CN101162776B - Lithium iron phosphate suitable for high multiplying power electrokinetic cell and method for producing the same - Google Patents
Lithium iron phosphate suitable for high multiplying power electrokinetic cell and method for producing the same Download PDFInfo
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- CN101162776B CN101162776B CN2007101241452A CN200710124145A CN101162776B CN 101162776 B CN101162776 B CN 101162776B CN 2007101241452 A CN2007101241452 A CN 2007101241452A CN 200710124145 A CN200710124145 A CN 200710124145A CN 101162776 B CN101162776 B CN 101162776B
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- China
- Prior art keywords
- lithium
- multiplying power
- phosphate
- electrokinetic cell
- applicable
- Prior art date
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000007772 electrode material Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 239000011246 composite particle Substances 0.000 claims abstract description 7
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 238000006253 efflorescence Methods 0.000 claims description 12
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- 206010037844 rash Diseases 0.000 claims description 12
- 238000007493 shaping process Methods 0.000 claims description 12
- 230000004927 fusion Effects 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229940062993 ferrous oxalate Drugs 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical group [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 10
- 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 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
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052744 lithium 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
- 239000000126 substance Substances 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 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 7
- 239000008103 glucose Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 239000003595 mist Substances 0.000 claims description 6
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-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
- 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
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 239000005715 Fructose Substances 0.000 claims description 4
- 229930091371 Fructose Natural products 0.000 claims description 4
- 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 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 210000000481 breast Anatomy 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000011295 pitch Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000012798 spherical particle Substances 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 239000010959 steel Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000000498 ball milling Methods 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- DJBQSLSCMPHXBH-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Fe+2].[Li+].[Fe+2] Chemical compound P(=O)([O-])([O-])[O-].[Fe+2].[Li+].[Fe+2] DJBQSLSCMPHXBH-UHFFFAOYSA-K 0.000 abstract 1
- 239000003575 carbonaceous material Substances 0.000 abstract 1
- 238000003754 machining Methods 0.000 abstract 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 19
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 4
- 235000014413 iron hydroxide Nutrition 0.000 description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 description 4
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 description 4
- 235000019785 monomagnesium phosphate Nutrition 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000005260 alpha ray Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000003913 materials processing Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000009467 reduction Effects 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
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- 239000010405 anode material Substances 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000010406 cathode material 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
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 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
- 239000012528 membrane Substances 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 239000007774 positive electrode material Substances 0.000 description 1
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- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 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 present invention discloses an iron phosphate lithium suitable for a high-rate power battery and a method for preparing the same; the technical problem to be solved is the low electrochemical property of an iron phosphate lithium material; the iron phosphate iron lithium of the invention uses lithium iron phosphate as a basal body; nanometer carbon material particles and particles formed by nanometer metal or/and nanometer metal oxide conducting layers are covered outside the basal body; the particles are combined to composite particles which are of a spherical shape or of a near-spherical shape with major to minor diameter ratio between 1.2 and 2.5. The preparation method comprises the following procedures: through the wet method and ball milling, the particles are sprayed to a spherical precursor, then through pretreatment, constant-temperature treatment and pulverization and plastic treatment, the spherical precursor is fused mechanically; compared with the prior art, the iron phosphate lithium electrode material has good crystallization, single structure, no dephasign, even grain diameter distribution, excellent material machining performance, good electric conduction performance, excellent rate performance, high actual capacity and simple preparation technique.
Description
Technical field
The present invention relates to a kind of positive electrode that is applicable to the high magnification power lithium-ion battery and preparation method thereof, particularly a kind of composite lithium iron phosphate positive electrode and preparation method thereof.
Background technology
Lithium ion battery has the voltage height as the new generation of green high-energy battery, and energy density is big, good cycle, and self discharge is little, memory-less effect, the advantage that operating temperature range is wide and being widely used.Positive electrode is again the important component part of lithium ion battery, and LiFePO4 becomes the focus of current research as positive electrode of new generation.Lithium iron phosphate positive material has theoretical capacity height (about 170mAh/g), and nontoxic, the raw material range of choice is wide, stable operating voltage, and Stability Analysis of Structures, fail safe is splendid, Heat stability is good, the plurality of advantages of high temperature and good cycle.The synthetic of LiFePO4 still is to synthesize the master with solid phase method at present; as Chinese patent publication number CN1581537, CN1753216, CN1762798 and the described method of CN1767238; promptly be that the carbonate of lithium (or hydroxide, phosphate), ferrous oxalate (or ferrous acetate, ferrous phosphate) and ammonium dihydrogen phosphate (or diammonium hydrogen phosphate) are mixed, high-temperature roasting forms under inert gas shielding.Preparation technology is simple for this method, and condition is easy to control, is convenient to suitability for industrialized production.But the product particle size distribution is wide, and crystalline size is bigger, and powder is made up of random particle, and bulk 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), LiMn2O4 (2.2g/cm
3) tap density; And the LiFePO4 conductivity is low, and high-rate charge-discharge capability is relatively poor, causes the practical application difficulty of material.For improving the serviceability of LiFePO4, people carry out doping treatment to LiFePO4, as the disclosed oxygen place doped method of Chinese patent publication number CN1772604, the disclosed transition element doped method of CN1785799, the disclosed rear-earth-doped method of CN1785800, the disclosed P site doped method of CN1785823, though said method can partly improve the serviceability of LiFePO4, is not easy to realize industrialized production.
