CN101188293A - Fe base lithium sale compound anode materials and its making method - Google Patents
Fe base lithium sale compound anode materials and its making method Download PDFInfo
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- CN101188293A CN101188293A CNA2007101248894A CN200710124889A CN101188293A CN 101188293 A CN101188293 A CN 101188293A CN A2007101248894 A CNA2007101248894 A CN A2007101248894A CN 200710124889 A CN200710124889 A CN 200710124889A CN 101188293 A CN101188293 A CN 101188293A
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- lithium
- sale
- anode materials
- nickel cobalt
- nickel
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- 239000010405 anode material Substances 0.000 title claims abstract description 48
- 229910052744 lithium Inorganic materials 0.000 title claims description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 56
- 150000001875 compounds Chemical class 0.000 title claims description 40
- 238000000034 method Methods 0.000 title abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 90
- 238000007599 discharging Methods 0.000 claims abstract description 55
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 57
- 238000007600 charging Methods 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 36
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 26
- 229910001148 Al-Li alloy Inorganic materials 0.000 claims description 25
- FCVHBUFELUXTLR-UHFFFAOYSA-N [Li].[AlH3] Chemical compound [Li].[AlH3] FCVHBUFELUXTLR-UHFFFAOYSA-N 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 25
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- 230000004927 fusion Effects 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000003595 mist Substances 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000012216 screening Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 229910013716 LiNi Inorganic materials 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 229930006000 Sucrose Natural products 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 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 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 239000002296 pyrolytic carbon Substances 0.000 claims description 8
- 239000005720 sucrose Substances 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000008107 starch Substances 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [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 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 159000000013 aluminium salts Chemical class 0.000 claims description 6
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 150000002506 iron compounds Chemical class 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 229930091371 Fructose Natural products 0.000 claims description 5
- 239000005715 Fructose Substances 0.000 claims description 5
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical group [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 229940062993 ferrous oxalate Drugs 0.000 claims description 5
- 229940116007 ferrous phosphate Drugs 0.000 claims description 5
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 5
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 5
- 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 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 235000014413 iron hydroxide Nutrition 0.000 claims description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- -1 ferrous lithium salt Chemical class 0.000 abstract description 19
- 238000012545 processing Methods 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000005611 electricity Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 4
- 230000001351 cycling effect Effects 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 238000007499 fusion processing Methods 0.000 abstract 1
- 239000010450 olivine Substances 0.000 abstract 1
- 229910052609 olivine Inorganic materials 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 33
- 239000002994 raw material Substances 0.000 description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 238000010410 dusting Methods 0.000 description 10
- 239000006148 magnetic separator Substances 0.000 description 10
- 238000009461 vacuum packaging Methods 0.000 description 10
- 229910052493 LiFePO4 Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 229910000398 iron phosphate Inorganic materials 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000012798 spherical particle Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011246 composite particle Substances 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000005260 alpha ray Effects 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002002 slurry Substances 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a ferrous lithium salt composite anode material and thepreparation method thereof. The technical problems which are needed to be solved are to enhance the high-rate electricity discharging of the anode material, and the manufacturing and the processing performances of battery electrodes are improved. The ferrous lithium salt composite anode material has lithium iron phosphate, and forms the composite material by adulterated with or covered by nickel-cobalt-manganese-lithium or nickel-cobalt-aluminum-lithium material. The weight ratio of the lithium iron phosphate and the nickel-cobalt-manganese-lithium or the nickel-cobalt-aluminum-lithium material is 9 to 7 : 1 to 3, and the micro-morphology is in a sphericity , or is like a sphericity, with a ration between a horizontal length and a vertical length of 1.2 to 2.5. The crystal is in the structure of an olivine type, a space group is Pbnm, and a particle diameter is 1 to 20microns. The preparation method comprises mixture, fusion processing and screen separation. Compared with the prior art, the ferrous lithium salt composite anode material has the advantages of capable of lowering specific surface area, capable of enhancing the voltage platform of the anode material, favorable processing performance, high tap density, favorable conductivity, favorable rate discharge performance and safe performance, capable of improving high and low temperature cycling performance, and favorable compatibility with various cathodes and electrolytes.
Description
Technical field
The present invention relates to positive electrode that a kind of lithium-ion-power cell uses and preparation method thereof, particularly a kind of ferrous phosphate base lithium salts positive electrode and preparation method thereof.
Background technology
Goodenough[J.Electrochem Soc. in 1997,144,1997,1188] etc. the people has synthesized iron content lithium salts LiFePO
4, with the positive electrode of this material, have high theoretical specific capacity (175mAh/g), greater than commercial LiCoO as lithium ion battery
2The actual capacity of 140mAh/g.This LiFePO 4 stable operating voltage (Fe with olivine-type crystal structure
2+/ Fe
3+Relatively the voltage of lithium metal is 3.4V), higher, the Stability Analysis of Structures of charge and discharge platform characteristic good, capacity, high-temperature behavior and good cycle, safety non-toxic, with low cost, bulk effect when cooperating with carbon negative pole material is little, and good with most of electrolyte system compatibility, cause that material supplier author pays close attention to greatly.But this material exists two problems, the one, and the ionic diffusion coefficient of this material and electronic conductivity are all very low, cause high-rate discharge ability poor, and reversible specific capacity is low; The 2nd, tap density is low, causes the volume of battery specific capacity low.This has just limited its application in actual battery greatly.In order to overcome above defective, Many researchers is taked suitable method, adopts iron position doped metal ion as patent US2003/0077514A1, improves LiFePO
4The electronics of positive electrode and ionic conduction, but make the tap density of material on the low side owing in raw material, added more carbon black, bring difficulty for the fabrication and processing of electrode.Therefore press for that research and development are a kind of to have a lithium iron phosphate positive material of conductivity and higher density preferably.
Summary of the invention
The purpose of this invention is to provide a kind of Fe base lithium sale compound anode materials and preparation method thereof, the technical problem that solve is to improve the high-rate discharge ability of positive electrode, improves the fabrication and processing performance of battery electrode.
The present invention is by the following technical solutions: a kind of Fe base lithium sale compound anode materials, has LiFePO 4, described ferrous phosphate lithium doping is or/and be coated with nickel cobalt manganese lithium or nickel cobalt aluminium lithium material, form composite material, the weight ratio of described LiFePO 4 and nickel cobalt manganese lithium or nickel cobalt aluminium lithium is 9～7: 1～3, and the spherical in shape or line of apsides of composite material microscopic pattern is than the class ball-type that is 1.2～2.5, and crystal is an olivine-type structure, space group is Pbnm, and particle diameter is 1～20 μ m.
Composite material of the present invention is coated with material with carbon element, and it accounts for 1～5wt.% of composite material.
The specific area of composite material of the present invention is 5～30m
2/ g, tap density is 1.5～2.0g/cm
3
Fe base lithium sale compound anode materials of the present invention is 2.5～4.2V at charging/discharging voltage, charges and discharge multiplying power when being 0.1C, and reversible capacity is greater than 150mAh/g.
