, washing, under stirring, add the 0.01mol/L watery hydrochloric acid of 50mL to carry out acidifying, high speed centrifugation (4000r/min) adds in the 100mL deionized water after separating, add 0.08g ammonium oleate and 0.08g polyethylene glycol in deionized water, under 30 ℃, 600 rpm strong stirring 4h obtain Fe again
2o
3.3H
2the O colloid.Take 1.57g1-ethyl-3-methylimidazole nitrate, 2.37g lithium hydroxide and 0.26g magnesium nitrate.These materials are added to Fe
2o
3.3H
2in the O colloid, continue to stir 2h with 600rpm and obtain uniform gluey mixed slurry.Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma.Presoma is put into crucible and is warming up to 500 ℃ at the microwave oven of nitrogen protection, is incubated after 20 min naturally coolingly, obtains the spherical porous LiFePO 4 powder that carbon coats.
According to the method assembled battery of embodiment 1, to be tested, charge-discharge magnification is under the 2C condition, the material initial discharge capacity reaches 143.1mAh/g, through 50 circulation volume conservation rates 98.4%.
Embodiment 7:
According to stoichiometric proportion Li
0.99mg
0.01fePO
4at first take 24.33g iron chloride (FeCl
3.6H
2o) and 2.45g ironic citrate (FeC
6h
5o
7) (mol ratio iron chloride: ironic citrate=9:1), be dissolved in deionized water and be made into Fe
3+the solution of concentration 0.1mol/L, adopt the ammoniacal liquor of mass concentration 10% as precipitation reagent, and 1.92g glutamic acid is dissolved in the 100mL deionized water as end liquid; By Fe
3+solution and precipitation reagent add end liquid simultaneously, regulate the addition of precipitation reagent and control pH=8.0 to Fe
2o
3.3H
2o precipitates fully; By after precipitate and separate, washing, under stirring, add the 0.01mol/L watery hydrochloric acid of 50mL to carry out acidifying, high speed centrifugation (4000r/min) adds in the 100mL deionized water after separating, add 0.08g ammonium oleate and 0.08g gelatin in deionized water, under 30 ℃, 600 rpm strong stirring 4h obtain Fe again
2o
3.3H
2the O colloid.Take 1.57g1-ethyl imidazol(e) tetrafluoroborate, 2.37g lithium hydroxide and 0.26g magnesium nitrate.These materials are added to Fe
2o
3.3H
2in the O colloid, continue to stir 2h with 600rpm and obtain uniform gluey mixed slurry.Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma.Presoma is put into crucible and is warming up to 500 ℃ at the microwave oven of nitrogen protection, is incubated after 20 min naturally coolingly, obtains the spherical porous LiFePO 4 powder that carbon coats.
According to the method assembled battery of embodiment 1, to be tested, charge-discharge magnification is under the 2C condition, the material initial discharge capacity reaches 137.4mAh/g, through 50 circulation volume conservation rates 97.6%.
Embodiment 8:
According to stoichiometric proportion Li
0.99mg
0.01fePO
4at first take 24.33g iron chloride (FeCl
3.6H
2o) and 2.45g ironic citrate (FeC
6h
5o
7) (mol ratio iron chloride: ironic citrate=9:1), be dissolved in deionized water and be made into Fe
3+the solution of concentration 0.1mol/L, adopt the ammoniacal liquor of mass concentration 10% as precipitation reagent, and 1.92g glutamic acid is dissolved in the 100mL deionized water as end liquid; By Fe
3+solution and precipitation reagent add end liquid simultaneously, regulate the addition of precipitation reagent and control pH=8.0 to Fe
2o
3.3H
2o precipitates fully; By after precipitate and separate, washing, under stirring, add the 0.01mol/L watery hydrochloric acid of 50mL to carry out acidifying, high speed centrifugation (4000r/min) adds in the 100mL deionized water after separating, add 0.08g ammonium oleate and 0.08g polyethylene glycol in deionized water, under 30 ℃, 600 rpm strong stirring 4h obtain Fe again
2o
3.3H
2the O colloid.Take 1.57g1-ethyl imidazol(e) tetrafluoroborate, 2.37g lithium hydroxide and 0.26g magnesium nitrate.These materials are added to Fe
2o
3.3H
2in the O colloid, continue to stir 2h with 600rpm and obtain uniform gluey mixed slurry.Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma.Presoma is put into crucible and is warming up to 500 ℃ at the microwave oven of nitrogen protection, is incubated after 20 min naturally coolingly, obtains carbon and coats spherical porous calcium phosphate iron powder for lithium.
