CN101630731B - Nanoscale lithium iron phosphate used as cathode material of lithium ion battery and preparation method thereof - Google Patents
Nanoscale lithium iron phosphate used as cathode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN101630731B CN101630731B CN2009101091030A CN200910109103A CN101630731B CN 101630731 B CN101630731 B CN 101630731B CN 2009101091030 A CN2009101091030 A CN 2009101091030A CN 200910109103 A CN200910109103 A CN 200910109103A CN 101630731 B CN101630731 B CN 101630731B
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- Prior art keywords
- iron phosphate
- compound
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- lithium iron
- lithium
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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 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 13
- 239000010406 cathode material Substances 0.000 title abstract 3
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- -1 lithium iron phosphate compound Chemical class 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 9
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 9
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 238000000498 ball milling Methods 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 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 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 5
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005955 Ferric phosphate Substances 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 229940032958 ferric phosphate Drugs 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- 239000004277 Ferrous carbonate Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 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 3
- 239000004372 Polyvinyl alcohol Substances 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
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- 239000002079 double walled nanotube Substances 0.000 claims description 3
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 3
- 229960004652 ferrous carbonate Drugs 0.000 claims description 3
- 235000019268 ferrous carbonate Nutrition 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 235000014413 iron hydroxide Nutrition 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000015 iron(II) carbonate Inorganic materials 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000002109 single walled nanotube Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229940065285 cadmium compound Drugs 0.000 claims description 2
- 150000001662 cadmium compounds Chemical class 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- 229940116007 ferrous phosphate Drugs 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- ATEAWHILRRXHPW-UHFFFAOYSA-J iron(2+);phosphonato phosphate Chemical compound [Fe+2].[Fe+2].[O-]P([O-])(=O)OP([O-])([O-])=O ATEAWHILRRXHPW-UHFFFAOYSA-J 0.000 claims description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 2
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 2
- 229940059939 kayexalate Drugs 0.000 claims description 2
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 claims description 2
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 229960005137 succinic acid Drugs 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 7
- 150000003018 phosphorus compounds Chemical class 0.000 abstract 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 10
- 229910052493 LiFePO4 Inorganic materials 0.000 description 9
- 239000010450 olivine Substances 0.000 description 7
- 229910052609 olivine Inorganic materials 0.000 description 7
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 238000003836 solid-state method Methods 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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
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Abstract
The invention relates to a nanoscale lithium iron phosphate used as a cathode material of a lithium ion battery and a preparation method thereof. A lithium compound, an iron compound, a phosphorous compound and a doped element compound are mixed according to a molar ratio to form a mixture A; the mixture A and a complexing agent are mixed according to a weight ratio of 1:0.1-10 and dissolved in asolvent to form a mixture B; the mixture B is ball milled, dried and pretreated to form a nanoscale lithium iron phosphate precursor C; and the nanoscale lithium iron phosphate precursor C and a conductive carbon dispersion D are mixed according to a weight ratio of 100:2-30 of the nanoscale lithium iron phosphate precursor C to conductive carbon to form the lithium iron phosphate compound with ananoscale grain size. The preparation method comprises the following steps: sintering the mixture B to obtain the lithium iron phosphate precursor; mixing the lithium iron phosphate precursor and theconductive carbon dispersion D according to the weight ratio of 100:2-30 of the nanoscale lithium iron phosphate precursor C to the conductive carbon; and sintering the mixture of the precursor C andthe dispersion D after balling and drying to obtain a nanoscale lithium iron phosphate powder material. The nanoscale lithium iron phosphate used as the cathode material of a lithium ion battery has the grain size of 30-500nm, a specific surface area of 1-50m<2>/g and tap density of 0.7-2.5g/cm<3> and has fine and even grain and high purity. Because doped elements and the conductive carbon are added, the electrochemical performance of the nanoscale lithium iron phosphate is enhanced. The preparation method has simple process and easy realization of industrialization.
Description
[technical field]
The present invention relates to LiFePO4 as anode material for lithium-ion batteries and preparation method thereof, particularly relate to a kind of nano-grade lithium iron phosphate and preparation method thereof.
