CN101969116B - Method for preparing lithium iron phosphate anode material doped with nano iron and iodide - Google Patents
Method for preparing lithium iron phosphate anode material doped with nano iron and iodide Download PDFInfo
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- CN101969116B CN101969116B CN2010102888654A CN201010288865A CN101969116B CN 101969116 B CN101969116 B CN 101969116B CN 2010102888654 A CN2010102888654 A CN 2010102888654A CN 201010288865 A CN201010288865 A CN 201010288865A CN 101969116 B CN101969116 B CN 101969116B
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- Prior art keywords
- lithium
- iodide
- iron
- preparation
- ferrous
- Prior art date
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Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 18
- 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 15
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 title claims abstract description 4
- 239000010405 anode material Substances 0.000 title abstract description 3
- 238000002360 preparation method Methods 0.000 claims abstract description 41
- -1 iodine ions Chemical class 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 14
- 239000010452 phosphate Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000000376 reactant Substances 0.000 claims abstract description 11
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 150000001722 carbon compounds Chemical class 0.000 claims abstract description 6
- 238000001238 wet grinding Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 239000011630 iodine Substances 0.000 claims abstract description 3
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 24
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 22
- 229940006461 iodide ion Drugs 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 239000010406 cathode material Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 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 9
- 239000002245 particle Substances 0.000 claims description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical group [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 230000001186 cumulative effect Effects 0.000 claims description 7
- 239000008247 solid mixture Substances 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 6
- 239000004254 Ammonium phosphate Substances 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 4
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229940045105 silver iodide Drugs 0.000 claims description 4
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000004277 Ferrous carbonate 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
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229940107816 ammonium iodide Drugs 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 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
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 3
- 235000019268 ferrous carbonate Nutrition 0.000 claims description 3
- 229960004652 ferrous carbonate Drugs 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000015 iron(II) carbonate Inorganic materials 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
- 238000012423 maintenance Methods 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 229910001640 calcium iodide Inorganic materials 0.000 claims description 2
- 229940046413 calcium iodide Drugs 0.000 claims description 2
- 238000001311 chemical methods and process Methods 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 238000000053 physical method Methods 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- HUIHCQPFSRNMNM-UHFFFAOYSA-K scandium(3+);triiodide Chemical compound [Sc+3].[I-].[I-].[I-] HUIHCQPFSRNMNM-UHFFFAOYSA-K 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
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical group OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 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
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- 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 invention relates to a method for preparing a lithium iron phosphate anode material doped with nano iron and iodide, which comprises: weighing components including lithium ions, ferrousions, nano iron, phosphate radicals and iodine ions in a molar ratio of 1.05:(1-x):x:(1-y):y accurately, mixing, adding a carbon compound or carbon powder in an amount which is 1 to 25 percent based on the total mass of the reactants, adding a wet grinding medium, grinding, mixing, performing vacuum drying at the temperature of 48 to 150 DEG C and under a pressure of 10 to 10,132Pa, placing the dry powder in an inertia atmosphere, and preparing controllable Fe2P-containing lithium iron phosphate by a two-stage sintering method. In the invention, the raw materials are low in cost and widely available, and the preparation process is simple. The prepared electrode material has high discharging performance, particularly high-rate discharge circular performance. The method lays a good foundation for industrialization.
Description
Technical field
The invention belongs to the battery manufacture technical field, what be specifically related to a kind of while dopen Nano iron and iodide ion is used for lithium ion battery, lithium battery, lithium ion polymer battery and ultracapacitor, can carry out the preparation method of the lithium iron phosphate cathode material of heavy-current discharge.
Technical background
LiFePO
4Have higher theoretical specific capacity, smooth voltage platform, outstanding cyclical stability and thermally-stabilised.From application point, preparation LiFePO
4Raw material resources abundant, cheap, environmentally safe, LiFePO
4Carry one of most potential anode material for lithium-ion batteries.Yet, although through numerous researchs and modification, in building-up process, LiFePO
4Positive electrode is still deposited in the preparation Fe
2+Easily oxidized, sample particle big or small wayward, electronic conductivity and ion diffusion rate are low, thereby cause sample problems such as capacity attenuation is larger under the heavy-current discharge condition.