The specific surface of LiFePO 4 of the present invention is 10～50m
2/ g, tap density is 1.0～1.4g/cm
3
The chemical formula of LiFePO 4 of the present invention is LiFePO
4The chemical formula of described nickel cobalt manganese lithium is LiNi
aCo
bMn
c, the chemical formula of described nickel cobalt aluminium lithium is LiNi
aCo
bAl
d, wherein the value of a, b, c, d is the constant greater than 0～1; Described material with carbon element adopts the organic substance pyrolytic carbon of sucrose, glucose, citric acid, fructose, cellulose or starch, native graphite micro mist, Delanium micro mist, conductive carbon black, one or more in the nano-sized carbon.
A kind of preparation method of Fe base lithium sale compound anode materials, may further comprise the steps: one, with LiFePO 4 and nickel cobalt manganese lithium or nickel cobalt aluminium lithium, press LiFePO 4: nickel cobalt manganese lithium or nickel cobalt aluminium lithium weight ratio 9～7: 1～3 are mixed, add the carbon coated material of LiFePO 4 and nickel cobalt manganese lithium or nickel cobalt aluminium lithium weight sum 1～5wt.% simultaneously, obtain the composite material that LiFePO 4 is coated with nickel cobalt manganese lithium or nickel cobalt aluminium lithium; Two, fusion treatment 2～4 hours under the rotating speed of 200～1100r/min forms the sphere or the line of apsides than the class ball-type Fe base lithium sale composite material granular that is 1.2～2.5; Three, adopt the screening of 200～400 purpose screen clothes, obtain the Fe base lithium sale compound anode materials that particle diameter is 1～20 μ m.
It is that 3000～12000 Gausses remove magnetisable material that method of the present invention is sent out Fe base lithium sale composite material granular employing magnetic field intensity.
The chemical formula of the LiFePO 4 of method of the present invention is LiFePO
4The chemical formula of described nickel cobalt manganese lithium is LiNi
aCo
bMn
c, the chemical formula of described nickel cobalt aluminium lithium is LiNi
aCo
bAl
d, wherein the value of a, b, c, d is the constant greater than 0～1; Described carbon coated material adopts organic substance pyrolytic carbon, native graphite micro mist, Delanium micro mist, conductive carbon black, one or more in the nano-sized carbon.
A kind of preparation method of Fe base lithium sale compound anode materials, may further comprise the steps: one, with lithium salts, iron compound, phosphate, cobalt salt, nickel salt, manganese salt or aluminium salt, by lithium: iron: cobalt: nickel: manganese or aluminium: the mol ratio of P elements is 0.9～1.2: 0.8～1: 0.01～0.1: 0.01～0.1: 0.01～0.1: 0.8～1 mixes, add lithium salts simultaneously, iron compound, phosphate, cobalt salt, nickel salt, the dispersant of manganese salt or aluminium salt weight sum 0.1～5wt.%, the material with carbon element predecessor of 1～5wt.%, under the rotating speed of 20～600r/min, wet ball grinding 4～48h, levigate microsphere particle to 5～300nm; Two,, under the condition that outlet temperature is 60～135 ℃, adopt wink-dry to make the spherical presoma that particle diameter is 1～200 μ m 100～400 ℃ of inlet temperatures; Three, spherical presoma is rubbed under rotating speed 20～200r/min pressed 10-30 minute, under 50～300MPa pressure roll-in 1-2 hour; Four, in protective atmosphere, with 2～5 ℃/min programming rate, preliminary treatment is 2～12 hours in 300～400 ℃ of temperature ranges, again with the heating rate of 2～5 ℃/min, be warmed up to 500～800 ℃, constant temperature was handled after 4～48 hours, naturally cooled to room temperature, obtained the ferrous phosphate lithium doping or/and be coated with nickel cobalt manganese lithium or the composite material of nickel cobalt aluminium lithium; Five, comminution by gas stream is the particulate of＜50 μ m; Six, particulate was carried out mechanical fusion treatment 2～4 hours under the rotating speed of 200～1100rpm, obtain the sphere or the line of apsides than the class ball-type Fe base lithium sale composite material granular that is 1.2～2.5; Seven, adopt the screening of 200～400 purpose screen clothes, obtain the Fe base lithium sale compound anode materials that particle diameter is 1～20 μ m.
The air mass flow that method comminution by gas stream of the present invention adopts is 10～200m
3/ min.
It is that 3000～12000 Gausses remove magnetisable material that the Fe base lithium sale composite material granular of method of the present invention adopts magnetic field intensity.
The lithium salts of method of the present invention is lithium carbonate, lithium hydroxide, lithium nitrate, lithium oxalate or lithium acetate; Described iron compound is ferrous sulfate, ferrous oxalate, ferric nitrate, di-iron trioxide or iron hydroxide; Described phosphate is ammonium phosphate, diammonium hydrogen phosphate or ammonium dihydrogen phosphate; Described cobalt salt is cobalt nitrate, cobalt acetate or cobaltous sulfate; Described nickel salt is nickel nitrate, nickel acetate or nickelous sulfate; Described manganese salt is manganese nitrate, manganese acetate or manganese sulfate; Described aluminium salt is aluminum nitrate, aluminium acetate, aluminum sulfate or alundum (Al; Described dispersant be ethanol, acetone, carboxymethyl cellulose one or more; Described material with carbon element adopts the organic substance pyrolytic carbon of sucrose, glucose, citric acid, fructose, cellulose or starch, native graphite micro mist, Delanium micro mist, conductive carbon black, one or more in the nano-sized carbon.
The protective gas of method of the present invention is an argon gas, nitrogen, nitrogen and hydrogen mixture or argon hydrogen gaseous mixture.
The present invention compared with prior art, the Fe base lithium sale compound anode materials of preparation, improved the voltage platform of lithium iron phosphate positive material, reduced specific area, processing characteristics is good, the tap density height, good conductivity, multiplying power discharging and security performance are good, and have improved height, the low temperature cycle performance, this positive electrode Stability Analysis of Structures, good with all kinds of negative poles and electrolyte compatibility, employed raw material wide material sources, the preparation method is simple, and cost is low, can be used as automobile, motorcycle, tractor, diesel engine, beeliner, electric locomotive, the startup power supply of passenger vehicle, and electric motor car, electric bicycle, recreation vehicle, cleaning cart and hybrid vehicle, fork truck, the electrical source of power of light-weight electric vehicles such as forklift also can be used as the high power electric tool, electric hammer, electric drill, the electrical source of power of weeder.
Description of drawings
Fig. 1 is the x x ray diffraction collection of illustrative plates of the iron phosphate compound anode material of lithium of the embodiment of the invention 1 preparation.
Fig. 2 is the stereoscan photograph of the iron phosphate compound anode material of lithium of the embodiment of the invention 1 preparation.
Fig. 3 is that the iron phosphate compound anode material of lithium of the embodiment of the invention 1 preparation is that 0.1C, charging/discharging voltage are the charging and discharging curve of 2.5-4.2V at charge-discharge magnification.
Fig. 4 is that the iron phosphate compound anode material of lithium of the embodiment of the invention 1 preparation is that 0.1C, charging/discharging voltage are the cycle performance curve of 2.5-4.2V at discharge-rate.
Fig. 5 is the presoma stereoscan photograph of the iron phosphate compound anode material of lithium of the embodiment of the invention 5 preparations.
Fig. 6 is the x x ray diffraction collection of illustrative plates of the iron phosphate compound anode material of lithium of the embodiment of the invention 5 preparations.