[background technology]
LiFePO4 (LiFePO
4) be a kind of anode material of lithium battery of developing in recent years with olivine structural, it has, and invertibity ground embeds and the characteristic of removal lithium embedded.Compare with traditional lithium ion secondary battery anode material, its former material source is more extensive, price is cheaper, avirulence, and non-environmental-pollution, especially its security performance and cycle life be other material can't compare, these are the most important technical indicator of electrokinetic cell just also, thereby makes countries in the world just competitively realize industrialization production.LiFePO4 has high-energy-density, and (its theoretical specific capacity is 170mAh/g, and the product actual specific capacity can surpass 140mAh/g (0.2C, 25 ℃); Because of it does not contain any harmful heavy metal element, and become present safest anode material for lithium-ion batteries; The lattice stability of LiFePO4 is good, the embedding of lithium ion and deviate from the influence of lattice little, so have good invertibity.It can discharge and recharge more than 2000 times under the 100%DOD condition, so long service life; With the lithium battery of LiFePO4, can use big multiplying power charging, the fastest can in 1 hour, battery being full of as positive electrode.Be characterized in that discharge capacity is big, cheap, do not cause environmental pollution.Yet LiFePO4 also has some deficiency, and is slow as its diffusion rate, and the electronic conductance rate variance is not suitable for discharging and recharging of big electric current, thereby is obstructed in power-type electrokinetic cell application facet.For this reason, people by at material surface coated with conductive material, the size carry out material modification, to reduce LiFePO4 of mixing solves to improve methods such as lithium ion diffusion rate.
At present, the production method of LiFePO4 mainly comprises high temperature solid-state method and hydrothermal synthesis method etc.Wherein, high temperature solid-state method is to mix necessarily measuring than raw material, and heating at a certain temperature makes solid predecomposition, the solid mixture after decomposing is ground evenly, then high temperature sintering.The advantage of high temperature solid-state method is that technology simply, easily realizes industrialization, but wayward, the skewness of product particle diameter, pattern is also irregular.Hydrothermal synthesis method is by Na
2HPO
4And FeCL
3Synthetic FePO
42H
2O is then with CH
3COOLi is by the synthetic LiFePO of hydro thermal method
4Compare with high temperature solid-state method, the temperature that hydro thermal method is synthesized is lower, about 150 ℃～200 ℃, the reaction time also only is about 1/5 of solid phase reaction, and can directly obtain LiFePO4, product crystal grain is less, thing phase homogeneous, be particularly suitable for the high-multiplying power discharge field, but the Fe inconsistent phenomenon takes place in this kind synthetic method easily in forming olivine structural, influence chemical property, and hydro thermal method needs high temperature high voltage resistant equipment, and it is big that the difficulty of suitability for industrialized production is wanted.
[summary of the invention]
The present invention is intended to address the above problem, and provide a kind of product to have nano-grade size, particle is tiny, even, purity is high, has the nano-grade lithium iron phosphate as anode material for lithium-ion batteries of higher charge/discharge capacity, good multiplying power discharging property and good circulation performance.
The present invention also aims to provide the preparation method of this nano-grade lithium iron phosphate.
For achieving the above object, the invention provides a kind of nano-grade lithium iron phosphate as anode material for lithium-ion batteries, it is by lithium compound, iron compound, phosphorus compound, doping element compound mixes formation mixture A in molar ratio mutually, mixture A mixed by 1: 0.1～10 weight ratio mutually with complexing agent and be dissolved in solvent and form mixture B, mixture B is through ball milling, vacuumize, preliminary treatment forms nano-grade lithium iron phosphate presoma C, nano-grade lithium iron phosphate presoma C and conductive carbon dispersion liquid D are pressed the mixed of nano-grade lithium iron phosphate presoma C and conductive carbon weight ratio 100: 2～30, and forming particle diameter is nano level lithium iron phosphate compound.
Among the mixture A, lithium compound, iron compound, phosphorus compound, doping element compound be Li in molar ratio: Fe: P: doped chemical is 0.95～1: 0.95～1: 0.95～1: 0～0.05 mixed.
Conductive carbon dispersion liquid D mixes conductive carbon and auxiliary agent by 1: 0.01～10 weight ratio and ultrasonic be distributed in the solvent and forming mutually.