The preparation LiFePO 4 can adopt the methods such as solid-phase sintering, liquid phase are synthesized, Hydrothermal Synthesis.Wherein, solid sintering technology prepares LiFePO 4 and has the advantages such as price is low, pollution is little, device efficiency is high, the sample chemical property is good, tap density is large.Preparing LiFePO 4 with solid-phase sintering method is that sintering prepares LiFePO 4 or ferrous phosphate doping lithium under different temperatures with mixing such as the compound of lithium salts, iron (or ferrous) compound, phosphate, doped chemical and conductive agents mostly.In preparation sample process, the reagent that electronic conductivity is high maybe can generate the high reagent of electronic conductivity and be added in the predecessor to realize improving the purpose of LiFePO 4 electronic conductivity.The inorganic conductive thing of using comprises nickel fiber, copper fiber, iron fiber, zinc fiber, acetylene black, carbon dust, boride, carbide, transition metal oxide [CN1948134A; CN101070148A; Kim K.et al., J.Power Sources, 2007,167:524-528; Kim J.-K.et al., Materials Letters, 2007,61:3822-3825.] etc.The organic conductive agent of using comprises sucrose, glucose, polyvinyl alcohol, dextrin, starch etc.For low deficiency, the studied mistake of multiple doping method of waiting of ionic conductance of improving LiFePO 4.The doped chemical of selecting comprises [the CN1958441A such as alkali metal ion, alkaline-earth metal ions, transition metal ions, halide ion, rare earth metal; Choi D.et al., J.Power Sources, 2007,163:1064-1069; Croce F et al, Electrochem.Solid State Lett., 2002,5 (3): A47-A50; Park K S et al.Solid State Commun., 2004,129:311-314.].Preparation process adopts " the mixed reactant of ball milling or the slurrying of first ball-milling reaction thing, the again combined method of further solid-phase sintering " mostly.
The compounds of various carbon or carbon containing that adopt coat processing more during preparation, or carry out modification [CN101070148A with the method that the carbon compound coating is combined with the method for ion doping; CN100347081C; CN1581537A; CN1982207A; CN1255887C].The part document has also been studied the doping ion and has been occupied lithium position, iron position, phosphate potential or the oxygen position of LiFePO 4 structure to the improvement effect of chemical property.Patent CN1790782A, CN1803592A and CN101037195A studies show that, the P site doped heavy-current discharge performance that can improve sample.Patent CN1790782A and patent CN1803592A have prepared the LiFePO 4 of phosphate potential replacement with lithium salts, ferrous salt and phosphate and substituent batch mixing by the method for twice ball milling and twice sintered combination.The substituent of selecting comprises that boron replaces sulphur and the silicon replacement source of source, tungsten replacement source, sulfurous organic compound, simple substance.Patent CN101037195A has prepared the LiFePO 4 that phosphate potential is mixed Ge, Sn, Se, Te or Bi.Park etc. [Park J S et al., Rare Metals, 2006,25:179-183.] studies show that excess carbon can reduction occur at high temperature in the reaction-ure mixture, make association in the LiFePO 4 go out the Fe of good conductivity
2P.But, because Fe
2P is that the carbon reduction obtains, and Fe in the Quality control
2The amount of P and structure are very difficult.
In the process of preparation LiFePO 4, be to carry out sintering in the atmosphere of non-oxidizable or reproducibility mostly.As, in hydrogen and nitrogen mixture, hydrogen and the atmosphere such as argon gas gaseous mixture, carbon monoxide, carry out the sintering preparation.In addition, many reducing agents also are used to improve LiFePO 4, as, patent documentation CN1821065A, CN1803591A, CN1834004A, CN1915804A, CN1800003A etc.Patent CN1821065A adopts the reducing agents such as hydrochloric acid hydroxylammonium, ascorbic acid.The reducing agent that patent CN1803591A adopts is ascorbic acid, hydrazine hydrate, stannous chloride, sodium borohydride or its mixture.The reducing agent that patent CN1834004A and CN1915804A adopt is sulfurous acid, ammonium sulfite, thiosulfuric acid or ATS (Ammonium thiosulphate).When adopting reducing atmosphere to carry out sintering, higher to the preparation environmental requirement.These reducibility gas are very wide in the explosion limit of air atmosphere, if leakage is slightly arranged, just may cause the serious accidents such as burning, blast.Many reducing agents such as stannous chloride, sodium borohydride etc., can be retained in the foreign ion of not wishing to stay in the LiFePO 4 product of preparation in preparation process, thereby pollute the product of preparation.So that side reaction occurs the LiFePO 4 of preparation, affect the storing performance of sample when depositing.And the reducing agents such as hydrochloric acid hydroxylammonium and ascorbic acid show strong not reproducibility in preparation process, and unstable.This compound decomposed before reaching the preparation temperature of LiFePO 4 already, can not play the purpose of reduction.
