CN101081696A - Ferric phosphate lithium material for lithium ion powder cell and preparation method thereof - Google Patents
Ferric phosphate lithium material for lithium ion powder cell and preparation method thereof Download PDFInfo
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- CN101081696A CN101081696A CNA2007100744558A CN200710074455A CN101081696A CN 101081696 A CN101081696 A CN 101081696A CN A2007100744558 A CNA2007100744558 A CN A2007100744558A CN 200710074455 A CN200710074455 A CN 200710074455A CN 101081696 A CN101081696 A CN 101081696A
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- Prior art keywords
- lithium
- phosphate
- ion powder
- lithium ion
- powder cell
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Links
- 239000000463 material Substances 0.000 title claims abstract description 72
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 title claims description 29
- 239000000843 powder Substances 0.000 title claims description 21
- 239000005955 Ferric phosphate Substances 0.000 title claims description 20
- 229940032958 ferric phosphate Drugs 0.000 title claims description 20
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims description 20
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims description 20
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000498 ball milling Methods 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 7
- 239000011246 composite particle Substances 0.000 claims abstract description 7
- 238000002203 pretreatment Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000007493 shaping process Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 40
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000010955 niobium Substances 0.000 claims description 16
- 150000003016 phosphoric acids Chemical class 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 12
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 11
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical group O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 11
- 229910052758 niobium Inorganic materials 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 9
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 9
- 239000000347 magnesium hydroxide Substances 0.000 claims description 9
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002296 pyrolytic carbon Substances 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003595 mist Substances 0.000 claims description 8
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- 235000012245 magnesium oxide Nutrition 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 239000011247 coating layer Substances 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 239000001095 magnesium carbonate Substances 0.000 claims description 6
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 6
- 229960001708 magnesium carbonate Drugs 0.000 claims description 6
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 6
- 235000012254 magnesium hydroxide Nutrition 0.000 claims description 6
- 235000019359 magnesium stearate Nutrition 0.000 claims description 6
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000011238 particulate composite Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 5
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 5
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- 229910021382 natural graphite Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 3
- 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 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 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 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 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 3
- 210000000481 breast Anatomy 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 238000006253 efflorescence Methods 0.000 claims description 3
- 239000011295 pitch Substances 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 206010037844 rash Diseases 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920003987 resole Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- 238000011068 loading method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 238000009413 insulation Methods 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910010710 LiFePO Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- -1 phosphoric acid salt Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- 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 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007704 transition Effects 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 present invention discloses lithium iron phosphate material for lithium ion power cell and its preparation process, and dissolves the technological problem of raising the discharge power and safety performance. The lithium iron phosphate material is spherical or spheroid composite particle with one base body of lithium iron phosphate and doping and modifying agent and one coating carbon layer. Its preparation process includes wet ball milling the mixture comprising lithium salt, ferric salt, phosphoric acid, doping and modifying agent and dispersant, spraying to pelletize, heating for pre-treatment, maintaining temperature, cooling, pulverizing and shaping. Compared with available technology, the present invention has the features of high crystallization, single structure, average composite particle size of 5-60 microns, specific surface area of 8.0-15.0 sq m/g, bulk density of 1.4-1.7 g/cu cm, high specific capacity, high safety, etc.
Description
Technical field
The present invention relates to positive electrode material of a kind of lithium-ion-power cell and preparation method thereof, particularly a kind of lithium iron phosphate positive material and preparation method thereof.
Background technology
Lithium ion battery has the voltage height as the new generation of green high tension battery, and energy density is big, good cycle, and self-discharge is little, memory-less effect, advantage such as operating temperature range is wide and being widely used.Positive electrode material is again the important component part of lithium ion battery, and iron lithium phosphate becomes the focus of current research as positive electrode material of new generation.Lithium iron phosphate positive material has the theoretical capacity height, and about 170mAh/g is nontoxic, and the starting material range of choice is wide, stable operating voltage, and Stability Analysis of Structures, security is splendid, Heat stability is good, plurality of advantages such as high temperature and good cycle.
