CN101339994B - Preparation of multi-position doped lithium iron phosphate positive electrode material and application thereof - Google Patents
Preparation of multi-position doped lithium iron phosphate positive electrode material and application thereof Download PDFInfo
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- CN101339994B CN101339994B CN2008101464864A CN200810146486A CN101339994B CN 101339994 B CN101339994 B CN 101339994B CN 2008101464864 A CN2008101464864 A CN 2008101464864A CN 200810146486 A CN200810146486 A CN 200810146486A CN 101339994 B CN101339994 B CN 101339994B
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- Prior art keywords
- lithium
- compound
- doped
- phosphate
- doping
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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 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000007774 positive electrode material Substances 0.000 title claims description 8
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 67
- 150000001875 compounds Chemical class 0.000 claims description 37
- 229910052744 lithium Inorganic materials 0.000 claims description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 31
- 239000012298 atmosphere Substances 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 238000000498 ball milling Methods 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 23
- 229910052742 iron Inorganic materials 0.000 claims description 22
- 229910045601 alloy Inorganic materials 0.000 claims description 20
- 239000000956 alloy Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052748 manganese Inorganic materials 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- -1 rare earth lanthanide compound Chemical class 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 12
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 11
- 230000007704 transition Effects 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 229910052773 Promethium Inorganic materials 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- 229940062993 ferrous oxalate Drugs 0.000 claims description 9
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 9
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical group [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-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
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 4
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 4
- 229940116007 ferrous phosphate Drugs 0.000 claims description 4
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 4
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 4
- 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 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 4
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 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
- 239000002904 solvent Substances 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 230000007547 defect Effects 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 15
- 239000010405 anode material Substances 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 34
- 238000010438 heat treatment Methods 0.000 description 25
- 238000007599 discharging Methods 0.000 description 23
- 238000007789 sealing Methods 0.000 description 21
- 239000011572 manganese Substances 0.000 description 20
- 239000004677 Nylon Substances 0.000 description 19
- 229920001778 nylon Polymers 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000005338 frosted glass Substances 0.000 description 15
- 239000012299 nitrogen atmosphere Substances 0.000 description 15
- 230000004087 circulation Effects 0.000 description 13
- 239000006229 carbon black Substances 0.000 description 12
- 238000009413 insulation Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 230000002441 reversible effect Effects 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910010710 LiFePO Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
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- 229910052802 copper Inorganic materials 0.000 description 3
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
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- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
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- 239000000919 ceramic Substances 0.000 description 1
- 229960001759 cerium oxalate Drugs 0.000 description 1
- RWACICCRNCPMDT-UHFFFAOYSA-N cerium sulfuric acid Chemical compound [Ce].S(O)(O)(=O)=O RWACICCRNCPMDT-UHFFFAOYSA-N 0.000 description 1
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XKJJKZIBLKQSLH-UHFFFAOYSA-N gadolinium;nitric acid Chemical compound [Gd].O[N+]([O-])=O XKJJKZIBLKQSLH-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002601 lanthanoid compounds Chemical class 0.000 description 1
- OXHNIMPTBAKYRS-UHFFFAOYSA-H lanthanum(3+);oxalate Chemical compound [La+3].[La+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OXHNIMPTBAKYRS-UHFFFAOYSA-H 0.000 description 1
- OCHFTUIYQBBEPA-UHFFFAOYSA-N lithium;oxoiron Chemical compound [Li].[Fe]=O OCHFTUIYQBBEPA-UHFFFAOYSA-N 0.000 description 1
- YEMADIHSKBJUTM-UHFFFAOYSA-N lutetium;nitric acid Chemical compound [Lu].O[N+]([O-])=O YEMADIHSKBJUTM-UHFFFAOYSA-N 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- VOEZDMCKEMNFOS-UHFFFAOYSA-N manganese oxalic acid dihydrate Chemical compound O.O.[Mn].OC(=O)C(O)=O VOEZDMCKEMNFOS-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- ILOTUXNTERMOJL-UHFFFAOYSA-K thulium(iii) chloride Chemical compound Cl[Tm](Cl)Cl ILOTUXNTERMOJL-UHFFFAOYSA-K 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical compound Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a multi-place doped lithium iron phosphate anode material and an application thereof, which belongs to the technical field of the preparation of electrochemical power materials. The multi-place doped lithium iron phosphate anode material is expressed by the following formula: Li1-xAxFe1-yByP1-zCzO4Ddelta, wherein, at least two of x, y, z and delta can not be zero at the same time. Multi-place doped anode material lithium iron phosphate powder which is used in a secondary lithium-ion battery and has good crystallization performance and even composition is prepared by adopting a solid phase method and a simple mixing and drying process; compared with the method doping in a certain crystal lattice place, the multi-place doped anode material lithium iron phosphate powder has wide doping material source, which can greatly improve the basic capacity and cycling electrical performance of matrix and is applied to a stable industrialized production and non-high-purity materials. The multi-place lithium iron phosphate is taken as the anode material and is usually used in the secondary lithium-ion battery and the secondary lithium-ion battery taken as a power source.