Fig. 7 is the stereoscan photograph of the iron phosphate compound anode material of lithium of the embodiment of the invention 5 preparations.
Fig. 8 is that the finished product battery of the embodiment of the invention 5 is that 1C, charging/discharging voltage are the discharge cycles curve of 2.5-4.2V at discharge-rate.
Fig. 9 be the embodiment of the invention 5 the finished product battery discharge-rate be 5C, 10C and 15C, charging/discharging voltage be 2.5-4.2V discharge curve.
Figure 10 is 65 ℃ on the finished product battery of the embodiment of the invention 5, be that 1C, charging/discharging voltage are the multiplying power high temperature charging and discharging curve of 2.5-4.2V at discharge-rate.
Figure 11 is the finished product battery-25 ℃ of the embodiment of the invention 5, be that 1C, charging/discharging voltage are the low temperature charging and discharging curve of 2.5-4.2V at discharge-rate.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
Embodiment 1
With 8.5Kg LiFePO 4 LiFePO
4With 1.5Kg nickel cobalt manganese lithium LiNi
0.33Co
0.33Mn
0.33And the nano-sized carbon of 0.1Kg mixes, put into Luoyang and open the star technological development Q50 of Co., Ltd type fusion machine, under the rotating speed of 1100rpm, carried out mechanical fusion treatment 2 hours, then through the CXJ-100-I of The Song Tombs mining machinery Co., Ltd of Gongyi City type magnetic separator, under 7000 gauss magnetic field intensity, remove magnetisable material, obtain Fe base lithium sale compound anode materials through the screening of 325 purpose dusting covers, vacuum packaging again.The specific surface of raw material LiFePO 4 is 40.12m
2/ g, tap density is 1.23g/cm
3As shown in Figure 1, the Fe base lithium sale compound anode materials that makes adopts Cu target K
αRay, wavelength 0.154056nm obtains x x ray diffraction collection of illustrative plates, and as can be seen from the figure, material crystals is an olivine-type structure, and space group is Pbnm.The stereoscan photograph that the SEM instrument of the KYKY2800B type that employing Beijing section instrument produces is 3000 times; as shown in Figure 2; the particle-matrix of material is coated with raw material of wood-charcoal material particulate, forms composite particles with LiFePO 4 and nickel cobalt manganese lithium, and the spherical in shape or line of apsides of composite particles is than the class ball-type that is 1.2.The average grain diameter that the Mastersizer 2000 that produces with Malvern Instruments Ltd records this material is 6 μ m, and specific area is 15.26m
2/ g, tap density 1.68g/cm
3
The chemical property of the material of embodiment 1 preparation is tested as follows, is positive active material with this material, and the lithium sheet is a negative pole, is assembled into the two-electrode experiment battery.Cathode film consist of m (active material): m (polytetrafluoroethylene) m: (carbon black)=92: 5: 3, the positive plate of thickness less than 0.1mm made in roll extrusion on aluminium foil, 100 ℃ dry 8 hours down; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard 2400); Electrolyte is 1mol/L LiPF
6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the MBRAUN glove box.The charge-discharge performance test of battery is at room temperature carried out, and carries out constant current charge-discharge loop test and cycle life test with Shenzhen new prestige cell tester BTS-5V50A.As shown in Figure 3, charging and discharging multiplying power is 0.1C, and when charging/discharging voltage was 2.5～4.2V, the capacity of battery reached 160mAh/g.Discharge-rate is 0.1C, charging/discharging voltage be 2.5-4.2V the cycle performance curve as shown in Figure 4, after 150 weeks of circulation, it is fine that capacity keeps, and do not see decay.
Embodiment 2
With 8Kg LiFePO 4 and 2Kg nickel cobalt aluminium lithium LiNi
0.33Co
0.33Al
0.33And the nano-sized carbon of 0.15Kg mixes, and puts into fusion machine fusion treatment 2 hours under the 1100rpm rotating speed, removes magnetisable material through 12000 Gauss's superelevation intensity magnetic separators then, obtains product through the screening of 325 purpose dusting covers, vacuum packaging again.The specific surface of raw material LiFePO 4 is 40.12m
2/ g, tap density is 1.23cm
3Adopt instrument, the method identical with embodiment 1, recording this material crystals is olivine-type structure, and space group is Pbnm, and the spherical in shape or line of apsides of the microscopic pattern of material is than the class ball-type that is 1.8, and average grain diameter is 7 μ m, and specific area is 17.47m
2/ g, tap density 1.61g/cm
3
Prepare electrode according to the method identical with embodiment 1, carry out electrochemical property test, charging and discharging multiplying power is 0.1C, when charging/discharging voltage was 2.5～4.2V, discharge-rate was 0.1C, and charging/discharging voltage is 2.5-4.2V, the capacity of battery reaches 158mAh/g, circulate after 150 weeks, it is fine that capacity keeps, and do not see decay.
Embodiment 3
With 9Kg LiFePO 4 and 1Kg nickel cobalt manganese lithium LiNi
0.05Co
0.05Mn
0.9And the conductive carbon black of 0.5Kg mixes, and puts into fusion machine fusion treatment 4 hours under the 200rpm rotating speed, removes magnetisable material through 3000 Gauss's superelevation intensity magnetic separators then, obtains product through the screening of 200 purpose dusting covers, vacuum packaging again.The specific surface of raw material LiFePO 4 is 41.12m
2/ g, tap density is 1.23cm
3Adopt instrument, the method identical with embodiment 1, recording this material crystals is olivine-type structure, and space group is Pbnm, and the spherical in shape or line of apsides of the microscopic pattern of material is than the class ball-type that is 2.5, and average grain diameter is 7 μ m, and specific area is 18.36m
2/ g, tap density 1.65g/cm
3
Prepare electrode according to the method identical with embodiment 1, carry out electrochemical property test, charging and discharging multiplying power is 0.1C, when charging/discharging voltage was 2.5～4.2V, discharge-rate was 0.1C, and charging/discharging voltage is 2.5-4.2V, the capacity of battery reaches 156mAh/g, circulate after 150 weeks, it is fine that capacity keeps, and do not see decay.
Embodiment 4
With 7Kg LiFePO 4 and 3Kg nickel cobalt aluminium lithium LiNi
0.8Co
0.1Al
0.1And the native graphite micro mist of 0.5Kg mixes, and puts into fusion machine fusion treatment 3 hours under the 1000rpm rotating speed, removes magnetisable material through 5000 Gauss's superelevation intensity magnetic separators then, obtains product through the screening of 400 purpose dusting covers, vacuum packaging again.The specific surface of raw material LiFePO 4 is 41.12m
2/ g, tap density is 1.23g/cm
3Adopt instrument, the method identical with embodiment 1, recording this material crystals is olivine-type structure, and space group is Pbnm, and the spherical in shape or line of apsides of the microscopic pattern of material is than the class ball-type that is 2.0, and average grain diameter is 5 μ m, and specific area is 14.67m
2/ g, tap density 1.70g/cm
3
Prepare electrode according to the method identical with embodiment 1, carry out electrochemical property test, charging and discharging multiplying power is 0.1C, when charging/discharging voltage was 2.5～4.2V, discharge-rate was 0.1C, and charging/discharging voltage is 2.5-4.2V, the capacity of battery reaches 162mAh/g, circulate after 150 weeks, it is fine that capacity keeps, and do not see decay.
