CN101081696B - 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
- Publication number
- CN101081696B CN101081696B CN2007100744558A CN200710074455A CN101081696B CN 101081696 B CN101081696 B CN 101081696B CN 2007100744558 A CN2007100744558 A CN 2007100744558A CN 200710074455 A CN200710074455 A CN 200710074455A CN 101081696 B CN101081696 B CN 101081696B
- Authority
- CN
- China
- Prior art keywords
- lithium
- phosphate
- under
- ball
- presoma
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 86
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 title claims description 26
- 239000000843 powder Substances 0.000 title claims description 17
- 239000005955 Ferric phosphate Substances 0.000 title claims description 16
- 229940032958 ferric phosphate Drugs 0.000 title claims description 16
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims description 16
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 28
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000011246 composite particle Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 6
- 238000007493 shaping process Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000002131 composite material Substances 0.000 claims description 27
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 19
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 229910019142 PO4 Inorganic materials 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- 239000010452 phosphate Substances 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000007921 spray Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229940062993 ferrous oxalate Drugs 0.000 claims description 13
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical group [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 12
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 12
- 238000009413 insulation Methods 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
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 11
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- 239000002296 pyrolytic carbon Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 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
- 239000003595 mist Substances 0.000 claims description 9
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 8
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 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
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-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
- 239000011238 particulate composite Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 235000014413 iron hydroxide Nutrition 0.000 claims description 5
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-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
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 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 compound [Ar] XKRFYHLGVUSROY-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
- 238000006253 efflorescence Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 206010037844 rash Diseases 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 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
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 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
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 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
- 229920000647 polyepoxide 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
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 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
- 238000006243 chemical reaction Methods 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
- 238000012545 processing Methods 0.000 claims description 2
- 239000004576 sand 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 4
- 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
- 238000002203 pretreatment Methods 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
- 238000012360 testing method Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 7
- 239000000347 magnesium hydroxide Substances 0.000 description 7
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 7
- 239000010955 niobium Substances 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 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
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 4
- 239000001095 magnesium carbonate Substances 0.000 description 4
- 229910000021 magnesium carbonate 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
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 description 4
- 235000019785 monomagnesium phosphate Nutrition 0.000 description 4
- 229910010710 LiFePO Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 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
- 238000011160 research Methods 0.000 description 2
- 238000004626 scanning electron microscopy 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
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material 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
- 239000003575 carbonaceous 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
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 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
- 239000003792 electrolyte Substances 0.000 description 1
- 239000002001 electrolyte material 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
- 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
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052758 niobium 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
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction 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
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 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-energy 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 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 the theoretical capacity height, and about 170mAh/g is nontoxic, and the raw material range of choice is wide, stable operating voltage, and Stability Analysis of Structures, fail safe is splendid, Heat stability is good, plurality of advantages such as high temperature and good cycle.
The synthetic of the LiFePO4 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 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 particle size distribution of product 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, 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 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 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 security 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 the LiFePO4 matrix through doping vario-property, 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 salts, molysite and phosphate are arranged in the reaction raw materials of LiFePO4 of the present invention, 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.
Doping vario-property agent of the present invention is magnesium oxide, magnesium hydroxide, magnesium carbonate, dolomol, magnesium dihydrogen phosphate or niobium pentaoxide, 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 native graphite, Delanium micro mist, organic substance 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 nano-tube, carbon nano-fiber or nano-sized carbon microballoon; 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.
The average grain diameter of composite particles of the present invention is 5～6 μ m, and specific 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, phosphate, account for the LiFePO 4 material mass ratio and be 1%～25% doping vario-property agent and dispersant, 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 preliminary treatment 2～12h, be warmed up to 500～800 ℃ and constant temperature 4～48h again, naturally cool to room temperature then; (4) above-mentioned material 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 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; Described doping vario-property agent is magnesium oxide, magnesium hydroxide, magnesium carbonate, dolomol, magnesium dihydrogen phosphate or niobium pentaoxide; Described composite carbon coating layer is one or more compositions in native graphite, Delanium micro mist, organic substance pyrolytic carbon and the nanometer conductive material; Described dispersant 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 inlet temperature is 250-280 ℃, and outlet temperature is 90 ℃.