Yet studies show that: Nanoscale Iron has very strong reproducibility, when undressed Nanoscale Iron runs into air, even dieseling can occur.When Nanoscale Iron during as one of pre-reaction material, can not increase the content of impurity in the product in the preparation product.
For these problems, we consider with Nanoscale Iron as reducing agent, add simultaneously iodide ion, by the synergy of Nanoscale Iron and iodide ion, the generation of dephasign in the inhibition system improves conductivity and the lithium ion diffusion coefficient of sample.Simultaneously, the Nanoscale Iron of adding may promote that association goes out more Fe in the LiFePO 4
2P increases the conductivity of product, has obviously improved the heavy-current discharge performance of sample.
Summary of the invention
The preparation method who the purpose of this invention is to provide the lithium iron phosphate cathode material of a kind of while dopen Nano iron and iodide ion.
For achieving the above object, the technical solution adopted in the present invention is:
According to lithium ion: ferrous ion: Nanoscale Iron: phosphate anion: the mol ratio of iodide ion is 1.05: (1-x): x: (1-y): y, accurately take by weighing the compound of lithium, ferrous compound, Nanoscale Iron, the salt compounds of phosphoric acid and the compound of iodine, mix, 1%～25% carbon compound or the carbon dust that add reactant quality summation, add again wet grinding media, ground and mixed 3 hours～12 hours, vacuumize under 48 ℃～150 ℃ of temperature, pressure 10Pa～10132Pa.The powder of drying is placed inert atmosphere, contain controlled Fe with the double sintering legal system is standby
2The LiFePO 4 of P.The x here and the span of y are: 0.001≤x≤0.10,0.001≤y≤0.08.
Described double sintering method: the powder of drying is placed inert atmosphere, heating rate according to 0.5 ℃/min～30 ℃/min, be heated to arbitrary temperature of 200 ℃～500 ℃ of temperature ranges by room temperature, keep temperature calcining 1 hour～12 hours, then according to the heating rate of 0.5 ℃/min～30 ℃/min, be warming up to arbitrary temperature of 550 ℃～850 ℃ of temperature ranges, the maintenance temperature was calcined 3 hours～24 hours, prepared to contain controlled Fe
2The LiFePO 4 of P.
The compound of described lithium is a kind of of lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium nitrate or lithium phosphate, or the mixture of its arbitrary proportion;
The compound of described ferrous iron is a kind of in ferrous oxide, ferrous oxalate, ferrous acetate, frerrous chloride, ferrous sulfate or the ferrous carbonate, or the mixture of its arbitrary proportion;
The salt compounds of described phosphoric acid is a kind of in ammonium phosphate, diammonium hydrogen phosphate and the ammonium dihydrogen phosphate, or the mixture of its arbitrary proportion;
Described carbon compound is a kind of in glucose, polyvinyl alcohol, polypropylene, polyacrylamide, sucrose, starch, graphite powder, the acetylene black, or the mixture of its arbitrary proportion;
Described inert atmosphere is a kind of of nitrogen, argon gas, carbon dioxide, or the mixture of its arbitrary proportion;
Described wet grinding media is a kind of in deionized water, distilled water, ethanol, acetone, propyl alcohol, methyl alcohol or the formaldehyde, or the mixture of its arbitrary proportion, and the addition of wet grinding media is 1/10 to 10 times of reactant mixture total solid capacity;
The compound of described iodine is sodium iodide, KI, lithium iodide, silver iodide, ammonium iodide, calcium iodide, scandium iodide, zinc iodide or hydroiodic acid;
Described Nanoscale Iron is the iron powder of chemistry or physical method preparation, the arbitrary interval of its particle diameter between between 1 nanometer～500 nanosection.
Described ground and mixed is that ball milling mixes or agitation grinding mixes, and the equipment of employing is general milling machine or high energy ball mill, or mixer grinder.When the equipment that adopts was general milling machine or high energy ball mill, ball milling speed was 200 rev/mins～900 rev/mins, and the positive electrode of preparation can be used as the positive electrode of lithium ion battery, lithium battery, lithium ion polymer battery and ultracapacitor.