Summary of the invention
The purpose of this invention is to provide a kind of LiFePO4 that high multiplying power electrokinetic cell is used and preparation method thereof that is applicable to, the technical problem that solves is to improve the chemical property of LiFePO 4 material and the multiplying power discharging and the security performance of lithium ion battery, and suitable suitability for industrialized production.
The present invention is by the following technical solutions: a kind of LiFePO4 that is applicable to that high multiplying power electrokinetic cell is used, described LiFePO4 electrode material is matrix with the lithium iron phosphate, matrix is coated with carbon nano-material particulate, nano metal or/and the nano-metal-oxide conductive layer forms particulate, described particulate is combined into composite particles, and the spherical in shape or line of apsides ratio of composite particles is 1.2～2.5 class spherical forms.
Lithium iron phosphate of the present invention is lithium salts, molysite and phosphate, and the mol ratio of lithium, iron, phosphorus is 1: 1: 1.
Lithium salts of the present invention is lithium carbonate, lithium fluoride, lithium acetate, lithium hydroxide, lithium nitrate or lithium dihydrogen phosphate; Described molysite is ferrous oxalate, ferrous acetate, di-iron trioxide, ferric nitrate or iron hydroxide; Described phosphate is lithium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, phosphoric acid or phosphorus pentoxide.
Carbon nano-material particulate of the present invention is one or more compositions of native graphite micro mist, Delanium micro mist, conductive carbon black, organic substance pyrolytic carbon and nanometer conductive material.
Organic substance pyrolytic carbon of the present invention is that polyvinyl alcohol, butadiene-styrene rubber breast, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, phenolic resins, epoxy resin, glucose, sucrose, fructose, cellulose, starch or pitch are presoma, through the formed pyrolytic carbon of high temperature cabonization; Described nanometer conductive material is carbon nano-tube, carbon nano-fiber or nano-sized carbon microballoon.
Nano metal of the present invention or nano-metal-oxide are nanometer metallic silver, metallic copper, metallic aluminium, magnesium oxide, chromium oxide, manganese oxide, cobalt oxide, aluminium oxide, magnesium hydroxide, magnesium carbonate, dolomol, magnesium dihydrogen phosphate, niobium pentaoxide.
The ratio that conductive layer of the present invention accounts for composite material is 1wt.%～25wt.%.
The average grain diameter of composite particles of the present invention is 5～60 μ m, specific area 8～13m
2/ g, tap density 1.4～1.7g/cm
3
A kind of method preparing phosphate iron lithium that is applicable to that high multiplying power electrokinetic cell is used, comprise the steps: one, be 1: 1: 1 ratio with lithium salts, molysite, phosphate in the mol ratio of lithium, iron, phosphorus, add that to account for lithium salts, molysite and phosphatic ratio be the dispersant of 1wt.%～2.5wt.% and to account for lithium salts, molysite and phosphatic ratio be 1wt.%～2.5wt.% material with carbon element predecessor, nano metal or/and the nano-metal-oxide conductive agent, wet ball grinding 4～48 hours is to slurry; Two, slurry is 150～400 ℃ of inlet temperatures, and outlet temperature is that spherical presoma is made in spraying under 60～135 ℃ the condition; Three, with the preliminary treatment 2～12 hours in 300～400 ℃ of temperature ranges in inert atmosphere of spherical presoma, 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; Four, with above-mentioned material efflorescence 10～80 minutes under 3000～6000rpm condition, the nodularization shaping was handled 40～180 minutes under 600～3000rpm condition then, obtained sphere or class spherical particle that matrix is coated with conductive layer; Five, particulate is carried out mechanical fusion treatment under the rotating speed of 200～1100rpm and be composite particles in 0.5～4 hour, obtain the sphere or the line of apsides than the LiFePO4 electrode material that is 1.2～2.5 class spherical forms.