The synthetic of the iron lithium phosphate of prior art is to synthesize the master with solid phase method; as Chinese patent literature CN1581537, CN1753216, the disclosed method of CN1762798, CN1767238; promptly be that the carbonate of lithium (or oxyhydroxide, phosphoric acid salt), Ferrox (or ferrous acetate, ferrous phosphate) and primary ammonium phosphate (or Secondary ammonium phosphate) are mixed, high-temperature roasting forms under protection of inert gas.Preparation technology is simple for this method, and condition is easy to control, is convenient to suitability for industrialized production.But the particle size distribution of product is wide, and crystalline size is bigger, and powder is by random granulometric composition, and tap density is low, and tap density generally has only 1.0g/cm
3About, be significantly less than present cobalt acid lithium (2.8g/cm
3), lithium manganate (2.2g/cm
3) tap density; And the iron lithium phosphate specific conductivity is low, and high-rate charge-discharge capability is relatively poor, causes the practical application difficulty of material.
For improving the use properties of iron lithium phosphate, generally be that it is carried out doping treatment, disclosed oxygen place doped as Chinese patent literature CN1772604, CN1785799 is disclosed transition element doped, CN1785800 is disclosed rear-earth-doped, CN1785823 is disclosed P site doped, though aforesaid method can partly improve the use properties of iron lithium phosphate, is not easy to realize industrialized production.
Summary of the invention
The purpose of this invention is to provide a kind of ferric phosphate lithium material for lithium ion powder cell and preparation method thereof, the technical problem that solve is to improve the multiplying power discharging and the safety performance of lithium-ion-power cell, and chemical property is good, is fit to suitability for industrialized production.
The present invention is by the following technical solutions: a kind of ferric phosphate lithium material for lithium ion powder cell, described LiFePO 4 material has lithium iron phosphate and doping vario-property agent matrix, matrix is coated with the composite carbon coating layer and forms particulate, particulate is combined into composite particulate material, and composite particles is spherical in shape or class is spherical.
Lithium iron phosphate of the present invention is lithium salts, molysite and phosphoric acid salt, and the mol ratio of lithium, iron, phosphorus is 1: 1: 1.
Lithium salts of the present invention is Quilonum Retard, lithium fluoride, Lithium Acetate, lithium hydroxide, lithium nitrate or monometallic; Described molysite is Ferrox, Iron diacetate, ferric oxide, iron nitrate or ironic hydroxide; Described phosphoric acid salt is monometallic, primary ammonium phosphate, Secondary ammonium phosphate, triammonium phosphate, phosphoric acid or Vanadium Pentoxide in FLAKES.
Doping vario-property agent of the present invention is magnesium oxide, magnesium hydroxide, magnesiumcarbonate, Magnesium Stearate, primary magnesium phosphate or Niobium Pentxoxide, and the mass ratio that accounts for composite particulate material is 1%～25%.
Composite carbon coating layer of the present invention is one or more compositions in natural graphite, synthetic graphite micro mist, organism pyrolytic carbon and the nanometer conductive material, and the mass ratio that accounts for composite particulate material is 1%～25%.
Nanometer conductive material of the present invention is conductive carbon black, carbon nanotube, carbon nano fiber or nano-sized carbon microballoon; Described organism pyrolytic carbon is that polyvinyl alcohol, styrene-butadiene rubber(SBR) breast, carboxymethyl cellulose, polystyrene, polymethylmethacrylate, tetrafluoroethylene, polyvinylidene difluoride (PVDF), polyacrylonitrile, resol, Resins, epoxy, glucose, sucrose, fructose, Mierocrystalline cellulose, starch or pitch are presoma, through the formed hot charcoal of high temperature cabonization.
The median size of composite particles of the present invention is 5～6 μ m, and specific surface area is 8～15m
2/ g, tap density is 1.4～1.7g/cm
3
A kind of preparation method of ferric phosphate lithium material for lithium ion powder cell, may further comprise the steps: (1) is 1: 1: 1 ratio in lithium, iron, phosphorus mol ratio with lithium salts, molysite, phosphoric acid salt, account for the LiFePO 4 material mass ratio and be 1%～25% doping vario-property agent and dispersion agent, wet ball grinding 4～48h obtains compound; (2) add in compound that to account for the LiFePO 4 material mass ratio be 1%～25% carbon encapsulated material, continue ball milling 4～48h, mist projection granulating is done the globulate presoma then; (3) with spherical presoma at 300～400 ℃ of pre-treatment 2～12h, be warmed up to 500～800 ℃ and constant temperature 4～48h again, naturally cool to room temperature then; (4) above-mentioned materials is added disintegrating apparatus, efflorescence is 10～80 minutes under 3000～6000rpm condition, joins then in the impact type nodularization pulverizer, and the nodularization shaping was handled 40～180 minutes under 600～3000rpm condition, obtained LiFePO 4 material.