The equipment of wet ball grinding is that micronizer, 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 preliminary treatment of the inventive method, intensification and constant temperature carry out in inert atmosphere, and its Equipment for Heating Processing is sealed type or cyclone furnace kiln; Described disintegrating apparatus is micronizer, airslide disintegrating mill, mechanical type pulverizer or compound pulverizer.
The stove that the inventive method adopts is push-plate type tunnel cave, tube furnace, bell jar stove or converter.
The inert gas 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 by presoma, advantages of good crystallization, and structure is single, does not contain dephasign, and the average grain diameter of composite particles is 5～60 μ m, and specific 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 capacity height, multiplying power discharging and security 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 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 electron microscopy 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 lithium carbonate (Li
2CO
3), 3600g ferrous oxalate (FeC
2O
42H
2O) and 2300g ammonium dihydrogen 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 outlet temperature, obtain spherical presoma 250 ℃ of inlet temperatures; 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 material is added micronizer, efflorescence 45min under 6000rpm, and then join in the impact type nodularization pulverizer, spheroidising 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 of the olivine-type structure of pure phase, there is not impurity peaks in the spectrogram, the product purity height.The average grain diameter that adopts Malvern MS2000 laser particle analyzer to record this material is 22 μ m, and specific 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 material): m (acetylene black): m (polytetrafluoroethylene) 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 vacuumizes 8 hours; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard 2400); Electrolyte is 1mol/l LiPF
6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) volume ratio 1: 1 is assembled into Experimental cell in 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 discharge capacity first reaches 123mAh/g, remain on 116mAh/g through 60 circulation volumes, conservation rate is 94%.
Adopt lithium carbonate (Li
2CO
3), ferrous oxalate (FeC
2O
42H
2O) and ammonium dihydrogen phosphate (NH
4H
2PO
4) the synthetic pure phase LiFePO4 of conventional 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 discharge 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 area is 20m
2More than/the g, prepare the specific area 8～15m of material much larger than the present invention
2/ g.
Embodiment 2
With 840g lithium hydroxide (LiOHH
2O), 1600g di-iron trioxide (Fe
2O
3) and 2300g ammonium dihydrogen 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 MalvernMS2000 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 outlet temperature, obtain spherical presoma 280 ℃ of inlet temperatures; 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 material is added micronizer, pulverize 10min under 6000rpm, and then join in the impact type nodularization pulverizer, spheroidising 40min under the 3000rpm condition obtains spherical composite lithium iron phosphate material.The average grain diameter that records this material is 11 μ m, and specific 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 discharge capacity first reaches 120mAh/g, remains on 114mAh/g through 60 circulation volumes, and conservation rate is 95%.
With 740g lithium carbonate (Li
2CO
3), 1600g di-iron trioxide (Fe
2O
3), 2300g ammonium dihydrogen 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 Malvern 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 outlet temperature, obtain spherical presoma 250 ℃ of inlet temperatures; 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 material is added micronizer, pulverize 80min under 5000rpm, and then join in the impact type nodularization pulverizer, spheroidising 180min under the 600rpm condition obtains spherical composite lithium iron phosphate material.The average grain diameter that records this material is 5 μ m, and specific 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 discharge capacity first reaches 118mAh/g, remains on 112mAh/g through 60 circulation volumes, and conservation rate is 95%.
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), 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 250nm.Add 990g glucose afterwards, continue ball milling 48h, use centrifugal spray granulating and drying machine then,, under 90 ℃ of conditions of outlet temperature, obtain spherical presoma 260 ℃ of inlet temperatures; 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 material is added micronizer, comminution of material 60min under 4000rpm, and then join in the impact type nodularization pulverizer, spheroidising 120min under the 1500rpm condition obtains spherical composite lithium iron phosphate material.The average grain diameter that records this material is 60 μ m, and specific 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 discharge capacity first reaches 119mAh/g, remains on 112mAh/g through 60 circulation volumes, and conservation rate is 94%.