Lithium compound is one or more the combination in lithia, lithium hydroxide, lithium acetate, lithium carbonate, lithium nitrate, lithium nitrite, lithium phosphate, lithium dihydrogen phosphate, lithium oxalate, lithium chloride, lithium molybdate, the lithium vanadate.
Iron compound is one or more the combination in ferric phosphate, ferrous phosphate, ferrous pyrophosphate, ferrous carbonate, frerrous chloride, ferrous hydroxide, ferrous nitrate, ferrous oxalate, iron chloride, iron hydroxide, ferric nitrate, ironic citrate, the di-iron trioxide.
Phosphorus compound is one or more the combination in phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ferric phosphate, the lithium dihydrogen phosphate.
Doping element compound is mainly a kind of or its combination in boron, the cadmium compound.
Doping element compound also comprises the compound of copper, magnesium, aluminium, zinc, manganese, titanium, zirconium, niobium, chromium and one or more the combination in the rare-earth compound.
Complexing agent is one or more the combination in citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, butanedioic acid, glycine, ethylenediamine tetra-acetic acid, sucrose, the glucose.
Solvent is one or more the combination in water, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, n-amyl alcohol, n-hexyl alcohol, n-heptanol, acetone, butanone, diacetyl, pentanone, cyclopentanone, hexanone, cyclohexanone, the cycloheptanone.
Auxiliary agent is one or more the combination in polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, kayexalate, polyoxyethylene nonylplenyl ether, hexadecyltrimethylammonium chloride, softex kw, OTAC, the octadecyl trimethylammonium bromide.
Conductive carbon is one or more the combination in Single Walled Carbon Nanotube, double-walled carbon nano-tube, multi-walled carbon nano-tubes, conductive black, the acetylene carbon black.
The percentage by weight of conductive carbon in nano-grade lithium iron phosphate is 0.1～10.
The present invention also provides the preparation method of this nano-grade lithium iron phosphate, and this method comprises the steps:
A, with lithium compound, iron compound, phosphorus compound, doping element compound Li: Fe: P in molar ratio: doped chemical is 0.95～1: 0.95～1: 0.95～1: 0～0.05 mixed forms mixture A;
B, mixture A mixed by 1: 0.1～10 weight ratio mutually with complexing agent and be dissolved in solvent, form mixture B;
C, with mixture B ball milling 10～48 hours in planetary ball mill;
D, place vacuum drier to obtain powder in 10～24 hours the mixture A behind the ball milling, the gained powder is pulverized with disintegrating apparatus at 80～180 ℃ temperature drying;
E, the powder after will pulverizing place the reducing atmosphere stove 300～700 ℃ temperature preliminary treatment 5～20 hours, obtain nano-grade lithium iron phosphate presoma C;
F, conductive carbon and auxiliary agent are mixed and ultrasonic being distributed in the solvent mutually by 1: 0.01～10 weight ratio, form conductive carbon dispersion liquid D;
G, described nano-grade lithium iron phosphate presoma C and conductive carbon dispersion liquid D are pressed the mixed of nano-grade lithium iron phosphate presoma C and conductive carbon weight ratio 100: 2～30, with compound ball milling 5～20 hours in planetary ball mill;
H, place vacuum drier to obtain powder in 10～24 hours the compound behind the ball milling at 80-180 ℃ temperature drying;
I, place nitrogen furnace 500-900 ℃ temperature sintering 10～30 hours the gained powder, obtain the nano-grade lithium iron phosphate powder body material.
Among the step e, the reducing atmosphere in the described reducing atmosphere stove is the gaseous mixture of hydrogen and nitrogen, and wherein the volume of hydrogen is 5%-50%, and all the other are nitrogen.
Nano-grade lithium iron phosphate particle diameter as anode material for lithium-ion batteries of the present invention is 30～500nm, and specific area is 1～50m
2/ g, tap density is 0.7～2.5g/cm
3, particle is tiny, even, purity is high.Owing to added doped chemical and added conductive carbon, strengthened its chemical property, have higher charge/discharge capacity, good multiplying power discharging property and good circulation performance.This preparation method's technology is simple, is easy to realize industrialization.
[embodiment]
The following example is to further explanation of the present invention and explanation, and the present invention is not constituted any limitation.