The lithium salts that the inventive method adopts is Quilonum Retard, lithium fluoride, Lithium Acetate, lithium hydroxide, lithium nitrate or monometallic; Described molysite is Ferrox, Iron diacetate, ferric oxide, iron nitrate or ironic hydroxide; Described phosphoric acid salt is monometallic, primary ammonium phosphate, Secondary ammonium phosphate, triammonium phosphate, phosphoric acid or Vanadium Pentoxide in FLAKES; Described doping vario-property agent is magnesium oxide, magnesium hydroxide, magnesiumcarbonate, Magnesium Stearate, primary magnesium phosphate or Niobium Pentxoxide; Described composite carbon coating layer is one or more compositions in natural graphite, synthetic graphite micro mist, organism pyrolytic carbon and the nanometer conductive material; Described dispersion agent is a deionized water.
Behind wet ball grinding 4～48h, the compound particle diameter is 5～300nm in the inventive method; The solid content of described wet ball grinding process is 5-60wt%.
The mist projection granulating of the inventive method adopts centrifugal spray granulating and drying machine, and its temperature in is 250-280 ℃, and temperature out is 90 ℃.
The equipment of wet ball grinding is that supper micron mill, wet method stir mill, circulating ultra-fine mill, ultra-fine sand mill or ball mill in the inventive method, and used mill is situated between and is Al
2O
3Ball, ZrO
2Ball, agate ball or Stainless Steel Ball, sphere diameter are 0.1～10mm.
The pre-treatment of the inventive method, intensification and constant temperature carry out in inert atmosphere, and its Equipment for Heating Processing is sealed or the cyclone furnace kiln; Described disintegrating apparatus is supper micron mill, micronizer mill, mechanical type pulverizer or compound pulverizer.
The stove that the inventive method adopts is push-plate type tunnel furnace, tube furnace, bell jar stove or converter.
The rare gas element that the inventive method adopts is argon gas, nitrogen, hydrogen or ammonia.
The present invention compared with prior art prepares spherical composite lithium iron phosphate positive electrode material by presoma, advantages of good crystallization, and structure is single, does not contain dephasign, and the median size of composite particles is 5～60 μ m, and specific surface area is 8.0～15.0m
2/ g, the material tap density is up to 1.4～1.7g/cm
3, having the good characteristics of specific storage height, multiplying power discharging and safety performance, its preparation method is easy to suitability for industrialized production.
Description of drawings
Fig. 1 is composite ferric lithium phosphate material LiFePO among the embodiment 1
4The x ray diffraction collection of illustrative plates of/C (Cu target K alpha-ray, wavelength 0.154056nm);
Fig. 2 is composite ferric lithium phosphate material LiFePO among the embodiment 1
4The scanning electronic microscope of/C (SEM) photo;
Fig. 3 is the charging and discharging curve of embodiment 1, and wherein: charge-discharge magnification is 0.2C, and charging/discharging voltage is 2.0～4.2V;
Fig. 4 is the cycle performance curve of embodiment 1, and wherein: charge-discharge magnification is 0.2C, and charging/discharging voltage is 2.0～4.2V;
Fig. 5 is the cycle performance curve of embodiment 4, and wherein: charge-discharge magnification is 1C, and charging/discharging voltage is 2.0～4.2V.
Specific implementation method
Below in conjunction with drawings and Examples the present invention is further described.