Comparative Examples 1
LiFePO 4 in the above-mentioned example is prepared electrode according to the method identical with embodiment 1, carry out electrochemical property test, charging and discharging multiplying power is 0.1C, and when charging/discharging voltage was 2.5～4.2V, discharge-rate was 0.1C, and charging/discharging voltage is 2.5-4.2V.Its electrical comparing result is listed in table 1.
From table 1 data as can be seen:
Contrast between the embodiment 1,2,3,4, along with the mass ratio increase of nickel cobalt aluminium lithium or nickel cobalt manganese lithium, the material granule particle diameter reduces, and has shortened lithium ion at intragranular the evolving path, thereby improves multiplying power discharging property.Mass ratio along with nickel cobalt aluminium lithium or nickel cobalt manganese lithium increases in addition, and the specific area of material reduces, and tap density increases, and in the course of processing of battery electrode, improves the pole piece compacting, is easy to coating, does not reunite.
Embodiment 1,2,3,4 and Comparative Examples 1 contrast, the positive electrode chemical property that contains nickel cobalt aluminium lithium or nickel cobalt manganese lithium obtains bright existing the lifting.
In the above-described embodiments, conductive carbon black and nano-sized carbon have been enumerated, the organic substance pyrolytic carbon of not enumerating among the embodiment, native graphite micro mist, Delanium micro mist.They all have common chemical property above organic compound: all contain carbon, can mix in composite material, increase the conductivity of LiFePO4.The compound of above carbon source in the process of implementing, can use wherein a kind of, two or more mix use.
Embodiment 5
With 443.34g lithium carbonate (Li
2CO
3), 1798.5g ferrous oxalate (FeC
2O
42H
2O), 1150g ammonium dihydrogen phosphate (NH
4H
2PO
4), 24.89g cobalt acetate (Co (CH
3COO)
2.4H
2O), 29.1g nickel nitrate (Ni (NO
3)
36H
2O) and 21.4g manganese acetate (Mn (CH
3COO)
24H
2O) mix, add 84g glucose simultaneously, 3.38g ethanol adopts ball mill by wet process (Zibo Qimingxing New Material Co., Ltd., model LGM), and particle diameter is the zirconia ball of 2mm, and ball milling is 12 hours under the 20rpm rotating speed, and is levigate to 100nm; The account for 5wt% of quality of ionized water of the quality that drops into raw material, use centrifugal spray granulating and drying machine (Jiangyin golden hair drying equipment Co., Ltd then, model LPG), 100 ℃ of inlet temperatures, under 60 ℃ of conditions of outlet temperature, utilize instaneous polymerization, dry spraying to make spherical presoma, adopt the scanning electron microscopy of the KYKY2800B type of Beijing section instrument product, as shown in Figure 5, in 3000 times SEM figure as can be seen presoma be ball-type or class ball-type.Use Linqu, Shandong nine prosperous mechanical ﹠ electrical equipment factory GP-7 forming roll press then, spherical presoma was rubbed pressure 30 minutes under rotating speed 20r/min, roll-in is 2 hours under 50MPa pressure, in tube furnace (Yongtai, Luoyang City testing furnace factory, model KSS-16G) in, charges into nitrogen protection, with the preliminary treatment 2 hours in 300 ℃ of 2 ℃/min programming rate, be warmed up to 600 ℃ and constant temperature 2 hours with the speed of 2 ℃/min then, naturally cool to room temperature; Above-mentioned material is joined in the airslide disintegrating mill (Kunshan Industrial Co., Ltd., model QYF type), and air mass flow is 50m
3/ min pulverizes the sphere or the class spherical particle that obtain less than 50 μ m; (star technological development Co., Ltd is opened in Luoyang at the fusion machine with particulate, the Q50 type) in, carried out mechanical fusion treatment under the rotating speed of 1100rpm 3 hours, then through the CXJ-100-I of The Song Tombs mining machinery Co., Ltd of Gongyi City type magnetic separator, under 3000 gauss magnetic field intensity, remove magnetisable material, obtain Fe base lithium sale compound anode materials through the screening of 200 purpose dusting covers, vacuum packaging again.As shown in Figure 6, the Fe base lithium sale compound anode materials that makes adopts Cu target K
αRay, wavelength 0.154056nm obtains x x ray diffraction collection of illustrative plates, and as can be seen from the figure, material crystals is an olivine-type structure, and space group is Pbnm.Adopt the scanning electron microscopy of the KYKY2800B type of Beijing section instrument product; 3000 times stereoscan photograph as shown in Figure 7; the particle-matrix of composite material is doped with, matrix is coated with the raw material of wood-charcoal material and nickel cobalt manganese nano metal; form particulate; particulate is combined into composite particles, and the spherical in shape or line of apsides ratio of composite particles is 1.2 class spherical forms.The average grain diameter that the Mastersizer 2000 that produces with Malvern Instruments Ltd records this material composite particles is 6 μ m, and specific area is 17.22m
2/ g, tap density 1.71g/cm
3
With the material of embodiment 5 preparation making 423048 square batteries and carrying out electrochemical property test as follows.Battery is produced as follows: with synthetic Fe base lithium sale compound anode materials is positive active material, cathode film consist of m (active material): m (polytetrafluoroethylene): m (carbon black)=92: 5: 3, stirred 4 hours at mixer, make slurries.Be coated on the 20 μ m aluminium foils (two sided coatings), the section roll-in of oven dry back, compacted density is controlled at 2.3g/cm
3, surface density is controlled at 15.6g/m
2With material with carbon element as negative pole; Import microporous polypropylene membrane (Celgard 2400) as barrier film, is provided with collector plate at electrode end with ultra-sonic welded, clips microporous polypropylene membrane and be rolled into squarely between this positive pole and negative pole, inserts 423048 type rectangular cell shells, makes battery; Electrolyte is 1mol/L LiPF
6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the MBRAUN glove box.Cycle life and multiplying power property testing have been carried out with the rectangular cell to assembling on the BS-9300R tester of Electrotechnical Branch of Qingtian Industry Co Ltd, Guangzhou's production: as shown in Figure 8, charging and discharging multiplying power is 1C, when charging/discharging voltage is 2.5～4.2V, circulates to hold after 2000 times and fall 9%; The high rate performance test: the electric current that battery is provided with 5C, 10C, 15C discharges and recharges, charging/discharging voltage is 2.5～4.2V, the multiplying power discharging result as shown in Figure 9, when the battery capacity during discharge-rate 15C is 5C 88.3%, when the battery capacity during discharge-rate 10C is 5C 92.7% shows that the multiplying power discharging property of material is better; High-temperature behavior test, as shown in figure 10, at 65 ℃, the 1C multiplying power, voltage is 2.5～4.2V, it is unattenuated substantially after 500 times to circulate; Cryogenic property test: as shown in figure 11, at-25 ℃, the 1C multiplying power, voltage is to hold after 2.5～4.2V circulation 500 times to fall 8%.