The lithium salts of the inventive method is lithium carbonate, lithium fluoride, lithium acetate, lithium hydroxide, lithium nitrate, lithium dihydrogen phosphate; Described microcosmic salt is ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, phosphoric acid, phosphorus pentoxide, lithium dihydrogen phosphate; Described molysite is ferrous oxalate, ferrous acetate, di-iron trioxide, ferric nitrate, iron chloride, iron hydroxide.
The material with carbon element particulate of the inventive method is one or more compositions of native graphite, Delanium micro mist, conductive carbon black, organic substance pyrolytic carbon and nanometer conductive material; Described nano metal or nano-metal-oxide are nanometer metallic silver, metallic copper, metallic aluminium, magnesium oxide, chromium oxide, manganese oxide, cobalt oxide, aluminium oxide, magnesium hydroxide, magnesium carbonate, dolomol, magnesium dihydrogen phosphate, niobium pentaoxide.
The organic substance pyrolytic carbon of the inventive method is that polyvinyl alcohol, butadiene-styrene rubber breast, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, phenolic resins, epoxy resin, glucose, sucrose, fructose, cellulose, starch or pitch are presoma, through the formed pyrolytic carbon of high temperature cabonization; Described nanometer conductive material is carbon nano-tube, carbon nano-fiber or nano-sized carbon microballoon.
The dispersant of the inventive method is an absolute ethyl alcohol.
The used equipment of the wet ball grinding of the inventive method is that wet method stirs ball mill grinding equipment such as mill, circulating ultra-fine mill, ultra-fine sand mill, ball mill, and used mill is situated between and is Al
2O
3Ball, ZrO
2Ball, agate ball or stainless steel ball, sphere diameter is at 0.1～10mm.
The account for 5～60wt% of quality of ionized water of the quality that the inventive method wet ball grinding drops into raw material, the solid granularity is 5～300nm after the fine grinding.
Centrifugal spray granulating and drying machine is adopted in the inventive method spraying; Preliminary treatment and constant temperature are handled and are adopted push-plate type tunnel cave, tube furnace, bell jar stove, rotary furnace, steel band stove, vacuum furnace sealed type or cyclone furnace kiln; Airslide disintegrating mill, mechanical type pulverizer or compound pulverizer are adopted in described efflorescence; Impact type nodularization pulverizer is adopted in the nodularization shaping; Described inert gas is argon gas, nitrogen, helium, neon.
The present invention compared with prior art, the LiFePO4 electrode material of complex spherical or almost spherical, advantages of good crystallization, structure is single, does not contain dephasign, particle size distribution is even, tap density is up to 1.4～1.7g/cm
3, specific area is 8.0～13.0m
2/ g, the pole piece compacted density reaches 1.9-2.8g/cm
3, the materials processing function admirable conducts electricity very well, and high rate performance is superior, the actual capacity height, preparation technology is simple, is fit to suitability for industrialized production.
Description of drawings
Fig. 1 is composite ferric lithium phosphate material LiFePO in the embodiment of the invention 1
4X x ray diffraction collection of illustrative plates (the Cu target K of/C
αRay, wavelength 0.154056nm).
Fig. 2-the 1st, composite ferric lithium phosphate material LiFePO in the embodiment of the invention 1
4The scanning electron microscopy of/C (SEM) photo, multiplication factor is 5000 times.
Fig. 2-the 2nd, scanning electron microscopy (SEM) photo of spherical presoma is made in spraying in the embodiment of the invention 1, and multiplication factor is 500 times.
Fig. 3 is the charging and discharging curve of the embodiment of the invention 1, and wherein: charge-discharge magnification is 0.1C, and charging/discharging voltage is 2.5～3.9V.
Fig. 4 is the multiplying power discharging curve of the embodiment of the invention 1, and wherein: discharge-rate is respectively 5C, 15C, 25C, and charging/discharging voltage is 2.0～4.1V.
Fig. 5 is the cycle performance curve of the embodiment of the invention 1, and wherein: discharge-rate is 5C, and charging/discharging voltage is 2.0～4.1V.
Fig. 6 is the charging and discharging curve of the embodiment of the invention 1, and wherein: discharge-rate is 15C, and charging/discharging voltage is 2.0～4.1V.
Fig. 7 is the charging and discharging curve of the embodiment of the invention 1, and wherein: discharge-rate is 25C, and charging/discharging voltage is 2.0～4.1V.
Specific implementation method
Below in conjunction with drawings and Examples the present invention is further described.