Embodiment 5
With 840g lithium hydroxide (LiOHH
2O), 3600g ferrous oxalate (FeC
2O
42H
2O) and 2640g diammonium hydrogen phosphate ((NH
4)
2HPO
4), with 80g niobium pentaoxide (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 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 outlet temperature, obtain spherical presoma 250 ℃ of inlet temperatures; 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 material is added micronizer, pulverize 30min under 6000rpm, and then join in the impact type nodularization pulverizer, spheroidising 90min under the 3000rpm condition obtains spherical composite lithium iron phosphate material.The average grain diameter that records this material is 10 μ m, and specific 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 discharge capacity first reaches 121mAh/g, remains on 117mAh/g through 60 circulation volumes, and conservation rate is 97%.
Embodiment 6
With 2080g lithium dihydrogen phosphate (LiH
2PO
4), 3600g ferrous oxalate (FeC
2O
42H
2O) (lithium dihydrogen phosphate serves as phosphate simultaneously) is with 80g niobium pentaoxide (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 outlet temperature, obtain spherical presoma 250 ℃ of inlet temperatures; 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 material is added micronizer, pulverize 30min under 6000rpm, and then join in the impact type nodularization pulverizer, spheroidising 60min under the 3000rpm condition obtains spherical composite lithium iron phosphate material.The average grain diameter that records this material is 10 μ m, and specific 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 discharge capacity first reaches 121mAh/g, remains on 117mAh/g through 60 circulation volumes, and conservation rate is 97%.
Embodiment 7
With 2080g lithium dihydrogen phosphate (LiH
2PO
4), 1600g di-iron trioxide (Fe
2O
3) (lithium dihydrogen phosphate serves as phosphate simultaneously) and 80g niobium pentaoxide (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 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 outlet temperature, obtain spherical presoma 250 ℃ of inlet temperatures; 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 material is added micronizer, pulverize 50min under 6000rpm, and then join in the impact type nodularization pulverizer, spheroidising 100min under the 3000rpm condition obtains spherical composite lithium iron phosphate material.The average grain diameter that records this material is 10 μ m, and specific 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 discharge capacity first reaches 115mAh/g, remains on 108mAh/g through 60 circulation volumes, and conservation rate is 93%.
Embodiment 8
With 2080g lithium dihydrogen phosphate (LiH
2PO
4), 2140g iron hydroxide (Fe (HO)
3), (lithium dihydrogen phosphate serves as phosphate simultaneously) and 80g niobium pentaoxide (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 outlet temperature, obtain spherical presoma 250 ℃ of inlet temperatures; 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 material is added micronizer, pulverize 50min under 6000rpm, and then join in the impact type nodularization pulverizer, spheroidising 100min under the 3000rpm condition obtains spherical composite lithium iron phosphate material.The average grain diameter that records this material is 12 μ m, and specific 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 discharge capacity first reaches 118mAh/g, remains on 108mAh/g through 60 circulation volumes, and conservation rate is 92%.
LiFePO
4Belong to olivine-type structure, space group 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 conductivity is lower than other lamellar compound.
The hot method composition principle that the present invention adopts LiFePO4 is at high temperature raw material lithium salts, ferrous salt, phosphate generation redox reaction, generating micro-molecular gas overflows and LiFePO4, according to this composition principle, available lithium salts is lithium carbonate, lithium fluoride, lithium acetate, lithium hydroxide, lithium nitrate or lithium dihydrogen phosphate; Available molysite is ferrous oxalate, ferrous acetate, di-iron trioxide, ferric nitrate or iron hydroxide; Phosphate can be lithium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, phosphoric acid or phosphorus pentoxide.For improving the chemical property of synthetic, the doping vario-property agent of employing is magnesium oxide, magnesium hydroxide, magnesium carbonate, dolomol, magnesium dihydrogen phosphate or niobium pentaoxide, 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 electric conductivity of material, reduce battery polarization, give full play to the capacity of positive electrode, and the synthetic atmosphere of control prevents ferrous oxidation, has adopted the carbon doping among the preparation method of the present invention, used material with carbon element can be the higher natural graphite powder of crystal structure, graphous graphite powder, nano-carbon material (raising conductivity), also can adopt various organic substance RESEARCH OF PYROCARBON, improve the synthetic atmosphere of material, anti-oxidation.Above-mentioned organic substance pyrolytic carbon can be 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 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, magnesium carbonate, dolomol, magnesium dihydrogen phosphate or niobium pentaoxide etc.