According to the method assembled battery of embodiment 1, to be tested, charge-discharge magnification is under the 2C condition, material initial discharge capacity 139.6mAh/g, through 50 circulation volume conservation rates 96.8%.
Claims (8)
1. the preparation method of the coated porous LiFePO 4 powder of carbon, the steps include:
(1) Fe
2o
3colloid preparation: take source of iron, be dissolved in deionized water and be mixed with Fe
3+in the solution of concentration 0.1～1mol/L, adopt the ammoniacal liquor of mass concentration 10% or urea liquid as precipitation reagent, the organic molecule dispersant is dissolved in deionized water as end liquid, mol ratio is: dispersant: Fe
3+=1:10, pH=6.8-7.0;
(2) by Fe
3+solution and precipitation reagent add end liquid simultaneously, control pH=7.0-13.0 to Fe
2o
3.nH
2o precipitates fully; By after precipitate and separate, washing, under stirring, with mol ratio HCl:Fe
2o
3=1:100-1:500 adds the watery hydrochloric acid of 0.01mol/L to carry out acidifying, obtains electropositive Fe
2o
3.nH
2the O colloidal particle; Colloidal particle by centrifugation after, add deionized water, add surfactant simultaneously, mass ratio is: surfactant: Fe
2o
3=1:10-1:100 stirs under 30-100 ℃, and mixing time continues 1-10h, obtains Fe
2o
3the Fe that mass ratio is 5-30%
2o
3.nH
2the O colloid;
(3) slurry preparation: according to stoichiometric proportion Li
xfe
ypO
4: M
z, wherein M is the doping ion, x=0.8-1.2, and y=0.8-1.2, z=0.01-0.1, take ,Lin source, lithium source and doping metals compound, and the addition of carbon source is Li
xfe
ypO
4: M
zmass ratio 5-20%; ,Lin source, lithium source, carbon source and doping metals compound are joined to Fe
2o
3.nH
2in the O colloid, continue to be stirred, form homodisperse gluey mixed slurry;
(4) presoma preparation: adopt the spray drying mode to carry out drying to slurry, inlet temperature is 110-130 ℃, obtain composition evenly, the spherical LiFePO 4 presoma of even particle size distribution;
(5) calcining: spray drying gained presoma is put into to crucible, be warming up to 500～800 ℃ under inert atmosphere protection, naturally cooling after insulation 10-40 min, obtain the spherical porous LiFePO 4 powder that carbon coats.
2. the preparation method of the coated porous LiFePO 4 powder of carbon according to claim 1, is characterized in that specifically ironic citrate (FeC of described source of iron
6h
5o
7), or iron chloride (FeCl
3.6H
2or ferric nitrate [Fe (NO O),
3)
39H
2o], or ferric sulfate [Fe
2(SO
4)
3], or the combination of above source of iron material.
3. the preparation method of the coated porous LiFePO 4 powder of carbon according to claim 1, is characterized in that specifically citric acid of described organic molecule dispersant, or glutamic acid, or ascorbic acid, or tartaric acid, or salicylic acid, or above several combination.
4. the preparation method of the coated porous LiFePO 4 powder of carbon according to claim 1, it is characterized in that specifically gelatin of described surfactant, or polyethylene glycol, or polyvinyl alcohol, or ammonium polymethacrylate, or ammonium oleate, or ammonium alginate, or the combination of the above surfactant materials.
5. the preparation method of the coated porous LiFePO 4 powder of carbon according to claim 1, is characterized in that specifically lithium carbonate (Li of described lithium source
2cO
3), or lithium hydroxide (LiOH), or lithium dihydrogen phosphate (LiH
2pO
4), or the combination of the above lithium source substance.
6. the preparation method of the coated porous LiFePO 4 powder of carbon according to claim 1, is characterized in that specifically diammonium hydrogen phosphate [(NH of described phosphorus source
4)
2hPO
4], or ammonium dihydrogen phosphate (NH
4h
2pO
4), or lithium dihydrogen phosphate (LiH
2pO
4), or phosphoric acid (H
3pO
4), or the combination of the above phosphorus source material.