With 740g Quilonum Retard (Li
2CO
3), 3600g Ferrox (FeC
2O
42H
2O) and 2300g primary ammonium phosphate (NH
4H
2PO
4), with the 50g magnesium hydroxide, adding in the 10kg deionized water, ball milling 24h in wet method agitating ball mill (model SX-30), the medium of use are the zirconia balls of diameter 1mm, adopting the MalvernMS2000 laser particle analyzer to record the compound particle diameter is 200nm.Add 990g glucose afterwards, continue ball milling 24h, use centrifugal spray granulating and drying machine then,, under 90 ℃ of conditions of temperature out, obtain spherical presoma 250 ℃ of temperature ins; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen, insulation 12h is warmed up to 800 ℃ and constant temperature 24h then under 300 ℃, naturally cools to room temperature; Above-mentioned materials is added supper micron mill, efflorescence 45min under 6000rpm, and then join in the impact type nodularization pulverizer, spheroidizing 120min under the 3000rpm condition obtains spherical composite lithium iron phosphate material.The result that this material obtains with Japanese D2000X x ray diffractometer x of science as shown in Figure 1, as can be seen, utilize method of the present invention, synthesized the spherical composite lithium iron phosphate positive electrode material of the olivine-type structure of pure phase, there is not impurity peaks in the spectrogram, the product purity height.The median size that adopts Malvern MS2000 laser particle analyzer to record this material is 22 μ m, and specific surface area is 9m
2/ g, tap density 1.7g/cm
3
The chemical property of gained material is tested as follows, is positive active material with synthetic composite lithium iron phosphate material, and the lithium sheet is a negative pole, is assembled into the two-electrode experiment battery.The mass ratio that consists of m (active substance): m (acetylene black): m (tetrafluoroethylene) of cathode film=85: 10: 5, the positive plate of thickness less than 0.1mm made in roll extrusion on aluminium foil, 120 ℃ of following vacuum-dryings 8 hours; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard 2400); Electrolytic solution is 1mol/l LiPF
6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) volume ratio 1: 1 is assembled into Experimental cell in glove box.The charge-discharge performance test of battery is at room temperature carried out, and (the new prestige BS9000 in Shenzhen) carries out the constant current charge-discharge loop test with cell tester.Charging/discharging voltage is 2.0～4.2V, charges and discharge multiplying power when being 0.2C, and the capacity of battery reaches 140mAh/g, circulate after 20 weeks, capacity keeps more than 98%, and 1C loading capacity first reaches 123mAh/g, remain on 116mAh/g through 60 circulation volumes, conservation rate is 94%.
Adopt Quilonum Retard (Li
2CO
3), Ferrox (FeC
2O
42H
2O) and primary ammonium phosphate (NH
4H
2PO
4) the synthetic pure phase iron lithium phosphate of ordinary method, make battery as stated above, carry out the constant current charge-discharge loop test.Charging/discharging voltage is 2.0～4.2V, charges and discharge multiplying power when being 0.2C, and specific discharge capacity is lower, 100mAh/g only, after 20 weeks of circulating, capacity keeps about 70%, 1C loading capacity first is 88mAh/g, remains on 53mAh/g through 60 circulation volumes, and conservation rate is 60%.And tap density is very low, has only 1.0g/cm
3, be significantly less than and adopt the present invention to prepare the tap density 1.7g/cm of material
3Specific surface area is 20m
2More than/the g, prepare the specific surface area 8～15m of material much larger than the present invention
2/ g.
With 840g lithium hydroxide (LiOHH
2O), 1600g ferric oxide (Fe
2O
3) and 2300g primary ammonium phosphate (NH
4H
2PO
4), 474g magnesium oxide adds in the 10kg deionized water, and ball milling 48h in wet method agitating ball mill (model SX-30), the medium of use are the zirconia balls of diameter 1mm, and adopting the MalvemMS2000 laser particle analyzer to record the compound particle diameter is 5nm.Add 990g glucose afterwards, continue ball milling 4h, use centrifugal spray granulating and drying machine then,, under 90 ℃ of conditions of temperature out, obtain spherical presoma 280 ℃ of temperature ins; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen, insulation 2h is warmed up to 750 ℃ and constant temperature 20h then under 400 ℃, naturally cools to room temperature; Above-mentioned materials is added supper micron mill, pulverize 10min under 6000rpm, and then join in the impact type nodularization pulverizer, spheroidizing 40min under the 3000rpm condition obtains spherical composite lithium iron phosphate material.The median size that records this material is 11 μ m, and specific surface area is 13m
2/ g, tap density 1.6g/cm
3Press the method for embodiment 1 and make battery, adopt identical method test, discharge and recharge scope 2.0～4.2V, charge and discharge multiplying power when being 0.2C, the capacity of battery reaches 138mAh/g, after 20 weeks of circulating, capacity keeps 99%, 1C loading capacity first reaches 120mAh/g, remains on 114mAh/g through 60 circulation volumes, and conservation rate is 95%.