Compare with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, preparation process is simple, and is consuming time few, and the electrode material of preparation forms evenly, have outstanding discharge performance, particularly good at the cycle performance of heavy-current discharge, for industrialization is laid a good foundation.
Embodiment
Below in conjunction with embodiment the present invention is further detailed.Embodiment further replenishes and explanation of the present invention, rather than the restriction to inventing.
Embodiment 1
The preparation of LiFePO 4 is comprised of following steps:
According to lithium ion: ferrous ion: Nanoscale Iron: phosphate anion: the mol ratio of iodide ion is 1.05: 0.999: 0.001: 0.999: 0.001, accurately take by weighing lithium carbonate, ferrous oxalate, (particle diameter is between 1nm～20nm) for the nanometer iron powder of reducing process preparation, ammonium phosphate and sodium iodide, mix, 1% the glucose that adds reactant quality summation, 1/10 the deionized water that adds again the cumulative volume of the solid mixture treat ball milling, mixed 3 hours with the rotating speed ball milling of general milling machine with 200 rev/mins, 48 ℃ of temperature, vacuumize in the vacuum drying chamber of pressure 10Pa.The powder of drying is placed nitrogen atmosphere, according to the heating rate of 0.5 ℃/min, be heated to 200 ℃ by room temperature, keep temperature calcining 1 hour, then the programming rate according to 0.5 ℃/min further is heated to 550 ℃, keeps temperature calcining 3 hours, prepares to contain controlled Fe
2The LiFePO 4 of P.
Embodiment 2
According to lithium ion: ferrous ion: Nanoscale Iron: phosphate anion: the iodide ion mol ratio is 1.05: 0.90: 0.10: 0.92: 0.08 mol ratio, accurately take by weighing lithium hydroxide, ferrous acetate, (particle diameter is between 20nm～100nm) for the nanometer iron powder of high energy ball mill ball milling preparation, diammonium hydrogen phosphate and lithium iodide, mix, 25% the polyvinyl alcohol that adds reactant quality summation, the ethanol that adds again 10 times of volumes of the solid mixture cumulative volume for the treatment of ball milling, mixed 3 hours with the rotating speed ball milling of high energy ball mill with 900 rev/mins, 150 ℃ of temperature, dry in the vacuum drying chamber of pressure 10132Pa.The powder of drying is placed argon gas atmosphere, according to the heating rate of 30 ℃/min, be heated to 500 ℃ by room temperature, keep temperature calcining 12 hours, and then further be heated to 850 ℃ according to the heating rate of 30 ℃/min, and keep temperature calcining 24 hours, prepare and contain controlled Fe
2The LiFePO 4 of P.
Embodiment 3
According to lithium ion: ferrous ion: Nanoscale Iron: phosphate anion: the iodide ion mol ratio is 1.05: 0.995: 0.005: 0.92: 0.08, (particle diameter is between 100nm～300nm), ammonium dihydrogen phosphate and silver iodide accurately to take by weighing the nanometer iron powder of lithium oxalate, frerrous chloride, chemical preparation, mix, 10% the starch that adds reactant quality summation, the acetone that adds again 1 times of volume treating ball milling solid mixture cumulative volume, mixed 12 hours vacuumize in the vacuum drying chamber of 100 ℃ of temperature, pressure 100Pa with mixer grinder.It is 1 that the powder of drying is placed nitrogen and argon gas volume ratio; In the atmosphere of 1 gaseous mixture, according to the heating rate of 5 ℃/min, be heated to 300 ℃ by room temperature, keep temperature calcining 10 hours, then the heating rate according to 20 ℃/min further is heated to 650 ℃, keeps temperature calcining 15 hours, prepares to contain controlled Fe
2The LiFePO 4 of P.