Claims (6)
1. ferric phosphate lithium material for lithium ion powder cell, it is characterized in that: described LiFePO 4 material has the LiFePO4 matrix through doping vario-property, matrix is coated with the composite carbon coating layer and forms particulate, particulate is combined into composite particulate material, composite particles is spherical in shape or class is spherical, the doping vario-property agent is a niobium pentaoxide, and the mass ratio that accounts for composite particulate material is 1%～25%;
Lithium salts, molysite and phosphate are arranged in the reaction raw materials of described LiFePO4, and the mol ratio of lithium, iron, phosphorus is 1: 1: 1;
Described lithium salts is lithium carbonate, lithium fluoride, lithium acetate, lithium nitrate or lithium dihydrogen phosphate; Described molysite is ferrous oxalate, ferrous acetate or ferric nitrate; Described phosphate is lithium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or triammonium phosphate;
Described composite carbon coating layer is more than one compositions in native graphite, Delanium micro mist, organic substance pyrolytic carbon and the nanometer conductive material, and the mass ratio that accounts for composite particulate material is 1%～25%;
Described nanometer conductive material is conductive carbon black, carbon nano-tube, carbon nano-fiber or nano-sized carbon microballoon; 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;
The average grain diameter of described composite particles is 5～60 μ m, and specific area is 8～15m
2/ g, tap density is 1.4～1.7g/cm
3
Described ferric phosphate lithium material for lithium ion powder cell prepares by the following method, may further comprise the steps: (1) is 1: 1: 1 ratio in lithium, iron, phosphorus mol ratio with lithium salts, molysite, phosphate, account for the LiFePO 4 material mass ratio and be 1%～25% doping vario-property agent and dispersant, 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 preliminary treatment 2～12h, be warmed up to 500～800 ℃ and constant temperature 4～48h again, naturally cool to room temperature then; (4) above-mentioned material 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.
2. ferric phosphate lithium material for lithium ion powder cell according to claim 1, it is characterized in that: described ferric phosphate lithium material for lithium ion powder cell is by the 840g lithium hydroxide, 3600g ferrous oxalate and 2640g diammonium hydrogen phosphate, with the 80g niobium pentaoxide, add in the 10kg deionized water, ball milling 24h in the wet method agitating ball mill, the medium that uses is the zirconia ball of diameter 1mm, add the 400g conductive carbon black afterwards, continue ball milling 24h, use centrifugal spray granulating and drying machine then, 250 ℃ of inlet temperatures, under 90 ℃ of conditions of outlet temperature, obtain spherical presoma; 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 material is added micronizer, pulverize 30min under 6000rpm, and then join in the impact type nodularization pulverizer, spheroidising 90min under the 3000rpm condition obtains spherical composite lithium iron phosphate material; The average grain diameter of the spherical composite lithium iron phosphate material of gained is 10 μ m, and specific area is 13m
2/ g, tap density 1.7g/cm
3
3. ferric phosphate lithium material for lithium ion powder cell according to claim 1, it is characterized in that: described ferric phosphate lithium material for lithium ion powder cell is by 2080g lithium dihydrogen phosphate, 3600g ferrous oxalate, with the 80g niobium pentaoxide, add in the 10kg deionized water, ball milling 24h in the wet method agitating ball mill, the medium that uses is the zirconia ball of diameter 1mm, add the 400g conductive carbon black afterwards, continue ball milling 24h, use centrifugal spray granulating and drying machine then, 250 ℃ of inlet temperatures, under 90 ℃ of conditions of outlet temperature, obtain spherical presoma; 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 material is added micronizer, pulverize 30min under 6000rpm, and then join in the impact type nodularization pulverizer, spheroidising 60min under the 3000rpm condition obtains spherical composite lithium iron phosphate material; The average grain diameter of the spherical composite lithium iron phosphate material of gained is 10 μ m, and specific area is 13m