Embodiment 3
With 740g Quilonum Retard (Li
2CO
3), 1600g ferric oxide (Fe
2O
3), 2300g primary ammonium phosphate (NH
4H
2PO
4), with the 50g magnesium hydroxide, adding in the 10kg deionized water, ball milling 4h in wet method agitating ball mill (model SX-30), the medium of use are the zirconia balls of diameter 1mm, adopting Malvem MS2000 laser particle analyzer to record the compound particle diameter is 300nm.Add the 400g conductive carbon black afterwards, continue ball milling 48h, use centrifugal spray granulating and drying machine then,, under 90 ℃ of conditions of temperature out, obtain spherical presoma 250 ℃ of temperature ins; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen, insulation 8h is warmed up to 800 ℃ and constant temperature 20h then under 350 ℃, naturally cools to room temperature; Above-mentioned materials is added supper micron mill, pulverize 80min under 5000rpm, and then join in the impact type nodularization pulverizer, spheroidizing 180min under the 600rpm condition obtains spherical composite lithium iron phosphate material.The median size that records this material is 5 μ m, and specific surface area is 13m
2/ g, tap density 1.4g/cm
3Press the method for embodiment 1 and make battery, adopt identical method test, discharge and recharge scope 2.0～4.2V, charge and discharge multiplying power when being 0.2C, the capacity of battery reaches 135mAh/g, after 20 weeks of circulating, capacity keeps 98.5%, 1C loading capacity first reaches 118mAh/g, remains on 112mAh/g through 60 circulation volumes, and conservation rate is 95%.
Embodiment 4
With 740g Quilonum Retard (Li
2CO
3), 3600g Ferrox (FeC
2O
42H
2O) and 2300g primary ammonium phosphate (NH
4H
2PO
4), with the 50g magnesium hydroxide, adding in the 10kg deionized water, ball milling 24h in wet method agitating ball mill (model SX-30), the medium of use are the zirconia balls of diameter 1mm, adopting the MalvemMS2000 laser particle analyzer to record the compound particle diameter is 250nm.Add 990g glucose afterwards, continue ball milling 48h, use centrifugal spray granulating and drying machine then,, under 90 ℃ of conditions of temperature out, obtain spherical presoma 260 ℃ of temperature ins; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen, insulation 12h is warmed up to 800 ℃ and constant temperature 20h then under 300 ℃, naturally cools to room temperature; Above-mentioned materials is added supper micron mill, pulverised material 60min under 4000rpm, and then join in the impact type nodularization pulverizer, spheroidizing 120min under the 1500rpm condition obtains spherical composite lithium iron phosphate material.The median size that records this material is 60 μ m, and specific surface area is 8m
2/ g, tap density 1.7g/cm
3Press the method for embodiment 1 and make battery, adopt identical method test, discharge and recharge scope 2.0～4.2V, charge and discharge multiplying power when being 0.2C, the capacity of battery reaches 137mAh/g, after 20 weeks of circulating, capacity keeps 99%, 1C loading capacity first reaches 119mAh/g, remains on 112mAh/g through 60 circulation volumes, and conservation rate is 94%.
With 840g lithium hydroxide (LiOHH
2O), 3600g Ferrox (FeC
2O
42H
2O) and 2640g Secondary ammonium phosphate ((NH
4)
2HPO
4), with 80g Niobium Pentxoxide (Nb
2O
5), adding in the 10kg deionized water, ball milling 24h in wet method agitating ball mill (model SX-30), the medium of use are the zirconia balls of diameter 1mm, adopting Malvem MS2000 laser particle analyzer to record the compound particle diameter is 150nm.Add the 400g conductive carbon black afterwards, continue ball milling 24h, use centrifugal spray granulating and drying machine then,, under 90 ℃ of conditions of temperature out, obtain spherical presoma 250 ℃ of temperature ins; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen, insulation 12h is warmed up to 750 ℃ and constant temperature 36h then under 300 ℃, naturally cools to room temperature; Above-mentioned materials is added supper micron mill, pulverize 30min under 6000rpm, and then join in the impact type nodularization pulverizer, spheroidizing 90min under the 3000rpm condition obtains spherical composite lithium iron phosphate material.The median size that records this material is 10 μ m, and specific surface area is 13m
2/ g, tap density 1.7g/cm
3Press the method for embodiment 1 and make battery, adopt identical method test, discharge and recharge scope 2.0～4.2V, charge and discharge multiplying power when being 0.2C, the capacity of battery reaches 137mAh/g, after 20 weeks of circulating, capacity keeps 98%, 1C loading capacity first reaches 121mAh/g, remains on 117mAh/g through 60 circulation volumes, and conservation rate is 97%.