Embodiment 6
With 654.9g lithium nitrate (LiNO
3), 798.4g di-iron trioxide (Fe2O3), 1188g diammonium hydrogen phosphate (NH
4H
2PO
4), 145.55g cobalt nitrate (Co (NO
3)
36H
2O), 124.33g nickel acetate (Ni (CH
3COO)
24H
2O) and 25.49g alundum (Al (Al
2O
3) mix, adding 211.68g sucrose simultaneously, 84.67g acetone adopts ball mill by wet process (Zibo Qimingxing New Material Co., Ltd., model LGM), and particle diameter is the zirconia ball of 3mm, and ball milling is 24 hours under the 200rpm rotating speed, and is levigate to 200nm; The account for 5wt% of quality of ionized water of the quality that drops into raw material, use centrifugal spray granulating and drying machine then, 400 ℃ of inlet temperatures, under 135 ℃ of conditions of outlet temperature, utilize instaneous polymerization, dry spraying to make spherical presoma, use Linqu, Shandong nine prosperous mechanical ﹠ electrical equipment factory GP-7 forming roll press then, spherical presoma is rubbed under rotating speed 100r/min pressed 20 minutes, roll-in is 1.5 hours under 100MPa pressure.Spherical presoma in tube furnace, is charged into nitrogen protection, and with the programming rate of 4 ℃/min, preliminary treatment is 6 hours in 350 ℃, is warmed up to 700 ℃ and constant temperature 6 hours with the speed of 4 ℃/min then, naturally cools to room temperature; Above-mentioned material is joined (Kunshan Industrial Co., Ltd., model QYF type) in the airslide disintegrating mill, and air mass flow is 100m
3/ min pulverizes the sphere or the class spherical particle that obtain less than 50 μ m; Particulate in the fusion machine, is carried out mechanical fusion treatment 3 hours under the rotating speed of 800rpm, remove magnetisable material through 7000 Gauss's superelevation intensity magnetic separators then; Obtain Fe base lithium sale compound anode materials through the screening of 325 purpose dusting covers, vacuum packaging again.Adopt instrument, the method identical with embodiment 3, recording this material crystals is olivine-type structure, and space group is Pbnm, and the spherical in shape or line of apsides of the microscopic pattern of material is than the class ball-type that is 1.7, and the average grain diameter that records this material is 6 μ m, and specific area is 17.55m
2/ g, tap density 1.75g/cm
3
Prepare battery according to the method identical, carry out electrochemical property test with embodiment 5.Cycle life test: charging and discharging multiplying power is 1C, and when charging/discharging voltage was 2.5～4.2V, the appearance that circulate after 2000 times fell 8%; The high rate performance test: the electric current that battery is provided with 5C, 10C, 15C discharges and recharges, charging/discharging voltage is 2.5～4.2V, when the battery capacity during discharge-rate 15C is 5C 89.4%, 93.1% the when battery capacity during discharge-rate 10C is 5C shows that the multiplying power discharging property of material is better; High-temperature behavior test, at 65 ℃, the 1C multiplying power, voltage is 2.5～4.2V, it is unattenuated substantially after 500 times to circulate; Cryogenic property test: at-25 ℃, the 1C multiplying power, voltage is to hold after 2.5～4.2V circulation 500 times to fall 7%.
Embodiment 7
With 377.6g lithium hydroxide (LiOH H
2O), 2222.8g ferrous sulfate (FeSO
47H
2O), 1192g ammonium phosphate ((NH
4)
3PO
4), 281.1g cobaltous sulfate (CoSO47H2O), 262.8g nickelous sulfate (NiSO4.6H2O) and 374.9g aluminum nitrate (Al (NO
3)
39H
2O) mix, add 400g starch simultaneously, the 170g carboxymethyl cellulose adopts ball mill by wet process (Zibo Qimingxing New Material Co., Ltd., model LGM), and particle diameter is the zirconia ball of 5mm, and ball milling is 4 hours under the 600rpm rotating speed, and is levigate to 300nm; The account for 5wt% of quality of ionized water of the quality that drops into raw material, use centrifugal spray granulating and drying machine then, 350 ℃ of inlet temperatures, under 100 ℃ of conditions of outlet temperature, utilize instaneous polymerization, dry spraying to make spherical presoma, use Linqu, Shandong nine prosperous mechanical ﹠ electrical equipment factory GP-7 forming roll press then, spherical presoma is rubbed under rotating speed 200r/min pressed 10 minutes, roll-in is 1 hour under 200MPa pressure.Spherical presoma in tube furnace, is charged into nitrogen protection, and with the programming rate of 5 ℃/min, preliminary treatment is 3 hours in 400 ℃, is warmed up to 800 ℃ and constant temperature 6 hours with the speed of 2 ℃/min then, naturally cools to room temperature; Above-mentioned material is joined (Kunshan Industrial Co., Ltd., model QYF type) in the airslide disintegrating mill, and air mass flow is 50m
3/ min pulverizes the sphere or the class spherical particle that obtain less than 50 μ m; Particulate in the fusion machine, is carried out mechanical fusion treatment 3 hours under the rotating speed of 1100rpm, remove magnetisable material through 8000 Gauss's superelevation intensity magnetic separators then; Obtain Fe base lithium sale compound anode materials through the screening of 325 purpose dusting covers, vacuum packaging again.Adopt instrument, the method identical with embodiment 5, recording this material crystals is olivine-type structure, and space group is Pbnm, and the spherical in shape or line of apsides of the microscopic pattern of material is than the class ball-type that is 2.5, and the average grain diameter that records this material is 5 μ m, and specific area is 17.78m
2/ g, tap density 1.77g/cm
3
Prepare battery according to the method identical, carry out electrochemical property test with embodiment 5.Cycle life test: charging and discharging multiplying power is 1C, and when charging/discharging voltage was 2.5～4.2V, the appearance that circulate after 2000 times fell 7.6%; The high rate performance test: the electric current that battery is provided with 5C, 10C, 15C discharges and recharges, charging/discharging voltage is 2.5～4.2V, when the battery capacity during discharge-rate 15C is 5C 90.6%, 93.5% the when battery capacity during discharge-rate 10C is 5C shows that the multiplying power discharging property of material is better; High-temperature behavior test, at 65 ℃, the 1C multiplying power, voltage is 2.5～4.2V, it is unattenuated substantially after 500 times to circulate; Cryogenic property test: at-25 ℃, the 1C multiplying power, voltage is to hold after 2.5～4.2V circulation 500 times to fall 6.8%.