7. the preparation method of the coated porous LiFePO 4 powder of carbon according to claim 1, is characterized in that specifically 1-ethyl-3-methylimidazole nitrate [EMIm] NO of described carbon source
3, or 1-butyl-3-methylimidazole nitrate [BMIm] NO
3, or 1-methyl imidazolium tetrafluoroborate [MIm] BF
4, or 1-ethyl imidazol(e) tetrafluoroborate [EIm] BF
4, or 1-methylimidazole dihydric phosphate [MIm] H
2pO
4, or 1-butyl imidazole dihydric phosphate [BIm] H
2pO
4, or 1-ethyl-3-methylimidazole dintrile amine [EMIm] N (CN)
2, or 1-butyl-3-methylimidazole dintrile amine [BMIm] N (CN)
2deng, or the combination of the above ionic liquid.
8. the preparation method of the coated porous LiFePO 4 powder of carbon according to claim 1, is characterized in that specifically magnesium nitrate [Mg (NO of described doping metals compound
3)
2.2H
2o], or magnesium oxalate [MgC
2o
4.2H
2o], or nickel nitrate [Ni (NO
3)
26H
2o], or nickel acetate [C
2h
3niO
2], or cobalt nitrate [Co (NO
3)
26H
2o], or cobalt acetate [C
4h
6o
4co4H
2o], or aluminum nitrate [Al (NO
3)
39H
2o], or the combination of the above doping metals compound.
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| CN109119615A (en) * | 2018-08-28 | 2019-01-01 | 重庆大学 | A kind of lithium manganese phosphate composite positive pole and preparation method thereof that doped metallic elements are modified |
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| CN111285342A (en) * | 2020-03-23 | 2020-06-16 | 蒋央芳 | Preparation method of lithium iron phosphate |
| CN112331846A (en) * | 2019-08-27 | 2021-02-05 | 万向一二三股份公司 | Preparation method of high-rate positive electrode material lithium iron phosphate |
| CN112397698A (en) * | 2020-11-16 | 2021-02-23 | 合肥国轩高科动力能源有限公司 | Composite conductive agent coated lithium iron phosphate material and preparation method and application thereof |
| CN113511641A (en) * | 2021-07-04 | 2021-10-19 | 桂林理工大学 | Method for preparing three-dimensional porous carbon/iron phosphate compound by salt crystal foaming with glucose as carbon source |
| CN113735091A (en) * | 2021-09-07 | 2021-12-03 | 湖北云翔聚能新能源科技有限公司 | Preparation method of nano spherical lithium iron phosphate and lithium iron phosphate material |
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| CN109119615A (en) * | 2018-08-28 | 2019-01-01 | 重庆大学 | A kind of lithium manganese phosphate composite positive pole and preparation method thereof that doped metallic elements are modified |
| CN109928376A (en) * | 2018-11-07 | 2019-06-25 | 贵州唯特高新能源科技有限公司 | A kind of preparation method of the high-pressure solid LiFePO4 of metal ion mixing |
| CN112331846A (en) * | 2019-08-27 | 2021-02-05 | 万向一二三股份公司 | Preparation method of high-rate positive electrode material lithium iron phosphate |
| CN111285342A (en) * | 2020-03-23 | 2020-06-16 | 蒋央芳 | Preparation method of lithium iron phosphate |
| CN112397698A (en) * | 2020-11-16 | 2021-02-23 | 合肥国轩高科动力能源有限公司 | Composite conductive agent coated lithium iron phosphate material and preparation method and application thereof |
| CN113511641A (en) * | 2021-07-04 | 2021-10-19 | 桂林理工大学 | Method for preparing three-dimensional porous carbon/iron phosphate compound by salt crystal foaming with glucose as carbon source |
| CN113735091A (en) * | 2021-09-07 | 2021-12-03 | 湖北云翔聚能新能源科技有限公司 | Preparation method of nano spherical lithium iron phosphate and lithium iron phosphate material |
| CN114604838A (en) * | 2022-05-10 | 2022-06-10 | 兰州兰石中科纳米科技有限公司 | Drying and calcining method for iron phosphate |
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