2/ g, tap density 1.6g/cm
3
4. ferric phosphate lithium material for lithium ion powder cell according to claim 1, it is characterized in that: described ferric phosphate lithium material for lithium ion powder cell is by 2080g lithium dihydrogen phosphate, 1600g di-iron trioxide, with the 80g niobium pentaoxide, add in the 10kg deionized water, ball milling 24h in the wet method agitating ball mill, the medium that uses is the zirconia ball of diameter 1mm, add the 400g conductive carbon black afterwards, continue ball milling 24h, use centrifugal spray granulating and drying machine then, 250 ℃ of inlet temperatures, under 90 ℃ of conditions of outlet temperature, obtain spherical presoma; 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 material is added micronizer, pulverize 50min under 6000rpm, and then join in the impact type nodularization pulverizer, spheroidising 100min under the 3000rpm condition obtains spherical composite lithium iron phosphate material; The average grain diameter of the spherical composite lithium iron phosphate material of gained is 10 μ m, and specific area is 13m
2/ g, tap density 1.6g/cm
3
5. ferric phosphate lithium material for lithium ion powder cell according to claim 1, it is characterized in that: described ferric phosphate lithium material for lithium ion powder cell by 2080g lithium dihydrogen phosphate, 2140g iron hydroxide, with the 80g niobium pentaoxide, add in the 10kg deionized water, ball milling 24h in the wet method agitating ball mill, the medium that uses is the zirconia ball of diameter 1mm, add the 400g conductive carbon black afterwards, continue ball milling 24h, use centrifugal spray granulating and drying machine then, 250 ℃ of inlet temperatures, under 90 ℃ of conditions of outlet temperature, obtain spherical presoma; 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 material is added micronizer, pulverize 50min under 6000rpm, and then join in the impact type nodularization pulverizer, spheroidising 100min under the 3000rpm condition obtains spherical composite lithium iron phosphate material; The average grain diameter of the spherical composite lithium iron phosphate material of gained is 12 μ m, and specific area is 15m
2/ g, tap density 1.6g/cm
3
6. 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, phosphate, account for the LiFePO 4 material mass ratio and be 1%～25% doping vario-property agent niobium pentaoxide and dispersant, 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 preliminary treatment 2～12h, be warmed up to 500～800 ℃ and constant temperature 4～48h again, naturally cool to room temperature then; (4) above-mentioned material 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;
Described lithium salts is lithium carbonate, lithium fluoride, lithium acetate, lithium nitrate or lithium dihydrogen phosphate; Described molysite is ferrous oxalate, ferrous acetate or ferric nitrate; Described phosphate is lithium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or triammonium phosphate; Described composite carbon coating layer is more than one compositions in native graphite, Delanium micro mist, organic substance pyrolytic carbon and the nanometer conductive material; Described dispersant is a deionized water;
Behind described wet ball grinding 4～48h, the compound particle diameter is 5～300nm;
Described mist projection granulating adopts centrifugal spray granulating and drying machine, and its inlet temperature is 250-280 ℃, and outlet temperature is 90 ℃;
The equipment of described wet ball grinding is that micronizer, 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;
Described preliminary treatment, intensification and constant temperature carry out in inert atmosphere, and its Equipment for Heating Processing is sealed type or cyclone furnace kiln; Described disintegrating apparatus is micronizer, airslide disintegrating mill, mechanical type pulverizer or compound pulverizer;