Embodiment 1
With lithium carbonate (molecular formula Li
2CO
3, 0.475mol) 35.15g, ferric nitrate (molecular formula Fe (NO
3)
39H
2O, 1mol) 404g, ammonium dihydrogen phosphate (molecular formula NH
4H
2PO
4, 1mol) 115g, aluminum nitrate (molecular formula Al (NO
3)
39H
2O, 0.05mol) 18.75g mixes mutually and obtains mixture A.Mixture A is mixed with malic acid 57.3g and water-soluble, obtain mixture B.With mixture B ball milling 10 hours in planetary ball mill, place vacuum drier to obtain powder in 24 hours the mixture B behind the ball milling at 80 ℃ temperature drying, the gained powder is pulverized with disintegrating apparatus.Powder after pulverizing is placed in hydrogen and nitrogen (volume of hydrogen is 5%, and all the other are nitrogen) the mixed atmosphere stove 300 ℃ temperature preliminary treatment 20 hours, obtain nano-grade lithium iron phosphate presoma C.Single Walled Carbon Nanotube 8g and polyvinyl alcohol 4g are mixed and ultrasonic being distributed in the aqueous solution mutually, form conductive carbon dispersion liquid D.Nano-grade lithium iron phosphate presoma C is mixed with conductive carbon dispersion liquid D, with compound ball milling 20 hours in planetary ball mill.Place vacuum drier to obtain powder in 24 hours the compound behind the ball milling at 80 ℃ temperature drying.Place nitrogen furnace 500 ℃ temperature sintering 30 hours the gained powder, obtain the nano-grade lithium iron phosphate powder body material.
Observing the product pattern through field emission scanning electron microscope (SEM) is olivine structural, and particle diameter is 30nm, detects with X-ray powder diffraction (XRD) to be LiFePO
4
The nano-grade lithium iron phosphate that will synthesize, PVDF and acetylene black add NMP by 85: 5: 10 mixed, stir and make slurry.Slurry is applied on the aluminium flake, 80 ℃ of oven dry down, as positive pole.With the lithium sheet is to electrode (negative pole), and the employing porous polypropylene film is a barrier film, and its thickness is 20 μ m, porosity 60%, the about 30 μ m in aperture.Adopt LiPF
6Organic solvent solution be electrolyte.Organic solvent is DMC: EC=1: 1.Positive pole, barrier film, negative pole are washed into suitable diameter, fold by the order of positive pole, barrier film, negative pole and put into CR2025 button cell shell, inject electrolyte, then with cell sealing.Battery is carried out the charge-discharge performance test.Adopt first constant current again the mode of constant voltage charge, the charging stopping potential is 3.8V, adopts constant-current discharge, cut-ff voltage is 2V, charging and discharging currents density: 0.5mA/cm
2First charge-discharge efficiency and specific discharge capacity are 95% and 140mAh/g, and circulating, specific discharge capacity is 112mAh/g after 1000 times.
Embodiment 2
With lithium hydroxide (molecular formula LiOH, 1mol) 24g, iron hydroxide (molecular formula Fe (OH)
3, 0.95mol) 101.65g, phosphoric acid (molecular formula H
3PO
4, 1mol) 98g, copper nitrate (molecular formula Cu (NO
3)
23H
2O, 0.05mol) 12.08g mixes mutually and obtains mixture A.Mixture A is mixed with 1178.65g sucrose and be dissolved in ethanol, obtain mixture B.With mixture B ball milling 20 hours in planetary ball mill, place vacuum drier to obtain powder in 20 hours the mixture B behind the ball milling at 100 ℃ temperature drying, the gained powder is pulverized with disintegrating apparatus.Powder after pulverizing is placed in hydrogen and nitrogen (volume of hydrogen is 10%, and all the other are nitrogen) the mixed atmosphere stove 400 ℃ temperature preliminary treatment 16 hours, obtain nano-grade lithium iron phosphate presoma C.Double-walled carbon nano-tube 10g and polyethylene glycol 100g are mixed and ultrasonic being distributed in the ethanol mutually, form conductive carbon dispersion liquid D.Nano-grade lithium iron phosphate presoma C is mixed with conductive carbon dispersion liquid D, with compound ball milling 16 hours in planetary ball mill.Place vacuum drier to obtain powder in 20 hours the compound behind the ball milling at 100 ℃ temperature drying.Place nitrogen furnace 600 ℃ temperature sintering 24 hours the gained powder, obtain the nano-grade lithium iron phosphate powder body material.