Embodiment 4
According to lithium ion: ferrous ion: Nanoscale Iron: phosphate anion: the iodide ion mol ratio is 1.05: 0.90: 0.10: 0.999: 0.001, accurately take by weighing lithium nitrate, ferrous carbonate, (particle diameter is between 100nm～500nm) for the nanometer iron powder of high energy ball mill preparation, ammonium phosphate and zinc iodide, mix, 15% the carbon dust that adds reactant quality summation, the propyl alcohol that adds again 5 times of volumes of the solid mixture cumulative volume for the treatment of ball milling, with the general milling machine with 300 rev/mins speed ball milling 10 hours, 120 ℃ of temperature, dry in vacuum drying chamber under the pressure 1000Pa.The powder of drying is placed the atmosphere of nitrogen and 1: 10 gaseous mixture of argon gas volume ratio, heating rate according to 5 ℃/min, be heated to 400 ℃ by room temperature, keep temperature calcining 8 hours, and then according to the heating rate of 10 ℃/min, further be heated to 800 ℃, keep temperature calcining 10 hours, obtain containing controlled Fe
2The LiFePO 4 of P.
Embodiment 5
According to lithium ion: ferrous ion: Nanoscale Iron: phosphate anion: the iodide ion mol ratio is 1.05: 0.992: 0.008: 0.999: 0.001, accurately take by weighing lithium nitrate, ferrous oxalate, (particle diameter is between 300nm～500nm) for the Nanoscale Iron of physics cutting preparation, diammonium hydrogen phosphate and silver iodide, mix, 20% the carbon dust that adds reactant quality summation, the methyl alcohol that adds again 1 times of volume of the solid mixture cumulative volume for the treatment of ball milling, with high energy ball mill with 800 rev/mins speed ball milling 12 hours, 150 ℃ of temperature, dry in vacuum drying chamber under the pressure 10000Pa.It is 1: 10 atmosphere that the powder of drying is placed carbon dioxide and nitrogen volume ratio, heating rate according to 30 ℃/min, be heated to 500 ℃ by room temperature, keep temperature calcining 12 hours, and then according to the heating rate of 20 ℃/min, further be heated to 750 ℃, keep temperature calcining 24 hours, obtain containing controlled Fe
2The LiFePO 4 of P.
Embodiment 6
According to lithium ion: ferrous ion: Nanoscale Iron: phosphate anion: the iodide ion mol ratio is 1.05: 0.99: 0.01: 0.95: 0.05, accurately take by weighing lithium hydroxide, ferrous acetate, (particle diameter is between 10nm～50nm) for the nanometer iron powder of chemical preparation, ammonium phosphate and ammonium iodide, mix, 5% the starch that adds reactant quality summation, the formaldehyde that adds again 5 times of volumes of the solid mixture cumulative volume for the treatment of ball milling, with high energy ball mill with 700 rev/mins rotating speed ball milling 12 hours, 150 ℃ of temperature, vacuumize in the vacuum drying chamber of pressure 10132Pa.The powder of drying is placed argon gas atmosphere, according to the heating rate of 15 ℃/min, be heated to 450 ℃ by room temperature, keep temperature calcining 12 hours, then according to the heating rate of 30 ℃/min, further be heated to 850 ℃, the maintenance temperature was calcined 3 hours, prepared to contain controlled Fe
2The LiFePO 4 of P.
Claims (9)
1. preparation method of the lithium iron phosphate cathode material of dopen Nano iron and iodide ion simultaneously, it is characterized in that: according to lithium ion: ferrous ion: Nanoscale Iron: phosphate anion: the iodide ion mol ratio is 1.05: (1-x): x: (1-y): y, accurately take by weighing the compound of lithium, ferrous compound, Nanoscale Iron, the salt compounds of phosphoric acid and the compound of iodine, mix, adding is according to 1%～25% carbon compound or carbon dust of reactant quality summation, add again wet grinding media, ground and mixed 3 hours～12 hours, 48 ℃～150 ℃ of temperature, vacuumize under pressure 10Pa～10132Pa, the powder of drying is placed inert atmosphere, contain controlled Fe with the double sintering legal system is standby
2The LiFePO 4 of P, the x here and the span of y are: 0.001≤x≤0.10,0.001≤y≤0.08;
Described double sintering method: the powder of drying is placed inert atmosphere, heating rate according to 0.5 ℃/min～30 ℃/min, be heated to arbitrary temperature of 200 ℃～500 ℃ of temperature ranges by room temperature, keep temperature calcining 1 hour～12 hours, then according to the heating rate of 0.5 ℃/min～30 ℃/min, further be heated to arbitrary temperature of 550 ℃～850 ℃ of temperature ranges, the maintenance temperature was calcined 3 hours～24 hours, prepared to contain controlled Fe
2The LiFePO 4 of P.