Described stove is push-plate type tunnel cave, tube furnace, bell jar stove or converter;
Described inert gas is argon gas, nitrogen, hydrogen or ammonia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100744558A CN101081696B (en) | 2007-05-15 | 2007-05-15 | Ferric phosphate lithium material for lithium ion powder cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100744558A CN101081696B (en) | 2007-05-15 | 2007-05-15 | Ferric phosphate lithium material for lithium ion powder cell and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101081696A CN101081696A (en) | 2007-12-05 |
| CN101081696B true CN101081696B (en) | 2010-08-25 |
Family
ID=38911527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100744558A Active CN101081696B (en) | 2007-05-15 | 2007-05-15 | Ferric phosphate lithium material for lithium ion powder cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101081696B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3476801A4 (en) * | 2017-08-02 | 2019-10-23 | Energy & Gongjo Co., Ltd. | Method for manufacturing cathode active material powder of secondary battery |
Families Citing this family (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101188293B (en) * | 2007-12-11 | 2010-10-20 | 深圳市贝特瑞新能源材料股份有限公司 | Fe base lithium sale compound anode materials and its making method |
| CN101483261B (en) * | 2008-01-11 | 2013-01-02 | 深圳市沃特玛电池有限公司 | High power lithium iron phosphate cell and manufacturing method thereof |
| EP2276698A1 (en) * | 2008-04-14 | 2011-01-26 | Dow Global Technologies Inc. | Lithium metal phosphate/carbon nanocomposites as cathode active materials for secondary lithium batteries |
| CA2732854C (en) * | 2008-08-05 | 2016-10-25 | Dow Global Technologies Inc. | Lithium metal phosphate/carbon nanocomposites as cathode active materials for rechargeable lithium batteries |
| CN101916851B (en) * | 2010-08-12 | 2013-10-23 | 深圳大学 | Preparation method and application of lithium iron phosphate-carbon fiber composite cathode material |
| CN102610796A (en) * | 2011-01-25 | 2012-07-25 | 庄育丰 | Preparation method of cathode materials for lithium ion battery |
| CN102593447B (en) * | 2011-03-23 | 2016-03-16 | 江苏菲思特新能源有限公司 | A kind of metal-doped method of lithium iron phosphate positive material |
| CN102664265A (en) * | 2011-05-25 | 2012-09-12 | 淄博赛动能源材料有限公司 | Process for preparing lithium iron phosphate by using liquid phase cocrystallization and mechanical alloying |
| US9065136B2 (en) * | 2011-09-14 | 2015-06-23 | Samsung Sdi Co., Ltd. | Positive electrode for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
| CN102522541A (en) * | 2011-12-02 | 2012-06-27 | 苏州冠硕新能源有限公司 | Anode material and preparation method thereof |
| CN102376955A (en) * | 2011-12-02 | 2012-03-14 | 浙江瑞邦科技有限公司 | Method for simply synthesizing lithium yttrium iron phosphate positive electrode material |
| CN102623701B (en) * | 2012-01-13 | 2014-08-06 | 厦门钨业股份有限公司 | Preparation method for low-temperature nanometer lithium iron phosphate cathode material |
| CN103296276A (en) * | 2012-02-28 | 2013-09-11 | 珠海银通新能源有限公司 | Carbon coating precursor of lithium ion battery anode material and preparation method thereof |
| CN102610819A (en) * | 2012-04-05 | 2012-07-25 | 宁波力邦新能源科技有限公司 | Preparing method of high-activity material |
| CN103426498B (en) * | 2012-05-17 | 2016-04-27 | 复旦大学 | A kind of carbon nanotube conducting slurry and preparation method thereof |
| CN102867953B (en) * | 2012-07-24 | 2015-01-21 | 龙能科技（苏州）有限公司 | Method for producing lithium ion battery cathode material by using hydroxide or hydroxyl oxide |
| KR101973052B1 (en) | 2012-08-10 | 2019-04-26 | 삼성에스디아이 주식회사 | Method for Preparation of Lithium Metal Phosphate |
| CN102916179B (en) * | 2012-09-29 | 2015-02-11 | 杭州金马能源科技有限公司 | Method for manufacturing industrialized high-energy lithium iron phosphate material |
| CN103066280B (en) * | 2012-12-28 | 2016-04-20 | 珠海泰坦能源电子技术有限公司 | spherical lithium iron phosphate anode material and preparation method thereof |