Embodiment 6
With 2080g monometallic (LiH
2PO
4), 3600g Ferrox (FeC
2O
42H
2O) (monometallic serves as phosphoric acid salt simultaneously) is with 80g Niobium Pentxoxide (Nb
2O
5), adding in the 10kg deionized water, ball milling 24h in wet method agitating ball mill (model SX-30), the medium of use are the zirconia balls of diameter 1mm, adopting Malvern MS2000 laser particle analyzer to record the compound particle diameter is 200nm.Add the 400g conductive carbon black afterwards, continue ball milling 24h, use centrifugal spray granulating and drying machine then,, under 90 ℃ of conditions of temperature out, obtain spherical presoma 250 ℃ of temperature ins; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen, insulation 12h is warmed up to 750 ℃ and constant temperature 36h then under 300 ℃, naturally cools to room temperature; Above-mentioned materials is added supper micron mill, pulverize 30min under 6000rpm, and then join in the impact type nodularization pulverizer, spheroidizing 60min under the 3000rpm condition obtains spherical composite lithium iron phosphate material.The median size that records this material is 10 μ m, and specific surface area is 13m
2/ g, tap density 1.6g/cm
3Press the method for embodiment 1 and make battery, adopt identical method test, discharge and recharge scope 2.0～4.2V, charge and discharge multiplying power when being 0.2C, the capacity of battery reaches 137mAh/g, after 20 weeks of circulating, capacity keeps 99%, 1C loading capacity first reaches 121mAh/g, remains on 117mAh/g through 60 circulation volumes, and conservation rate is 97%.
Embodiment 7
With 2080g monometallic (LiH
2PO
4), 1600g ferric oxide (Fe
2O
3) (monometallic serves as phosphoric acid salt simultaneously) and 80g Niobium Pentxoxide (Nb
2O
5), adding in the 10kg deionized water, ball milling 24h in wet method agitating ball mill (model SX-30), the medium of use are the zirconia balls of diameter 1mm, adopting Malvem MS2000 laser particle analyzer to record the compound particle diameter is 240nm.Add the 400g conductive carbon black afterwards, continue ball milling 24h, use centrifugal spray granulating and drying machine then,, under 90 ℃ of conditions of temperature out, obtain spherical presoma 250 ℃ of temperature ins; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen, insulation 12h is warmed up to 700 ℃ and constant temperature 36h then under 300 ℃, naturally cools to room temperature; Above-mentioned materials is added supper micron mill, pulverize 50min under 6000rpm, and then join in the impact type nodularization pulverizer, spheroidizing 100min under the 3000rpm condition obtains spherical composite lithium iron phosphate material.The median size that records this material is 10 μ m, and specific surface area is 13m
2/ g, tap density 1.6g/cm
3Press the method for embodiment 1 and make battery, adopt identical method test, discharge and recharge scope 2.0～4.2V, charge and discharge multiplying power when being 0.2C, the capacity of battery reaches 132mAh/g, after 20 weeks of circulating, capacity keeps 97%, 1C loading capacity first reaches 115mAh/g, remains on 108mAh/g through 60 circulation volumes, and conservation rate is 93%.
With 2080g monometallic (LiH
2PO
4), 2140g ironic hydroxide (Fe (HO)
3), (monometallic serves as phosphoric acid salt simultaneously) and 80g Niobium Pentxoxide (Nb
2O
5), adding in the 10kg deionized water, ball milling 24h in wet method agitating ball mill (model SX-30), the medium of use are the zirconia balls of diameter 1mm, adopting Malvern MS2000 laser particle analyzer to record the compound particle diameter is 200nm.Add the 400g conductive carbon black afterwards, continue ball milling 24h, use centrifugal spray granulating and drying machine then,, under 90 ℃ of conditions of temperature out, obtain spherical presoma 250 ℃ of temperature ins; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen, insulation 12h is warmed up to 750 ℃ and constant temperature 24h then under 300 ℃, naturally cools to room temperature; Above-mentioned materials is added supper micron mill, pulverize 50min under 6000rpm, and then join in the impact type nodularization pulverizer, spheroidizing 100min under the 3000rpm condition obtains spherical composite lithium iron phosphate material.The median size that records this material is 12 μ m, and specific surface area is 15m
2/ g, tap density 1.6g/cm
3Press the method for embodiment 1 and make battery, adopt identical method test, discharge and recharge scope 2.0～4.2V, charge and discharge multiplying power when being 0.2C, the capacity of battery reaches 136mAh/g, after 20 weeks of circulating, capacity keeps 99%, 1C loading capacity first reaches 118mAh/g, remains on 108mAh/g through 60 circulation volumes, and conservation rate is 92%.
LiFePO
4Belong to olivine-type structure, spacer is Pnmb.In the a-c plane at lithium atom place, include PO
4Tetrahedron, this has just limited the mobile space of lithium ion, so its specific conductivity is lower than other lamellar compound.