With 405.6g lithium hydroxide (LiOH H
2O), 2522.8g ferrous sulfate (FeSO
47H
2O), 1232g ammonium phosphate ((NH
4)
3PO
4), 221.1g cobaltous sulfate (CoSO47H2O), 232.8g nickelous sulfate (NiSO4.6H2O) and 334.9g aluminum nitrate (Al (NO
3)
39H
2O) mix, add 150g sucrose simultaneously, the 120g carboxymethyl cellulose adopts ball mill by wet process (Zibo Qimingxing New Material Co., Ltd., model LGM), and particle diameter is the zirconia ball of 5mm, and ball milling is 48 hours under the 600rpm rotating speed, and is levigate to 300nm; The account for 5wt% of quality of ionized water of the quality that drops into raw material, use centrifugal spray granulating and drying machine then, 350 ℃ of inlet temperatures, under 100 ℃ of conditions of outlet temperature, utilize instaneous polymerization, dry spraying to make spherical presoma, use Linqu, Shandong nine prosperous mechanical ﹠ electrical equipment factory GP-7 forming roll press then, spherical presoma is rubbed under rotating speed 200r/min pressed 10 minutes, roll-in is 1 hour under 300MPa pressure.Spherical presoma in tube furnace, is charged into nitrogen protection, and with the programming rate of 5 ℃/min, preliminary treatment is 12 hours in 400 ℃, is warmed up to 500 ℃ and constant temperature 48 hours with the speed of 5 ℃/min then, naturally cools to room temperature; Above-mentioned material is joined (Kunshan Industrial Co., Ltd., model QYF type) in the airslide disintegrating mill, and air mass flow is 10m
3/ min pulverizes the sphere or the class spherical particle that obtain less than 50 μ m; Particulate in the fusion machine, is carried out mechanical fusion treatment 2,4 hours under the rotating speed of 200rpm, remove magnetisable material through 12000 Gauss's superelevation intensity magnetic separators then; Obtain Fe base lithium sale compound anode materials through the screening of 400 purpose dusting covers, vacuum packaging again.Adopt instrument, the method identical with embodiment 5, recording this material crystals is olivine-type structure, and space group is Pbnm, and the spherical in shape or line of apsides of the microscopic pattern of material is than the class ball-type that is 2.5, and the average grain diameter that records this material is 5 μ m, and specific area is 17.86m
2/ g, tap density 1.75g/cm
3
Prepare battery according to the method identical, carry out electrochemical property test with embodiment 5.Cycle life test: charging and discharging multiplying power is 1C, and when charging/discharging voltage was 2.5～4.2V, the appearance that circulate after 2000 times fell 7.8%; The high rate performance test: the electric current that battery is provided with 5C, 10C, 15C discharges and recharges, charging/discharging voltage is 2.5～4.2V, when the battery capacity during discharge-rate 15C is 5C 90.2%, 93% the when battery capacity during discharge-rate 10C is 5C shows that the multiplying power discharging property of material is better; High-temperature behavior test, at 65 ℃, the 1C multiplying power, voltage is 2.5～4.2V, it is unattenuated substantially after 500 times to circulate; Cryogenic property test: at-25 ℃, the 1C multiplying power, voltage is to hold after 2.5～4.2V circulation 500 times to fall 6.9%.
Embodiment 9
With 282.6g lithium hydroxide (LiOH H
2O), 2222.8g ferrous sulfate (FeSO
47H
2O), 1192g ammonium phosphate ((NH
4)
3PO
4), 301.1g cobaltous sulfate (CoSO47H2O), 295.8g nickelous sulfate (NiSO4.6H2O) and 401.9g aluminum nitrate (Al (NO
3)
39H
2O) mix, add 300g starch simultaneously, the 140g carboxymethyl cellulose adopts ball mill by wet process (Zibo Qimingxing New Material Co., Ltd., model LGM), and particle diameter is the zirconia ball of 5mm, and ball milling is 366 hours under the 600rpm rotating speed, and is levigate to 300nm; The account for 5wt% of quality of ionized water of the quality that drops into raw material, use centrifugal spray granulating and drying machine then, 350 ℃ of inlet temperatures, under 100 ℃ of conditions of outlet temperature, utilize instaneous polymerization, dry spraying to make spherical presoma, use Linqu, Shandong nine prosperous mechanical ﹠ electrical equipment factory GP-7 forming roll press then, spherical presoma is rubbed under rotating speed 200r/min pressed 10 minutes, roll-in is 1 hour under 300MPa pressure.Spherical presoma in tube furnace, is charged into nitrogen protection, and with the programming rate of 5 ℃/min, preliminary treatment is 12 hours in 400 ℃, is warmed up to 750 ℃ and constant temperature 30 hours with the speed of 4 ℃/min then, naturally cools to room temperature; Above-mentioned material is joined (Kunshan Industrial Co., Ltd., model QYF type) in the airslide disintegrating mill, and air mass flow is 200m
3/ min pulverizes the sphere or the class spherical particle that obtain less than 50 μ m; Particulate in the fusion machine, is carried out mechanical fusion treatment 4 hours under the rotating speed of 1100 (lacking 200 data embodiment) rpm, remove magnetisable material through 10000 Gauss's superelevation intensity magnetic separators then; Obtain Fe base lithium sale compound anode materials through the screening of 400 purpose dusting covers, vacuum packaging again.Adopt instrument, the method identical with embodiment 5, recording this material crystals is olivine-type structure, and space group is Pbnm, and the spherical in shape or line of apsides of the microscopic pattern of material is than the class ball-type that is 2.5, and the average grain diameter that records this material is 5 μ m, and specific area is 17.69m
2/ g, tap density 1.76g/cm
3
Prepare battery according to the method identical, carry out electrochemical property test with embodiment 5.Cycle life test: charging and discharging multiplying power is 1C, and when charging/discharging voltage was 2.5～4.2V, the appearance that circulate after 2000 times fell 7.9%; The high rate performance test: the electric current that battery is provided with 5C, 10C, 15C discharges and recharges, charging/discharging voltage is 2.5～4.2V, when the battery capacity during discharge-rate 15C is 5C 90.1%, 93.2% the when battery capacity during discharge-rate 10C is 5C shows that the multiplying power discharging property of material is better; High-temperature behavior test, at 65 ℃, the 1C multiplying power, voltage is 2.5～4.2V, it is unattenuated substantially after 500 times to circulate; Cryogenic property test: at-25 ℃, the 1C multiplying power, voltage is to hold after 2.5～4.2V circulation 500 times to fall 7.0%.
Comparative Examples 2:
With 369.45g lithium carbonate (Li
2CO
3), 1798.5g ferrous oxalate (FeC
2O
42H
2O), 1150g ammonium dihydrogen phosphate (NH
4H
2PO
4) mix, adding 211.68g sucrose simultaneously, 84.67g acetone adopts ball mill by wet process (Zibo Qimingxing New Material Co., Ltd., model LGM), and particle diameter is the zirconia ball of 3mm, and ball milling is 24 hours under the 200rpm rotating speed, and is levigate to 200nm; The account for 5wt% of quality of ionized water of the quality that drops into raw material, use centrifugal spray granulating and drying machine then, 400 ℃ of inlet temperatures, under 135 ℃ of conditions of outlet temperature, utilize instaneous polymerization, dry spraying to make spherical presoma, use Linqu, Shandong nine prosperous mechanical ﹠ electrical equipment factory GP-7 forming roll press then, spherical presoma is rubbed under rotating speed 100r/min pressed 20 minutes, roll-in is 1.5 hours under 100MPa pressure.Spherical presoma in tube furnace, is charged into nitrogen protection, and with the programming rate of 4 ℃/min, preliminary treatment is 6 hours in 350 ℃, is warmed up to 700 ℃ and constant temperature 6 hours with the speed of 4 ℃/min then, naturally cools to room temperature; Above-mentioned material is joined (Kunshan Industrial Co., Ltd., model QYF type) in the airslide disintegrating mill, and air mass flow is 100m
3/ min pulverizes the sphere or the class spherical particle that obtain less than 50 μ m; Particulate in the fusion machine, is carried out mechanical fusion treatment 3 hours under the rotating speed of 800rpm, remove magnetisable material through 7000 Gauss's superelevation intensity magnetic separators then; Obtain lithium iron phosphate positive material through the screening of 325 purpose dusting covers, vacuum packaging again.Adopt instrument, the method identical with embodiment 3, the average grain diameter that records this material is 12 μ m, and specific area is 17.78m
2/ g, tap density 1.77g/cm
3
Prepare battery according to the method identical, carry out electrochemical property test with embodiment 5.Cycle life test: charging and discharging multiplying power is 1C, and when charging/discharging voltage was 2.5～4.2V, the appearance that circulate after 2000 times fell 15%; The high rate performance test: the electric current that battery is provided with 5C, 10C, 15C discharges and recharges, charging/discharging voltage is 2.5～4.2V, when the battery capacity during discharge-rate 15C is 5C 72%, 83.1% the when battery capacity during discharge-rate 10C is 5C shows that the multiplying power discharging property of material is better; High-temperature behavior test, at 65 ℃, the 1C multiplying power, voltage is 2.5～4.2V, circulate to decay 8% substantially after 500 times; Cryogenic property test: at-25 ℃, the 1C multiplying power, voltage is to hold after 2.5～4.2V circulation 500 times to fall 25%.Its electrical comparing result is listed in table 2.