Embodiment 1
With 2080g lithium dihydrogen phosphate (LiH
2PO
4) and 1600g di-iron trioxide (Fe
2O
3) add in the deionized water of 97.68kg, the absolute ethyl alcohol that adds 50mL then slowly adds 1200g glucose at last as dispersant in above-mentioned compound, the 4g nanometer aluminium powder, at ball mill by wet process, zirconia ball, particle diameter is the interior ball milling of the ball of 2-5mm 6 hours, 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 (LPG of Jiangyin golden hair drying equipment Co., Ltd) then, 400 ℃ of inlet temperatures, under 135 ℃ of conditions of outlet temperature, utilize instaneous polymerization, dry spraying to make spherical presoma, shown in Fig. 2-2, presoma is a ball-type as can be seen in 500 times SEM figure; With spherical presoma in the KSS-16G tube furnace that Yongtai, Luoyang City testing furnace factory produces, charge into nitrogen protection, 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 in the fluidized bed air flow crusher (close friend's board QYF type that Kunshan Industrial Co., Ltd. produces), efflorescence is 60 minutes under the 3000rpm condition, and then join in the impact type nodularization pulverizer, the nodularization shaping was handled 180 minutes under the 600rpm condition, obtained sphere or class spherical particle that matrix is coated with conductive layer; Particulate was carried out mechanical fusion treatment 0.5 hour in the star technological development Q50 of Co., Ltd type fusion machine is opened in Luoyang, under the rotating speed of 1100rpm, be the ball-type or the class ball-type composite particles of metallic cover, shown in Fig. 2-1, obtain the sphere or the line of apsides than the LiFePO4 electrode material that is 1.5 class spherical forms.X x ray diffraction collection of illustrative plates (the Cu target K of the LiFePO4 electrode material that present embodiment makes
αRay, wavelength 0.154056nm) as shown in Figure 1, as can be seen from the figure, utilize the method for high temperature solid-phase sintering of the present invention, synthesized the spherical lithium iron phosphate anode material of the olivine-type structure of pure phase, there are not impurity peaks, product purity height in the spectrogram.The average grain diameter that the Mastersizer 2000 that produces with Malvern Instruments Ltd records this material is 10 μ m, and specific area records on ST-08SSA TESTING INSTRUMENT instrument, and specific area is 11.5m
2/ g, tap density is 1.45g/cm
3
The electrochemical property test of above-mentioned material is tested as follows, is positive active material with synthetic LiFePO4, and the lithium sheet is a negative pole, is assembled into the two-electrode experiment battery.Cathode film consist of m (active material): m (acetylene black): m (polytetrafluoroethylene)=85: 10: 5, 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 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 new prestige cell tester BTS-5V50A carries out the constant current charge-discharge loop test with Shenzhen.Charging/discharging voltage is 2.5～3.9V, charges and discharge multiplying power when being 0.1C, and the capacity of battery reaches 151mAh/g, and after 50 weeks of circulating, it is fine that capacity keeps, and do not see decay, and test result as shown in Figure 3.
The XRD analysis of product carries out Cu target, K on X ' the Pert Pro type X-ray diffraction instrument that Dutch PANalytical produces
αLine, sweep limits are 10～80 °.The qualitative analysis of thing phase is by getting with the card contrast the diffraction maximum PDF on the X diffractometer.
The morphology analysis of product is to carry out on the SEM instrument of the KYKY2800B type that Beijing section instrument produces, amplification be respectively 5000 times and 500 times.
The pole piece of finished product battery is film-making on the automanual tensile pulp machine that produces of five metals Electronics Equipment Co., Ltd forever in Shenzhen three.After the pole piece oven dry, reach on the DYG-703 type twin rollers that power power supply Industrial Co., Ltd. produces in Shaoyang and to carry out compressing tablet, regulate the compacting ratio by the parameter of adjusting twin rollers.In this example, the compacting of pole piece ratio is 2.2.After battery was made, multiplying power discharging property was to test on the BS-9300R tester that Electrotechnical Branch of Qingtian Industry Co Ltd, Guangzhou produces.Capacity according to battery, the electric current that battery is provided with 5C, 15C, 25C discharges and recharges, the multiplying power discharging result as shown in Figure 4, when the battery capacity during discharge-rate 25C is 5C 89.3%, when the battery capacity during discharge-rate 15C is 5C 93.3% shows that the multiplying power discharging property of material is better.Discharge-rate is 5C, charging/discharging voltage be 2.0～4.1V the cycle performance result as shown in Figure 5, the capability retention of the 500 all batteries that circulate is 99.0%.Discharge-rate is 15C, and charging/discharging voltage is that 2.0～4.1V discharges and recharges the result as shown in Figure 6, and the capability retention of the 500 all batteries that circulate is 97.9%.Discharge-rate is 25C, and charging/discharging voltage is that 2.0～4.1V discharges and recharges the result as shown in Figure 7, and the capability retention of the 500 all batteries that circulate is 95.2%.The test of finished product battery is all tested in following example, and method of testing is with example 1.