| CN103151525B (en) * | 2013-03-21 | 2015-04-22 | 浙江美思锂电科技有限公司 | Full-automatic production process of lithium iron phosphate and devices thereof |
| CN104425814B (en) * | 2013-09-09 | 2017-03-29 | 北京国能电池科技有限公司 | The preparation method of LiMn2O4, lithium manganate material, anode material for lithium-ion batteries |
| CN104617293B (en) * | 2013-11-04 | 2018-04-27 | 国联汽车动力电池研究院有限责任公司 | A kind of preparation method of the carbon coated lithium ferrous phosphate composite material of fluorine richness |
| CN103682363A (en) * | 2013-12-30 | 2014-03-26 | 云南磷化集团有限公司 | Method for using novel material mixing dispersing agents for preparing lithium iron phosphate battery materials |
| CN103887509B (en) * | 2014-03-24 | 2016-07-06 | 佛山市德方纳米科技有限公司 | Iron phosphate lithium-based composite conductor positive electrode and preparation method, positive pole and lithium battery |
| CN104157870A (en) * | 2014-08-13 | 2014-11-19 | 青岛乾运高科新材料股份有限公司 | Two-step high-energy ball milling method for preparation of lithium manganate solid solution anode material rich in lithium |
| CN106103337A (en) * | 2014-12-26 | 2016-11-09 | 恒耀能源股份有限公司 | The manufacture method of nano-powder, the electrode comprising this nano-powder and comprise the battery of this electrode |
| CN108390061B (en) * | 2016-03-18 | 2021-07-02 | 日照华轩新能源有限公司 | Hydrothermal preparation method of lithium iron phosphate |
| CN108063250A (en) * | 2016-08-15 | 2018-05-22 | 海宁永欣科技咨询有限公司 | The production technology of the nanometer lithium iron phosphate cathode material of improvement |
| CN106099071A (en) * | 2016-08-18 | 2016-11-09 | 周新凤 | A kind of MPS solar energy lithium electricity positive electrode and preparation method thereof |
| CN106328906A (en) * | 2016-11-03 | 2017-01-11 | 深圳市沃特玛电池有限公司 | Nano spherical lithium iron phosphate positive electrode material and preparation method thereof, lithium iron phosphate positive electrode sheet and lithium iron phosphate battery |
| CN106410164B (en) * | 2016-11-24 | 2019-02-12 | 盐城工学院 | A kind of anode material and its preparation method and application |
| CN106948032B (en) * | 2017-05-02 | 2019-05-14 | 中南大学 | Cellulose base Carbon fibe, preparation method and its method for being used to prepare electrode material |
| CN108134061A (en) * | 2017-12-21 | 2018-06-08 | 洛阳名力科技开发有限公司 | A kind of preparation method of carbon-coated iron phosphate lithium positive pole composite material |
| CN108550826A (en) * | 2018-05-03 | 2018-09-18 | 沈阳国科金能新材料有限公司 | A kind of preparation method and application of high-carbon content low specific surface area LiFePO4 |
| CN109037659A (en) * | 2018-09-04 | 2018-12-18 | 贝特瑞（天津）纳米材料制造有限公司 | A kind of preparation method of bilayer carbon-coated LiFePO 4 for lithium ion batteries material |
| CN109360935A (en) * | 2018-09-28 | 2019-02-19 | 桑顿新能源科技有限公司 | A kind of lithium ion battery cellular hard carbon coated LiFePO 4 for lithium ion batteries positive electrode, preparation method, porous electrode and lithium battery |
| CN110970618A (en) * | 2019-12-20 | 2020-04-07 | 贝特瑞（天津）纳米材料制造有限公司 | Preparation method of low-cost lithium iron phosphate composite material |
| CN111533103A (en) * | 2020-05-08 | 2020-08-14 | 蒋达金 | High-compaction ferric phosphate and preparation method of high-compaction lithium ferric phosphate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1797823A (en) * | 2004-12-21 | 2006-07-05 | 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 |
-
2007
- 2007-05-15 CN CN2007100744558A patent/CN101081696B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1797823A (en) * | 2004-12-21 | 2006-07-05 | 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 |
Non-Patent Citations (2)
| Title |
|---|
| 张培新等.镁离子掺杂对磷酸铁锂结构和性能的影响.功能材料37 12.2006,37(12),1942-1945. |
| 张培新等.镁离子掺杂对磷酸铁锂结构和性能的影响.功能材料37 12.2006,37(12),1942-1945. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3476801A4 (en) * | 2017-08-02 | 2019-10-23 | Energy & Gongjo Co., Ltd. | Method for manufacturing cathode active material powder of secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101081696A (en) | 2007-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101081696B (en) | Ferric phosphate lithium material for lithium ion powder cell and preparation method thereof | |