Observing the product pattern through field emission scanning electron microscope (SEM) is olivine structural, and particle diameter is 50nm, detects with X-ray powder diffraction (XRD) to be LiFePO
4
The preparation of pole piece, the assembling of Experimental cell and electrochemical property test are with embodiment 1.The first charge-discharge efficiency of sample and specific discharge capacity are 96% and 145mAh/g, and circulating, specific discharge capacity is 116mAh/g after 1000 times.
Embodiment 3
With lithium nitrate (molecular formula LiNO
3, 1mol) 69g, ferrous oxalate (molecular formula FeC
2O
42H
2O, 1mol) 179.9g, diammonium hydrogen phosphate (molecular formula (NH
4)
2HPO
4, 0.95mol) 125.4g, boron oxide (molecular formula B
2O
3, 0.025mol) 1.74g mixes mutually and obtains mixture A.Mixture A is mixed mutually with glucose 752g and be dissolved in propyl alcohol, obtain mixture B.With mixture B ball milling 30 hours in planetary ball mill, place vacuum drier to obtain powder in 16 hours the mixture B behind the ball milling at 120 ℃ temperature drying, the gained powder is pulverized with disintegrating apparatus.Powder after pulverizing is placed in hydrogen and nitrogen (volume of hydrogen is 20%, and all the other are nitrogen) the mixed atmosphere stove 500 ℃ temperature preliminary treatment 12 hours, obtain nano-grade lithium iron phosphate presoma C.Multi-walled carbon nano-tubes 15g and polyethylene glycol oxide 45g are mixed and ultrasonic being distributed in the propyl alcohol mutually, form conductive carbon dispersion liquid D.Nano-grade lithium iron phosphate presoma C is mixed with conductive carbon dispersion liquid D, with compound ball milling 12 hours in planetary ball mill.Place vacuum drier to obtain powder in 16 hours the compound behind the ball milling at 120 ℃ temperature drying.Place nitrogen furnace 700 ℃ temperature sintering 20 hours the gained powder, obtain the nano-grade lithium iron phosphate powder body material.
Observing the product pattern through field emission scanning electron microscope (SEM) is olivine structural, and particle diameter is 100nm, detects with X-ray powder diffraction (XRD) to be LiFePO
4
The preparation of pole piece, the assembling of Experimental cell and electrochemical property test are with embodiment 1.The first charge-discharge efficiency of sample and specific discharge capacity are 97% and 148mAh/g, and circulating, specific discharge capacity is 118mAh/g after 1000 times.
Embodiment 4
With lithium oxalate (molecular formula Li
2C
2O
4, 0.49mol) 49.98g g, ferrous carbonate (molecular formula FeCO
3, 1mol) 115.86g, ammonium dihydrogen phosphate (molecular formula NH
4H
2PO
4, 1mol) 115g, cadmium nitrate (molecular formula Cd (NO
3)
24H
2O, 0.02mol) 6.17g mixes mutually and obtains mixture A.Mixture A is mixed with the 287g citric acid and be dissolved in isopropyl alcohol, obtain mixture B.With mixture B ball milling 40 hours in planetary ball mill, place vacuum drier to obtain powder in 12 hours the mixture B behind the ball milling at 150 ℃ temperature drying, the gained powder is pulverized with disintegrating apparatus.Powder after pulverizing is placed in hydrogen and nitrogen (volume of hydrogen is 30%, and all the other are nitrogen) the mixed atmosphere stove 600 ℃ temperature preliminary treatment 8 hours, obtain nano-grade lithium iron phosphate presoma C.Conductive black 20g and polyethylene glycol oxide 40g are mixed and ultrasonic being distributed in the isopropyl alcohol mutually, form conductive carbon dispersion liquid D.Nano-grade lithium iron phosphate presoma C is mixed with conductive carbon dispersion liquid D, with compound ball milling 8 hours in planetary ball mill.Place vacuum drier to obtain powder in 12 hours the compound behind the ball milling at 150 ℃ temperature drying.Place nitrogen furnace 800 ℃ temperature sintering 15 hours the gained powder, obtain the nano-grade lithium iron phosphate powder body material.