Embodiment 2
With 2080g lithium dihydrogen phosphate (LiH
2PO
4), 3600g ferrous oxalate (FeC
2O
42H
2O) add in the deionized water of 9.97kg, add the 50mL absolute ethyl alcohol then, in above-mentioned compound, add 300g nano-sized carbon microballoon at last as dispersant, the 3g copper nanoparticle, wet ball grinding 24 hours, levigate to 150nm; The 60wt% of quality that the quality that drops into raw material accounts for ionized water uses centrifugal spray granulating and drying machine then, 350 ℃ of inlet temperatures, under 115 ℃ of conditions of outlet temperature, utilizes instaneous polymerization, drying to make spherical presoma; With spherical presoma in tube furnace, charge into argon gas, in 400 ℃ of following preliminary treatment 5 hours,, be warmed up to 700 ℃ and constant temperature 12 hours then with the heating rate of 5 ℃/min, naturally cool to room temperature; Above-mentioned material is added disintegrating apparatus, efflorescence is 30 minutes under the 4000rpm condition, and then join in the impact type nodularization pulverizer, the nodularization shaping was handled 60 minutes under the 1000rpm condition, under the rotating speed of 800rpm, carried out mechanical fusion treatment 2 hours, and obtained the sphere or the line of apsides than the LiFePO4 electrode material that is 1.7 class spherical forms.The average grain diameter of this material is 11 μ m, and specific area is 15m
2/ g, tap density 1.25g/cm
3Prepare electrode according to the method identical with example 1, carry out electrochemical property test, charge and discharge multiplying power when being 0.1C, the capacity of battery reaches 150mAh/g.Circulate after 50 weeks, it is fine that capacity keeps, and do not see decay.
Embodiment 3
With 740g lithium carbonate (Li
2CO
3), 3600g ferrous oxalate (FeC
2O
42H
2O) and 2300g ammonium dihydrogen phosphate (NH
4H
2PO
4) add in the deionized water of 20kg, add the 200mL absolute ethyl alcohol then as dispersant, in above-mentioned compound, add the 65g carbon nano-fiber at last, the nano oxidized magnesium dust of 20g, wet ball grinding 4 hours, levigate to 200nm; The 33.6wt% of quality that the quality that drops into raw material accounts for ionized water uses centrifugal spray granulating and drying machine then, 300 ℃ of inlet temperatures, under 100 ℃ of conditions of outlet temperature, utilizes instaneous polymerization, dry spraying to make spherical presoma; With spherical presoma in tube furnace, charge into nitrogen, in 350 ℃ of following preliminary treatment 6 hours,, be warmed up to 600 ℃ and constant temperature 24 hours then with the heating rate of 4 ℃/min, naturally cool to room temperature; Above-mentioned material is joined in the disintegrating apparatus, efflorescence is 60 minutes under the 4000rpm condition, and then join in the impact type nodularization pulverizer, the nodularization shaping was handled 80 minutes under the 1000rpm condition, under the rotating speed of 600rpm, carried out mechanical fusion treatment 3 hours, and obtained the sphere or the line of apsides than the LiFePO4 electrode material that is 1.8 class spherical forms.The average grain diameter that records this material is 12 μ m, and specific area is 12m
2/ g, tap density 1.6g/cm
3Prepare electrode according to the method identical with example 1, carry out electrochemical property test, charge and discharge multiplying power when being 0.1C, the capacity of battery reaches 148mA hour/g, and after 50 weeks of circulating, it is fine that capacity keeps, and do not see decay.
Embodiment 4
With 740g lithium carbonate (Li
2CO
3), 3600g ferrous oxalate (FeC
2O
42H
2O) and 2300g ammonium dihydrogen phosphate (NH
4H
2PO
4) add in the deionized water of 15.89kg, add the 150mL absolute ethyl alcohol then as dispersant, in above-mentioned compound, add 500g glucose at last, 10g nanometer niobium pentaoxide powder, wet ball grinding 36 hours, levigate to 150nm; The 45wt% of quality that the quality that drops into raw material accounts for ionized water uses centrifugal spray granulating and drying machine then, 200 ℃ of inlet temperatures, under 60 ℃ of conditions of outlet temperature, utilizes instaneous polymerization, drying to make spherical presoma; With spherical presoma in tube furnace, charge into argon gas, in 400 ℃ of following preliminary treatment 5 hours, the heating rate of 3 ℃/min was warmed up to 700 ℃ and constant temperature 12 hours then, naturally cooled to room temperature; Above-mentioned material is added disintegrating apparatus, efflorescence is 60 minutes under the 3000rpm condition, and then join in the impact type nodularization pulverizer, the nodularization shaping was handled 120 minutes under the 1500rpm condition, under the rotating speed of 800rpm, carried out mechanical fusion treatment 2 hours, and obtained the sphere or the line of apsides than the LiFePO4 electrode material that is 2.5 class spherical forms.The average grain diameter that records this material is 15 μ m, and specific area is 13m
2/ g, tap density 1.6g/cm
3Prepare electrode according to the method identical with example 1, carry out electrochemical property test, discharge and recharge scope 2.5～3.9V, charge and discharge multiplying power when being 0.1C, the capacity of battery reaches 141mAh/g.Finished product battery 1C discharge capacity first reaches 128.5mAh/g, increases to some extent through 50 circulation back capacity, is 130.1mAh/g, and conservation rate has good big multiplying power discharging property 102%.