From table 2 data as can be seen:
Contrast between the embodiment 5,6,7,8,9, along with the increase of the doping of nickel cobalt aluminium or nickel cobalt manganese, the material granule particle diameter reduces, and has shortened lithium ion at intragranular the evolving path, thereby improves multiplying power discharging property.Mass ratio along with nickel cobalt aluminium lithium or nickel cobalt manganese lithium increases in addition, and the specific area of material reduces, and tap density increases, and in the course of processing of battery electrode, improves the pole piece compacting, is easy to coating, does not reunite.
The contrast of embodiment 5,6,7,8,9 and Comparative Examples 2 contains the positive electrode high rate performance and the bright existing lifting of high temperature performance of nickel cobalt aluminium lithium or nickel cobalt manganese lithium.
In the above-described embodiments, enumerate lithium carbonate, lithium hydroxide and lithium nitrate, do not enumerated lithium oxalate or lithium acetate among the embodiment.Because lithium oxalate or lithium acetate all contain lithium ion, and under the condition of high temperature, all can form LiFePO4, so it is equally applicable to this patent with the compound of phosphorus source, source of iron.
In the above-described embodiments, ferrous oxalate, ferrous sulfate and di-iron trioxide have been enumerated, ferric nitrate of not enumerating among the embodiment and iron hydroxide.Ferric nitrate and iron hydroxide all contain the iron ion of trivalent, therefore all can pass through carbothermic method, are reduced into the iron ion of divalence, and form LiFePO4 with lithium source, P source compound, so it is equally applicable to this patent.
In the above-described embodiments, enumerated manganese acetate.Manganese nitrate of not enumerating among the embodiment and manganese sulfate.Manganese nitrate and manganese sulfate all contain the manganese ion of divalence, this metal ion species all can enter into the lattice of LiFePO4 under the condition of high temperature, form defective, increase the electric conductivity of LiFePO4, thus improve material capacity, improve the cycle life of material.
In the above-described embodiments, alundum (Al and aluminum nitrate have been enumerated.The oxalic acid aluminium of not enumerating among the embodiment.Oxalic acid aluminium contains the aluminium ion of trivalent, and this metal ion species all can enter into the lattice of LiFePO4 under the condition of high temperature, forms defective, increases the electric conductivity of LiFePO4, thus improve material capacity, improve the cycle life of material.
In the above-described embodiments, glucose, sucrose and starch have been enumerated, the citric acid of not enumerating among the embodiment, fructose, cellulose, organic substance pyrolytic carbon, native graphite micro mist, Delanium micro mist, conductive carbon black, nano-sized carbon.They all have common chemical property above organic compound: all contain carbon, thereby had the chemical general character of reduction, and in the process of reaction, unnecessary carbon can be mixed in LiFePO4, increases the conductivity of LiFePO4.The compound of above carbon source in the process of implementing, can use wherein a kind of, two or more mix use.
Table 1 embodiment 1,2,3,4 and Comparative Examples 1 testing electrical property be contrast table as a result
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative Examples 1 | |
| Specific area m 2/g | 15.26 | 17.47 | 18.36 | 14.67 | 40.12 |
| Tap density g/cm 3 | 1.68 | 1.61 | 1.65 | 1.70 | 1.23 |
| Average grain diameter μ m | 6 | 7 | 7 | 5 | 12 |
| G/cm is compared in compacting 3 | 2.3 | 2.3 | 2.3 | 2.3 | 2.1 |
| 0.1C discharge capacity mAh/g first | 160 | 158 | 156 | 162 | 143 |
| Efficient % first | 97 | 96 | 96 | 97 | 94 |
Table 2 embodiment 5,6,7,8,9 and Comparative Examples 2 testing electrical properties are contrast table as a result
| Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | Comparative Examples 2 | |
| Specific area m 2/g | 17.22 | 17.55 | 17.78 | 17.86 | 17.69 | 30.87 |
| Tap density g/cm 3 | 1.71 | 1.75 | 1.77 | 1.75 | 1.74 | 1.45 |
| Particle diameter μ m | 6 | 6 | 5 | 5 | 5. | 12 |
| G/cm is compared in compacting 3 | 2.3 | 2.3 | 2.3 | 2.3 | 2.3 | 2.1 |
| % falls in 2000 appearances of 1C circulation | 9 | 8 | 7 | 7.5 | 7.7 | 15 |
| 15C/5C electricity multiplying power % | 88.5 | 89.3 | 90.6 | 90.2 | 90.1 | 72 |
| 10C/5C electricity multiplying power % | 92.7 | 93.1 | 93.5 | 93 | 93.2 | 83.1 |
| 65 ℃, the 1C multiplying power circulates to hold for 500 times and falls % | Unattenuated | Unattenuated | Unattenuated | Unattenuated | Unattenuated | 8 |
| -25 ℃, the 1C multiplying power circulates to hold for 500 times and falls % | 7 | 8 | 6.8 | 6.9 | 7.0 | 25 |
Claims (14)
1. Fe base lithium sale compound anode materials, has LiFePO 4, it is characterized in that: described ferrous phosphate lithium doping is or/and be coated with nickel cobalt manganese lithium or nickel cobalt aluminium lithium material, form composite material, the weight ratio of described LiFePO 4 and nickel cobalt manganese lithium or nickel cobalt aluminium lithium is 9～7: 1～3, and the spherical in shape or line of apsides of composite material microscopic pattern is than the class ball-type that is 1.2～2.5, and crystal is an olivine-type structure, space group is Pbnm, and particle diameter is 1～20 μ m.
2. Fe base lithium sale compound anode materials according to claim 1 is characterized in that: described composite material is coated with material with carbon element, and it accounts for 1～5wt.% of composite material.
3. Fe base lithium sale compound anode materials according to claim 2 is characterized in that: the specific area of described composite material is 5～30m
2/ g, tap density is 1.5～2.0g/cm
3
4. Fe base lithium sale compound anode materials according to claim 3 is characterized in that: described Fe base lithium sale compound anode materials is 2.5～4.2V at charging/discharging voltage, charges and discharge multiplying power when being 0.1C, and reversible capacity is greater than 150mAh/g.