| CN101162776B (en) | Lithium iron phosphate suitable for high multiplying power electrokinetic cell and method for producing the same | |
| CN100461507C (en) | Making method for nano LiFePO4-carbon composite cathode material | |
| CN101955175B (en) | Industrial preparation method for lithium iron phosphate | |
| CN107275606B (en) | Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof | |
| CN101800311B (en) | Method for preparing lithium iron phosphate with high rate discharge by using ultrasonic coprecipitation | |
| WO2018120147A1 (en) | Method for preparing graphene/ternary material composite for use in lithium ion batteries and product thereof | |
| CN101591012B (en) | Preparation method of lithium iron phosphate as cathode material of lithium ion battery | |
| CN103515594A (en) | Carbon coated lithium manganese phosphate/lithium iron phosphate core-shell structure material as well as preparation method thereof | |
| CN102427131A (en) | Preparation method for metal magnesium-doped lithium manganese phosphate/carbon cathode material of lithium ion battery | |
| CN102745663B (en) | Method for preparing lithium iron phosphate material | |
| CN101752555A (en) | Method for preparing lithium ion battery anode material LiFePO4 | |
| CN102623705B (en) | Lithium ion battery cathode material LiFePO4/C, and preparation method and application thereof | |
| CN102427134A (en) | Mixed conductor composite material LiFePO4-MXy and preparation method thereof | |
| CN104993121A (en) | Nickel and manganese blended lithium ion battery positive material and preparation method thereof | |
| CN102856553A (en) | Preparation method of hydrothermal synthesis carbon coated lithium iron phosphate | |
| CN105047921A (en) | Lithium ion battery cathode material composite lithium iron phosphate and preparation method thereof and lithium ion battery | |
| CN103996852A (en) | Preparation method of novel nano lithium vanadium phosphate positive electrode material | |
| CN102386411A (en) | High-capacity lithium ion battery anode material LiFePO4/C and preparation method thereof | |
| CN103413918B (en) | A kind of synthetic method of anode material for lithium ion battery cobalt phosphate lithium | |
| CN101789505B (en) | Lithium ion battery cathode material antimony-doped lithium iron phosphate and preparation method thereof | |
| CN103413944A (en) | Lithium manganese phosphate positive electrode material and preparation method thereof | |
| CN102208624A (en) | Method for preparing carbon-coated LiFePO4 anode material by using low-temperature solid-phase method | |
| CN104681814B (en) | A kind of anode material for lithium-ion batteries LiFePO with porous star pattern4And preparation method thereof | |
| CN100490221C (en) | Composite doped modified lithium-ion battery anode material and its manufacture method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth, Patentee after: Shenzhen BTR New Energy Material Co., Ltd. Address before: 518106 Gongming office, Guangming District, Guangdong, Shenzhen Province, eighth village industrial town, Liantang Village Patentee before: Shenzhen BTR New Energy Material Co., Ltd. |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20151105 Address after: 518106, Shenzhen New District, Guangdong, Gongming Province Office of the new high-tech Industrial Park West Tian community fifth Patentee after: Shenzhen Battery Nanotechnology Co., Ltd. Address before: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth, Patentee before: Shenzhen BTR New Energy Material Co., Ltd. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20210209 Address after: 301800 9 Xingbao Road, Jiuyuan Industrial Park, Baodi District, Tianjin Patentee after: BEITERUI (TIANJIN) NANO MATERIAL MANUFACTURING Co.,Ltd. Address before: 518106 Guangdong Shenzhen Guangming New District Gongming office, saitan community high tech Industrial Park fifth Patentee before: SHENZHEN CITY BATTERY NANOMETER TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right |