The hot method composition principle that the present invention adopts iron lithium phosphate is at high temperature raw material lithium salts, ferrous salt, phosphoric acid salt generation redox reaction, generating micro-molecular gas overflows and iron lithium phosphate, according to this composition principle, the available lithium salts is Quilonum Retard, lithium fluoride, Lithium Acetate, lithium hydroxide, lithium nitrate or monometallic; The available molysite is Ferrox, Iron diacetate, ferric oxide, iron nitrate or ironic hydroxide; Phosphoric acid salt can be monometallic, primary ammonium phosphate, Secondary ammonium phosphate, triammonium phosphate, phosphoric acid or Vanadium Pentoxide in FLAKES.For improving the chemical property of synthetics, the doping vario-property agent of employing is magnesium oxide, magnesium hydroxide, magnesiumcarbonate, Magnesium Stearate, primary magnesium phosphate or Niobium Pentxoxide, Mg wherein simultaneously
2+, Nb
5+Enter LiFePO Deng metal ion
4Replace Li wherein in the lattice
+The position, conductivity of electrolyte materials is improved greatly; In order further to improve the conductivity of material, reduce battery polarization, give full play to the capacity of positive electrode material, and the synthetic atmosphere of control prevents ferrous oxidation, has adopted the carbon doping among the preparation method of the present invention, used carbon material can be the higher natural graphite powder of crystalline structure, graphous graphite powder, nano-carbon material (raising specific conductivity), also can adopt various organism RESEARCH OF PYROCARBON, improve the synthetic atmosphere of material, anti-oxidation.Above-mentioned organism pyrolytic carbon can be that polyvinyl alcohol, styrene-butadiene rubber(SBR) breast, carboxymethyl cellulose, polystyrene, polymethylmethacrylate, tetrafluoroethylene, polyvinylidene difluoride (PVDF), polyacrylonitrile, resol, Resins, epoxy, glucose, sucrose, fructose, Mierocrystalline cellulose, starch or pitch etc. are presoma, through the formed pyrolytic carbon of high temperature cabonization.The doping vario-property agent is the compound that contains metallic elements such as Mg, Nb, as magnesium oxide, magnesium hydroxide, magnesiumcarbonate, Magnesium Stearate, primary magnesium phosphate or Niobium Pentxoxide etc.
Claims (15)
1. ferric phosphate lithium material for lithium ion powder cell, it is characterized in that: described LiFePO 4 material has lithium iron phosphate and doping vario-property agent matrix, matrix is coated with the composite carbon coating layer and forms particulate, and particulate is combined into composite particulate material, and composite particles is spherical in shape or class is spherical.
2. ferric phosphate lithium material for lithium ion powder cell according to claim 1 is characterized in that: described lithium iron phosphate is lithium salts, molysite and phosphoric acid salt, and the mol ratio of lithium, iron, phosphorus is 1: 1: 1.
3. ferric phosphate lithium material for lithium ion powder cell according to claim 2 is characterized in that: described lithium salts is Quilonum Retard, lithium fluoride, Lithium Acetate, lithium hydroxide, lithium nitrate or monometallic; Described molysite is Ferrox, Iron diacetate, ferric oxide, iron nitrate or ironic hydroxide; Described phosphoric acid salt is monometallic, primary ammonium phosphate, Secondary ammonium phosphate, triammonium phosphate, phosphoric acid or Vanadium Pentoxide in FLAKES.
4. ferric phosphate lithium material for lithium ion powder cell according to claim 3, it is characterized in that: described doping vario-property agent is magnesium oxide, magnesium hydroxide, magnesiumcarbonate, Magnesium Stearate, primary magnesium phosphate or Niobium Pentxoxide, and the mass ratio that accounts for composite particulate material is 1%～25%.
5. ferric phosphate lithium material for lithium ion powder cell according to claim 4, it is characterized in that: described composite carbon coating layer is one or more compositions in natural graphite, synthetic graphite micro mist, organism pyrolytic carbon and the nanometer conductive material, and the mass ratio that accounts for composite particulate material is 1%～25%.