5. Fe base lithium sale compound anode materials according to claim 4 is characterized in that: the specific surface of described LiFePO 4 is 10～50m
2/ g, tap density is 1.0～1.4g/cm
3
6. Fe base lithium sale compound anode materials according to claim 5 is characterized in that: the chemical formula of described LiFePO 4 is LiFePO
4The chemical formula of described nickel cobalt manganese lithium is LiNi
aCo
bMn
c, the chemical formula of described nickel cobalt aluminium lithium is LiNi
aCo
bAl
d, wherein the value of a, b, c, d is the constant greater than 0～1; Described material with carbon element adopts the organic substance pyrolytic carbon of sucrose, glucose, citric acid, fructose, cellulose or starch, native graphite micro mist, Delanium micro mist, conductive carbon black, one or more in the nano-sized carbon.
7. the preparation method of a Fe base lithium sale compound anode materials, may further comprise the steps: one, with LiFePO 4 and nickel cobalt manganese lithium or nickel cobalt aluminium lithium, press LiFePO 4: nickel cobalt manganese lithium or nickel cobalt aluminium lithium weight ratio 9～7: 1～3 are mixed, add the carbon coated material of LiFePO 4 and nickel cobalt manganese lithium or nickel cobalt aluminium lithium weight sum 1～5wt.% simultaneously, obtain the composite material that LiFePO 4 is coated with nickel cobalt manganese lithium or nickel cobalt aluminium lithium; Two, fusion treatment 2～4 hours under the rotating speed of 200～1100r/min forms the sphere or the line of apsides than the class ball-type Fe base lithium sale composite material granular that is 1.2～2.5; Three, adopt the screening of 200～400 purpose screen clothes, obtain the Fe base lithium sale compound anode materials that particle diameter is 1～20 μ m.
8. the preparation method of Fe base lithium sale compound anode materials according to claim 7 is characterized in that: it is that 3000～12000 Gausses remove magnetisable material that described Fe base lithium sale composite material granular adopts magnetic field intensity.
9. the preparation method of Fe base lithium sale compound anode materials according to claim 8, it is characterized in that: the chemical formula of described LiFePO 4 is LiFePO
4The chemical formula of described nickel cobalt manganese lithium is LiNi
aCo
bMn
c, the chemical formula of described nickel cobalt aluminium lithium is LiNi
aCo
bAl
d, wherein the value of a, b, c, d is the constant greater than 0～1; Described carbon coated material adopts organic substance pyrolytic carbon, native graphite micro mist, Delanium micro mist, conductive carbon black, one or more in the nano-sized carbon.
10. the preparation method of a Fe base lithium sale compound anode materials, may further comprise the steps: one, with lithium salts, iron compound, phosphate, cobalt salt, nickel salt, manganese salt or aluminium salt, by lithium: iron: cobalt: nickel: manganese or aluminium: the mol ratio of P elements is 0.9～1.2: 0.8～1: 0.01～0.1: 0.01～0.1: 0.01～0.1: 0.8～1 mixes, add lithium salts simultaneously, iron compound, phosphate, cobalt salt, nickel salt, the dispersant of manganese salt or aluminium salt weight sum 0.1～5wt.%, the material with carbon element predecessor of 1～5wt.%, under the rotating speed of 20～600r/min, wet ball grinding 4～48h, levigate microsphere particle to 5～300nm; Two,, under the condition that outlet temperature is 60～135 ℃, adopt wink-dry to make the spherical presoma that particle diameter is 1～200 μ m 100～400 ℃ of inlet temperatures; Three, spherical presoma is rubbed under rotating speed 20～200r/min pressed 10-30 minute, under 50～300MPa pressure roll-in 1-2 hour; Four, in protective atmosphere, with 2～5 ℃/min programming rate, preliminary treatment is 2～12 hours in 300～400 ℃ of temperature ranges, again with the heating rate of 2～5 ℃/min, be warmed up to 500～800 ℃, constant temperature was handled after 4～48 hours, naturally cooled to room temperature, obtained the ferrous phosphate lithium doping or/and be coated with nickel cobalt manganese lithium or the composite material of nickel cobalt aluminium lithium; Five, comminution by gas stream is the particulate of＜50 μ m; Six, particulate was carried out mechanical fusion treatment 2～4 hours under the rotating speed of 200～1100rpm, obtain the sphere or the line of apsides than the class ball-type Fe base lithium sale composite material granular that is 1.2～2.5; Seven, adopt the screening of 200～400 purpose screen clothes, obtain the Fe base lithium sale compound anode materials that particle diameter is 1～20 μ m.
11. the preparation method according to the Fe base lithium sale compound anode materials of claim 10 is characterized in that: the air mass flow that described comminution by gas stream adopts is 10～200m
3/ min.
12. the preparation method according to the Fe base lithium sale compound anode materials of claim 11 is characterized in that: it is that 3000～12000 Gausses remove magnetisable material that described Fe base lithium sale composite material granular adopts magnetic field intensity.
13. the preparation method of Fe base lithium sale compound anode materials according to claim 12 is characterized in that: described lithium salts is lithium carbonate, lithium hydroxide, lithium nitrate, lithium oxalate or lithium acetate; Described iron compound is ferrous sulfate, ferrous oxalate, ferric nitrate, di-iron trioxide or iron hydroxide; Described phosphate is ammonium phosphate, diammonium hydrogen phosphate or ammonium dihydrogen phosphate; Described cobalt salt is cobalt nitrate, cobalt acetate or cobaltous sulfate; Described nickel salt is nickel nitrate, nickel acetate or nickelous sulfate; Described manganese salt is manganese nitrate, manganese acetate or manganese sulfate; Described aluminium salt is aluminum nitrate, aluminium acetate, aluminum sulfate or alundum (Al; Described dispersant be ethanol, acetone, carboxymethyl cellulose one or more; Described material with carbon element adopts the organic substance pyrolytic carbon of sucrose, glucose, citric acid, fructose, cellulose or starch, native graphite micro mist, Delanium micro mist, conductive carbon black, one or more in the nano-sized carbon.
14. the preparation method of Fe base lithium sale compound anode materials according to claim 13 is characterized in that: described protective gas is an argon gas, nitrogen, nitrogen and hydrogen mixture or argon hydrogen gaseous mixture.
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| CN109273696B (en) * | 2018-11-02 | 2020-10-30 | 新疆舰目摩托车有限公司 | Processing method of lithium iron phosphate as positive electrode material of power lithium battery |
| CN114156423A (en) * | 2020-09-08 | 2022-03-08 | 东莞新能安科技有限公司 | Pole piece, battery and electronic device |
| CN114156423B (en) * | 2020-09-08 | 2023-10-03 | 东莞新能安科技有限公司 | Pole piece, battery and electronic device |
| CN112993412A (en) * | 2021-02-19 | 2021-06-18 | 芜湖天弋能源科技有限公司 | Preparation method of high-performance lithium iron phosphate battery |
| CN115621460A (en) * | 2022-09-27 | 2023-01-17 | 楚能新能源股份有限公司 | Positive electrode material and preparation method thereof |
| CN115621460B (en) * | 2022-09-27 | 2023-07-11 | 楚能新能源股份有限公司 | Positive electrode material and preparation method thereof |
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