Embodiment 5
With 840g lithium hydroxide (LiOHH
2O), 3600g ferrous oxalate (FeC
2O
42H
2O) and 2640g diammonium hydrogen phosphate ((NH
4)
2HPO
4) add in the deionized water of 17.81kg, add the 200mL absolute ethyl alcohol then as dispersant, in above-mentioned compound, slowly add the 40g carbon nano-tube at last, 5g nano-calcium carbonate magnesium dust, wet ball grinding 36 hours, levigate to 80nm; The 40wt% of quality that the quality that drops into raw material accounts for ionized water uses centrifugal spray granulating and drying machine then, 350 ℃ of inlet temperatures, under 100 ℃ of conditions of outlet temperature, utilizes instaneous polymerization, drying to make spherical presoma; With spherical presoma in tube furnace, charge into nitrogen, in 350 ℃ of following preliminary treatment 5 hours, the heating rate of 4 ℃/min was warmed up to 650 ℃ and constant temperature 12 hours then, naturally cooled to room temperature; Above-mentioned material is added disintegrating apparatus, efflorescence is 30 minutes under the 5000rpm condition, and then join in the impact type nodularization pulverizer, the nodularization shaping was handled 100 minutes under the 2000rpm condition, under the rotating speed of 600rpm, carried out mechanical fusion treatment 2 hours, and obtained the sphere or the line of apsides than the LiFePO4 electrode material that is 1.9 class spherical forms.The average grain diameter that records this material is 20 μ m, and specific area is 12m
2/ g, tap density 1.5g/cm
3Prepare electrode according to the method identical with example 1, carry out electrochemical property test, charge and discharge multiplying power when being 0.1C, the capacity of battery reaches 148mAh/g.Circulate after 50 weeks, it is fine that capacity keeps, and do not see decay.
Embodiment 6
With 840g lithium hydroxide (LiOHH
2O), 1600g di-iron trioxide (Fe
2O
3) and 2300g ammonium dihydrogen phosphate (NH
4H
2PO
4) add in the deionized water of 10.3kg, add the 200mL absolute ethyl alcohol then as dispersant, add the 400g conductive carbon black at last, the 10g magnesium oxide powder, wet ball grinding 48 hours, levigate to 5nm; The 50wt% of quality that the quality that drops into raw material accounts for ionized water uses centrifugal spray granulating and drying machine then, 400 ℃ of inlet temperatures, under 120 ℃ of conditions of outlet temperature, utilizes instaneous polymerization, drying to make spherical presoma; With above-mentioned presoma in tube furnace, charge into nitrogen, in 300 ℃ of following preliminary treatment 6 hours, be warmed up to 650 ℃ and constant temperature 12 hours with the heating rate of 4 ℃/min then, naturally cool to room temperature; Above-mentioned material is joined in the disintegrating apparatus, efflorescence is 10 minutes under the 6000rpm condition, and then join in the impact type nodularization pulverizer, the nodularization shaping was handled 40 minutes under the 3000rpm condition, under the rotating speed of 200rpm, carried out mechanical fusion treatment 4 hours, and obtained the sphere or the line of apsides than the LiFePO4 electrode material that is 2.1 class spherical forms.The average grain diameter that records this material is 5 μ m, and specific area is 14m
2/ g, tap density 1.5g/cm
3Prepare electrode according to the method identical with example 1, carry out electrochemical property test, charge and discharge multiplying power when being 0.1C, the capacity of battery reaches 146mAh/g, and after 50 weeks of circulating, it is fine that capacity keeps, and do not see decay.