2. the preparation method of the lithium iron phosphate cathode material of a kind of while dopen Nano iron according to claim 1 and iodide ion, the salt compounds that it is characterized in that described phosphoric acid is a kind of in ammonium phosphate, diammonium hydrogen phosphate and the ammonium dihydrogen phosphate, or the mixture of its arbitrary proportion; Described Nanoscale Iron is the iron powder of chemistry or physical method preparation, and its particle diameter is between arbitrary interval of 1 nanometer～500 nanometer range.
3. the preparation method of the lithium iron phosphate cathode material of a kind of while dopen Nano iron according to claim 1 and iodide ion, it is characterized in that vacuum drying pressure is 10Pa～10132Pa, ground and mixed is that ball milling mixes or agitation grinding mixes, the equipment that adopts is general milling machine or high energy ball mill, or mixer grinder; When the equipment that adopts was general milling machine or high energy ball mill, ball milling speed was 200 rev/mins～900 rev/mins.
4. the preparation method of the lithium iron phosphate cathode material of a kind of while dopen Nano iron according to claim 1 and iodide ion, the compound that it is characterized in that described lithium is a kind of of lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium nitrate or lithium phosphate, or the mixture of its arbitrary proportion.
5. the preparation method of the lithium iron phosphate cathode material of a kind of while dopen Nano iron according to claim 1 and iodide ion, the compound that it is characterized in that described ferrous iron is a kind of in ferrous oxide, ferrous oxalate, ferrous acetate, frerrous chloride, ferrous sulfate or the ferrous carbonate, or the mixture of its arbitrary proportion.
6. the preparation method of the lithium iron phosphate cathode material of a kind of while dopen Nano iron according to claim 1 and iodide ion, the compound that it is characterized in that described iodine is sodium iodide, KI, lithium iodide, silver iodide, ammonium iodide, calcium iodide, scandium iodide, zinc iodide or hydroiodic acid.
7. the preparation method of the lithium iron phosphate cathode material of a kind of while dopen Nano iron according to claim 1 and iodide ion, it is characterized in that described carbon compound is a kind of in glucose, polyvinyl alcohol, polypropylene, polyacrylamide, sucrose, the starch, or the mixture of its arbitrary proportion.
8. the preparation method of the lithium iron phosphate cathode material of a kind of while dopen Nano iron according to claim 1 and iodide ion is characterized in that described inert atmosphere is a kind of of nitrogen, argon gas, carbon dioxide, or the mixture of its arbitrary volume ratio.
9. the preparation method of the lithium iron phosphate cathode material of a kind of while dopen Nano iron according to claim 1 and iodide ion, it is characterized in that described wet grinding media is a kind of in deionized water, distilled water, ethanol, acetone, propyl alcohol, methyl alcohol or the formaldehyde, or the mixture of its arbitrary proportion, addition is to treat 1/10 to 10 times of volume of ball milling solid mixture cumulative volume.
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| CN101339994A (en) * | 2008-09-01 | 2009-01-07 | 罗绍华 | Preparation of multi-position doped lithium iron phosphate positive electrode material and application thereof |
| CN101447564A (en) * | 2007-11-26 | 2009-06-03 | 比亚迪股份有限公司 | Preparation method of anode active material of lithium ion secondary cell |
| CN101453019A (en) * | 2007-12-07 | 2009-06-10 | 比亚迪股份有限公司 | Positive pole active substance containing lithium iron phosphate, preparation, positive pole and battery thereof |
| CN101673823A (en) * | 2009-09-24 | 2010-03-17 | 福建师范大学 | Method for preparing lithium iron phosphate cathode material simultaneously blended with nickel and iodine by sintering method |
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| CN101447564A (en) * | 2007-11-26 | 2009-06-03 | 比亚迪股份有限公司 | Preparation method of anode active material of lithium ion secondary cell |
| CN101453019A (en) * | 2007-12-07 | 2009-06-10 | 比亚迪股份有限公司 | Positive pole active substance containing lithium iron phosphate, preparation, positive pole and battery thereof |
| CN101339994A (en) * | 2008-09-01 | 2009-01-07 | 罗绍华 | Preparation of multi-position doped lithium iron phosphate positive electrode material and application thereof |
| CN101673823A (en) * | 2009-09-24 | 2010-03-17 | 福建师范大学 | Method for preparing lithium iron phosphate cathode material simultaneously blended with nickel and iodine by sintering method |
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