Observing the product pattern through field emission scanning electron microscope (SEM) is olivine structural, and particle diameter is 200nm, detects with X-ray powder diffraction (XRD) to be LiFePO
4
The preparation of pole piece, the assembling of Experimental cell and electrochemical property test are with embodiment 1.The first charge-discharge efficiency of sample and specific discharge capacity are 97% and 150mAh/g, and circulating, specific discharge capacity is 120mAh/g after 1000 times.
Embodiment 5
With lithium acetate (molecular formula C
2H
3LiO
22H
2O, 0.99mol) 101g, di-iron trioxide (molecular formula Fe
2O
3, 0.495mol) 79.2g, diammonium hydrogen phosphate (molecular formula (NH
4)
2HPO
4, 0.99mol) 130.68g, cadmium nitrate (molecular formula Cd (NO
3)
24H
2O, 0.01mol) 3.08g, boron oxide (molecular formula B
2O
3, 0.01mol) 0.7g mixes mutually and obtains mixture A.Mixture A is mixed with tartaric acid 157.33g and be dissolved in isobutanol, obtain mixture B.With mixture B ball milling 48 hours in planetary ball mill, place vacuum drier to obtain powder in 10 hours the mixture B behind the ball milling at 180 ℃ temperature drying, the gained powder is pulverized with disintegrating apparatus.Powder after pulverizing is placed in hydrogen and nitrogen (volume of hydrogen is 50%, and all the other are nitrogen) the mixed atmosphere stove 700 ℃ temperature preliminary treatment 5 hours, obtain nano-grade lithium iron phosphate presoma C.Acetylene carbon black 30g and polyethylene glycol 30g are mixed and ultrasonic being distributed in the isobutanol mutually, form conductive carbon dispersion liquid D.Nano-grade lithium iron phosphate presoma C is mixed with conductive carbon dispersion liquid D, with compound ball milling 5 hours in planetary ball mill.Place vacuum drier to obtain powder in 10 hours the compound behind the ball milling at 180 ℃ temperature drying.Place nitrogen furnace 900 ℃ temperature sintering 10 hours the gained powder, obtain the nano-grade lithium iron phosphate powder body material.
Observing the product pattern through field emission scanning electron microscope (SEM) is olivine structural, and particle diameter is 300nm, detects with X-ray powder diffraction (XRD) to be LiFePO
4
The preparation of pole piece, the assembling of Experimental cell and electrochemical property test are with embodiment 1.The first charge-discharge efficiency of sample and specific discharge capacity are 97% and 135mAh/g, and circulating, specific discharge capacity is 108mAh/g after 1000 times.
Claims (10)
1. nano-grade lithium iron phosphate as anode material for lithium-ion batteries, it is characterized in that, this nano-grade lithium iron phosphate is by lithium compound, iron compound, phosphorus compound, doping element compound mixes formation mixture A in molar ratio mutually, mixture A mixed by 1: 0.1～10 weight ratio mutually with complexing agent and be dissolved in solvent and form mixture B, mixture B is through ball milling, vacuumize, preliminary treatment forms nano-grade lithium iron phosphate presoma C, nano-grade lithium iron phosphate presoma C and conductive carbon dispersion liquid D are pressed the mixed of nano-grade lithium iron phosphate presoma C and conductive carbon weight ratio 100: 2～30, and forming particle diameter is nano level lithium iron phosphate compound.
2. nano-grade lithium iron phosphate as claimed in claim 1, it is characterized in that, among the described mixture A, lithium compound, iron compound, phosphorus compound, doping element compound be Li in molar ratio: Fe: P: doped chemical is 0.95～1: 0.95～1: 0.95～1: 0～0.05 mixed.
3. nano-grade lithium iron phosphate as claimed in claim 1, it is characterized in that, described conductive carbon dispersion liquid D mixes conductive carbon and auxiliary agent by 1: 0.01～10 weight ratio and ultrasonic be distributed in the solvent and forming mutually, and described auxiliary agent is one or more the combination in polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, kayexalate, polyoxyethylene nonylplenyl ether, hexadecyltrimethylammonium chloride, softex kw, OTAC, the octadecyl trimethylammonium bromide.