Embodiment 7
With 2080g lithium dihydrogen phosphate (LiH
2PO
4), 1600g di-iron trioxide (Fe
2O
3) and the 23.2g magnesium hydroxide add in the deionized water of 11.81kg, add the 100mL absolute ethyl alcohol then as dispersant, in above-mentioned compound, add 1000g starch at last, 20g nanometer dolomol powder, wet ball grinding 35 hours, levigate to 100nm; The 40wt% of quality that the quality that drops into raw material accounts for ionized water uses centrifugal spray granulating and drying machine then, 150 ℃ of inlet temperatures, under 100 ℃ of conditions of outlet temperature, utilizes instaneous polymerization, drying to make spherical presoma; With above-mentioned presoma in tube furnace, charge into nitrogen, in 350 ℃ of following preliminary treatment 12 hours, the heating rate of 3 ℃/min was warmed up to 500 ℃ and constant temperature 48 hours then, naturally cooled to room temperature; Above-mentioned material is added disintegrating apparatus, efflorescence is 30 minutes under the 5000rpm condition, and then join in the impact type nodularization pulverizer, the nodularization shaping was handled 80 minutes under the 2000rpm condition, under the rotating speed of 1000rpm, carried out mechanical fusion treatment 2 hours, and obtained the sphere or the line of apsides than the LiFePO4 electrode material that is 2.3 class spherical forms.The average grain diameter of this material is 8 μ m, and specific area is 11m
2/ g, tap density 1.3g/cm
3Prepare electrode according to the method identical with example 1, carry out electrochemical property test, charge and discharge multiplying power when being 0.1C, the capacity of battery reaches 147mAh/g.Circulate after 50 weeks, it is fine that capacity keeps, and do not see decay.
Embodiment 8
With 2080g lithium dihydrogen phosphate (LiH
2PO
4), 3600g ferrous oxalate (FeC
2O
42H
2O) and 53.2g niobium pentaoxide (Nb
2O
5) add in the deionized water of 22.61kg, add the 100mL absolute ethyl alcohol then as dispersant, in above-mentioned compound, slowly add 1000g glucose at last, 50g nanometer magnesium dihydrogen phosphate, wet ball grinding 4 hours, levigate to 300nm; The 30wt% of quality that the quality that drops into raw material accounts for ionized water uses centrifugal spray granulating and drying machine then, 350 ℃ of inlet temperatures, under 100 ℃ of conditions of outlet temperature, utilizes instaneous polymerization, drying to make spherical presoma; With above-mentioned presoma in tube furnace, charge into argon gas, in 300 ℃ of following preliminary treatment 2 hours, the heating rate of 5 ℃/min was warmed up to 800 ℃ and constant temperature 4 hours then, naturally cooled to room temperature; Above-mentioned material is added disintegrating apparatus, efflorescence is 80 minutes under the 4000rpm condition, and then join in the impact type nodularization pulverizer, the nodularization shaping was handled 60 minutes under the 1000rpm condition, under the rotating speed of 600rpm, carried out mechanical fusion treatment 3 hours, and obtained the sphere or the line of apsides than the LiFePO4 electrode material that is 2.4 class spherical forms.The average grain diameter of this material is 8 μ m, and specific area is 13m
2/ g, tap density 1.35g/cm
3Prepare electrode according to the method identical with example 1, carry out electrochemical property test, charge and discharge multiplying power when being 0.1C, the capacity of battery reaches 150mAh/g.Circulate after 50 weeks, it is fine that capacity keeps, and do not see decay.
In the above-described embodiments, lithium carbonate, lithium hydroxide and lithium dihydrogen phosphate have been enumerated, the lithium fluoride of not enumerating among the embodiment, lithium acetate and lithium nitrate.Because lithium fluoride, lithium acetate and lithium nitrate 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 acetate 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, lithium dihydrogen phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate have been enumerated, the triammonium phosphate of not enumerating among the embodiment, phosphoric acid and phosphorus pentoxide.Because triammonium phosphate, phosphoric acid and phosphorus pentoxide, contain phosphate radical or contain the acid anhydrides of phosphoric acid, so it all can provide phosphate radical in reaction, form LiFePO4 with lithium source, Fe source compound, so it is equally applicable to this patent.
In the above-described embodiments, glucose, conductive carbon black and starch have been enumerated, the native graphite micro mist of not enumerating among the embodiment, Delanium micro mist, polyvinyl alcohol, butadiene-styrene rubber breast, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, phenolic resins, epoxy resin, sucrose, fructose, cellulose and pitch.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.
In the above-described embodiments, nano-metallic copper, nano metal aluminium, magnesium oxide, magnesium hydroxide, magnesium carbonate, dolomol, magnesium dihydrogen phosphate and niobium pentaoxide have been enumerated, the nanometer metallic silver of not enumerating among the embodiment, chromium oxide, manganese oxide, cobalt oxide and aluminium oxide.These metals, metal oxide all can enter into the lattice of LiFePO4 in the process of carbon reduction, form defective, increase the electric conductivity of LiFePO4, thus improve material capacity, improve the cycle life of material.