6. ferric phosphate lithium material for lithium ion powder cell according to claim 5 is characterized in that: described nanometer conductive material is conductive carbon black, carbon nanotube, carbon nano fiber or nano-sized carbon microballoon; Described organism pyrolytic carbon is that polyvinyl alcohol, styrene-butadiene rubber(SBR) breast, carboxymethyl cellulose, polystyrene, polymethylmethacrylate, tetrafluoroethylene, polyvinylidene difluoride (PVDF), polyacrylonitrile, resol, Resins, epoxy, glucose, sucrose, fructose, Mierocrystalline cellulose, starch or pitch are presoma, through the formed pyrolytic carbon of high temperature cabonization.
7. ferric phosphate lithium material for lithium ion powder cell according to claim 6 is characterized in that: the median size of described composite particles is 5～60 μ m, and specific surface area is 8～15m
2/ g, tap density is 1.4～1.7g/cm
3
8. the preparation method of a ferric phosphate lithium material for lithium ion powder cell, may further comprise the steps: (1) is 1: 1: 1 ratio in lithium, iron, phosphorus mol ratio with lithium salts, molysite, phosphoric acid salt, account for the LiFePO 4 material mass ratio and be 1%～25% doping vario-property agent and dispersion agent, wet ball grinding 4～48h obtains compound; (2) add in compound that to account for the LiFePO 4 material mass ratio be 1%～25% carbon encapsulated material, continue ball milling 4～48h, mist projection granulating is done the globulate presoma then; (3) with spherical presoma at 300～400 ℃ of pre-treatment 2～12h, be warmed up to 500～800 ℃ and constant temperature 4～48h again, naturally cool to room temperature then; (4) above-mentioned materials is added disintegrating apparatus, efflorescence is 10～80 minutes under 3000～6000rpm condition, joins then in the impact type nodularization pulverizer, and the nodularization shaping was handled 40～180 minutes under 600～3000rpm condition, obtained LiFePO 4 material.
9. the preparation method of ferric phosphate lithium material for lithium ion powder cell according to claim 8, it is characterized in that: described lithium salts is Quilonum Retard, lithium fluoride, Lithium Acetate, lithium hydroxide, lithium nitrate or monometallic; Described molysite is Ferrox, Iron diacetate, ferric oxide, iron nitrate or ironic hydroxide; Described phosphoric acid salt is monometallic, primary ammonium phosphate, Secondary ammonium phosphate, triammonium phosphate, phosphoric acid or Vanadium Pentoxide in FLAKES; Described doping vario-property agent is magnesium oxide, magnesium hydroxide, magnesiumcarbonate, Magnesium Stearate, primary magnesium phosphate or Niobium Pentxoxide; Described composite carbon coating layer is one or more compositions in natural graphite, synthetic graphite micro mist, organism pyrolytic carbon and the nanometer conductive material; Described dispersion agent is a deionized water.
10. the preparation method of ferric phosphate lithium material for lithium ion powder cell according to claim 9, it is characterized in that: behind described wet ball grinding 4～48h, the compound particle diameter is 5～300nm; The solid content of described wet ball grinding process is 5-60wt%.
11. the preparation method of ferric phosphate lithium material for lithium ion powder cell according to claim 10 is characterized in that: described mist projection granulating adopts centrifugal spray granulating and drying machine, and its temperature in is 250-280 ℃, and temperature out is 90 ℃.
12. the preparation method of ferric phosphate lithium material for lithium ion powder cell according to claim 11, it is characterized in that: the equipment of described wet ball grinding is that supper micron mill, wet method stir mill, circulating ultra-fine mill, ultra-fine sand mill or ball mill, and used mill is situated between and is Al
2O
3Ball, ZrO
2Ball, agate ball or Stainless Steel Ball, sphere diameter are 0.1～10mm.
13. the preparation method of ferric phosphate lithium material for lithium ion powder cell according to claim 12 is characterized in that: described pre-treatment, intensification and constant temperature carry out in inert atmosphere, and its Equipment for Heating Processing is sealed or the cyclone furnace kiln; Described disintegrating apparatus is supper micron mill, micronizer mill, mechanical type pulverizer or compound pulverizer.
14. the preparation method of ferric phosphate lithium material for lithium ion powder cell according to claim 13 is characterized in that: described stove is push-plate type tunnel furnace, tube furnace, bell jar stove or converter.
15. the preparation method of ferric phosphate lithium material for lithium ion powder cell according to claim 14 is characterized in that: described rare gas element is argon gas, nitrogen, hydrogen or ammonia.
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| CN100377392C (en) * | 2004-12-21 | 2008-03-26 | 中国科学院物理研究所 | Anode material lithium ferric phosphate containing oxygen vacancy in use for secondary battery of lithium ion, and application |
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