4. as arbitrary described nano-grade lithium iron phosphate in the claim 1 to 3, it is characterized in that the particle diameter of described nano-grade lithium iron phosphate is 30～500nm, specific area is 1～50m
2/ g, tap density is 0.7～2.5g/cm
3
5. nano-grade lithium iron phosphate as claimed in claim 2, it is characterized in that described lithium compound is one or more the combination in lithia, lithium hydroxide, lithium acetate, lithium carbonate, lithium nitrate, lithium nitrite, lithium phosphate, lithium dihydrogen phosphate, lithium oxalate, lithium chloride, lithium molybdate, the lithium vanadate; Described iron compound is one or more the combination in ferric phosphate, ferrous phosphate, ferrous pyrophosphate, ferrous carbonate, frerrous chloride, ferrous hydroxide, ferrous nitrate, ferrous oxalate, iron chloride, iron hydroxide, ferric nitrate, ironic citrate, the di-iron trioxide; Described phosphorus compound is one or more the combination in phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ferric phosphate, the lithium dihydrogen phosphate; Described complexing agent is one or more the combination in citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, butanedioic acid, glycine, ethylenediamine tetra-acetic acid, sucrose, the glucose; Described solvent is one or more the combination in water, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, n-amyl alcohol, n-hexyl alcohol, n-heptanol, acetone, butanone, diacetyl, pentanone, cyclopentanone, hexanone, cyclohexanone, the cycloheptanone.
6. nano-grade lithium iron phosphate as claimed in claim 2 is characterized in that, described doping element compound is mainly a kind of or its combination in boron, the cadmium compound.
7. nano-grade lithium iron phosphate as claimed in claim 6 is characterized in that, described doping element compound also comprises the compound of copper, magnesium, aluminium, zinc, manganese, titanium, zirconium, niobium, chromium and one or more the combination in the rare-earth compound.
8. nano-grade lithium iron phosphate as claimed in claim 3 is characterized in that, described conductive carbon is one or more the combination in Single Walled Carbon Nanotube, double-walled carbon nano-tube, multi-walled carbon nano-tubes, conductive black, the acetylene carbon black; The percentage by weight of described conductive carbon in nano-grade lithium iron phosphate is 0.1～10.
9. the preparation method of nano-grade lithium iron phosphate as claimed in claim 1 is characterized in that, it comprises the steps:
A, with lithium compound, iron compound, phosphorus compound, doping element compound Li: Fe: P in molar ratio: doped chemical is 0.95～1: 0.95～1: 0.95～1: 0～0.05 mixed forms mixture A;
B, mixture A mixed by 1: 0.1～10 weight ratio mutually with complexing agent and be dissolved in solvent, form mixture B;
C, with mixture B ball milling 10～48 hours in planetary ball mill;
D, place vacuum drier to obtain powder in 10～24 hours the mixture A behind the ball milling, the gained powder is pulverized with disintegrating apparatus at 80～180 ℃ temperature drying;
E, the powder after will pulverizing place the reducing atmosphere stove 300～700 ℃ temperature preliminary treatment 5～20 hours, obtain nano-grade lithium iron phosphate presoma C;
F, conductive carbon and auxiliary agent are mixed and ultrasonic being distributed in the solvent mutually by 1: 0.01～10 weight ratio, form conductive carbon dispersion liquid D;
G, be 100: 2～30 mixed by the weight ratio of nano-grade lithium iron phosphate presoma C and conductive carbon, with compound ball milling 5～20 hours in planetary ball mill with described nano-grade lithium iron phosphate presoma C and conductive carbon dispersion liquid D;
H, place vacuum drier to obtain powder in 10～24 hours the compound behind the ball milling at 80-180 ℃ temperature drying;
I, place nitrogen furnace 500-900 ℃ temperature sintering 10～30 hours the gained powder, obtain the nano-grade lithium iron phosphate powder body material.
10. preparation method as claimed in claim 9 is characterized in that, in the step (e), the reducing atmosphere in the described reducing atmosphere stove is the gaseous mixture of hydrogen and nitrogen, and wherein the volume of hydrogen is 5%-50%, and all the other are nitrogen.
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| CN113292058A (en) * | 2021-05-21 | 2021-08-24 | 衢州华友钴新材料有限公司 | Preparation method of nano-doped lithium iron phosphate |
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