Iron phosphate lithium electrode material of the present invention has, be applicable to lithium ion power battery cathode material, have the good characteristics of specific capacity height, multiplying power discharging and security performance, the materials processing function admirable, the compacted density height of pole piece, adhesive property is good, and preparation method of the present invention is easy to suitability for industrialized production simultaneously.
Claims (8)
1. method preparing phosphate iron lithium that is applicable to that high multiplying power electrokinetic cell is used, comprise the steps: one, be 1: 1: 1 ratio with lithium salts, molysite, phosphate in the mol ratio of lithium, iron, phosphorus, add that to account for lithium salts, molysite and phosphatic ratio be the dispersant of 1wt.%～2.5wt.% and to account for lithium salts, molysite and phosphatic ratio be 1wt.%～2.5wt.% material with carbon element predecessor, nano metal or/and the nano-metal-oxide conductive agent, wet ball grinding 4～48 hours is to slurry; Two, slurry is 150～400 ℃ of inlet temperatures, and outlet temperature is that spherical presoma is made in spraying under 60～135 ℃ the condition; Three, with the preliminary treatment 2～12 hours in 300～400 ℃ of temperature ranges in inert atmosphere of spherical presoma, 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; Four, with above-mentioned material efflorescence 10～80 minutes under 3000～6000rpm condition, the nodularization shaping was handled 40～180 minutes under 600～3000rpm condition then, obtained sphere or class spherical particle that matrix is coated with conductive layer; Five, particulate is carried out mechanical fusion treatment under the rotating speed of 200～1100rpm and be composite particles in 0.5～4 hour, obtain the sphere or the line of apsides than the LiFePO4 electrode material that is 1.2～2.5 class spherical forms.
2. the method preparing phosphate iron lithium that is applicable to that high multiplying power electrokinetic cell is used according to claim 1 is characterized in that: described lithium salts is lithium carbonate, lithium fluoride, lithium acetate, lithium nitrate or lithium dihydrogen phosphate; Described phosphate is ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate or lithium dihydrogen phosphate; Described molysite is ferrous oxalate, ferrous acetate, ferric nitrate or iron chloride.
3. the method preparing phosphate iron lithium that is applicable to that high multiplying power electrokinetic cell is used according to claim 2 is characterized in that: described material with carbon element is made up of more than one of native graphite, Delanium micro mist, conductive carbon black and organic substance pyrolytic carbon; Described nano metal or nano-metal-oxide are nanometer metallic silver, metallic copper, metallic aluminium, magnesium oxide, chromium oxide, manganese oxide, cobalt oxide, aluminium oxide or niobium pentaoxide.
4. the method preparing phosphate iron lithium that is applicable to that high multiplying power electrokinetic cell is used according to claim 3, it is characterized in that: described organic substance pyrolytic carbon is that polyvinyl alcohol, butadiene-styrene rubber breast, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, phenolic resins, epoxy resin, glucose, sucrose, fructose, cellulose, starch or pitch are presoma, through the formed pyrolytic carbon of high temperature cabonization; Described nanometer conductive material is carbon nano-tube, carbon nano-fiber or nano-sized carbon microballoon.
5. the method preparing phosphate iron lithium that is applicable to that high multiplying power electrokinetic cell is used according to claim 4 is characterized in that: described dispersant is an absolute ethyl alcohol.
6. the method preparing phosphate iron lithium that is applicable to that high multiplying power electrokinetic cell is used according to claim 5 is characterized in that: the used equipment of described wet ball grinding is that wet method stirs mill, circulating ultra-fine mill or ultra-fine sand mill, and used mill is situated between and is Al
2O
3Ball, ZrO
2Ball, agate ball or stainless steel ball, sphere diameter is at 0.1～10mm.
7. the method preparing phosphate iron lithium that is applicable to that high multiplying power electrokinetic cell is used according to claim 6 is characterized in that: the account for 5～60wt% of quality of ionized water of the quality that described wet ball grinding drops into raw material, the solid granularity is 5～300nm after the fine grinding.
8. the method preparing phosphate iron lithium that is applicable to that high multiplying power electrokinetic cell is used according to claim 7 is characterized in that: centrifugal spray granulating and drying machine is adopted in described spraying; Preliminary treatment and constant temperature are handled and are adopted push-plate type tunnel cave, tube furnace, bell jar stove, rotary furnace, steel band stove, vacuum furnace, sealed type or cyclone furnace kiln; Airslide disintegrating mill, mechanical type pulverizer or compound pulverizer are adopted in described efflorescence; Impact type nodularization pulverizer is adopted in the nodularization shaping; Described inert gas is argon gas, nitrogen, helium or neon.
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