Description
Technical field
The invention belongs to the electrochemical power source technical field of material.Be particularly related to as using a kind of multi-position doped lithium iron phosphate positive electrode material preparation method and the application thereof of secondary lithium battery and power source always with secondary lithium battery.
Background technology
In 1997 at first by J.B.Goodenough etc. at U.S. Pat A5, propose LiFePO in 910,382
4As the secondary lithium battery positive electrode.In the same year, M.Armand etc. are at U.S. Pat A6, disclose LiFePO in 514,640
4Carry out the material that mix in the iron position and phosphate potential substitutes.LiFePO
4Have cheap, nontoxic, nonhygroscopic, Environmental compatibility is fine, rich in mineral resources, multiple advantage such as capacity is higher, stability is fine.But the electronic conductivity of this material is relatively poor, has greatly limited the application of material under higher current density.In order to address this problem, at present report about improving the method for performance, mainly contain the surface and mix or coated with conductive material with carbon element or conductive metal particle, can improve the intergranular electronic conductivity of fertile material; Mix micro-high volence metal ion and partly replace Li
+Electronic conductivity in the parent lattice is improved in the position; Transition elements replaces Fe
2+The position, the ionic conductivity of raising material.From existing result, the method that adds electric conducting material can increase substantially the circulation volume of lithium iron phosphate positive material, particularly improves the rate capacities performance, and the doping effect of carrying out lithium position and iron position separately is limited.Simultaneously, because high-purity〉99.95% cost of material is relatively costly, thus use raw material to make the product property instability than low-purity, and according to the electronic ceramic knowhow, the performance that the introducing of many alloys and ratio optimization can stable prods.
Existing patent mostly is the doping vario-property on a certain lattice position of LiFePO4, as in the doping on the iron position: the relative lithium in iron position position excessive 10% in Chinese patent CN1585168A, two step solid phase calcination methods are introduced Cr salt in the iron position in an embodiment, obtain the LiFePO4 that chromium is mixed in the iron position.Iron position doping of Zn ion in Chinese patent CN1792780A is through two step solid phase calcination methods and sol-gal processes obtain the mixing LiFe of zinc ion
1-xZn
xPO
4Synthetic Li in Chinese patent CN1794497A
xFe
yM
zPO
4Compound, wherein dopant ion is one or both among Mg, Al, Ca, Ni, Zn, Cu, Ti, Mn, the Zr, relative scale is Li/ (Fe+Mn)=0.99-1.05, P/ (Fe+Mn)=1, Fe/Mn=9-99.Synthetic LiFe in Chinese patent CN1837033A
1-xM
xPO
4Compound, wherein dopant ion is at least a kind of among Al, Mg, Ti, Zr, Co, Ni, Mn, V, Nb, Rh, Ba, the Cr, doping M/Li＜0.3.Solid phase synthesis LiFe among the Chinese patent CN1921187A
0.99M
0.01PO
4/ C compound, M is Cr, Zn, Ca in the formula.Adopt the synthetic LiFe of microwave among the Chinese patent CN101121508A
1-xM
xPO
4, M is La, Co, Ni, Mn, Cr, Cu, Nd, Pr, Gd, Ce, Mo in the formula, 0＜x＜0.1.Adopt coprecipitation introducing dopant ion Co, Ni, Mn to obtain LiFe among the Chinese patent CN101049922A
1-xM
xPO
4Compound.Adopt solution deposit to obtain LiFe among the Chinese patent CN1805181A
1-xM
xPO
4, M is Co, Ni, Mn, Cr in the formula, 0＜x＜0.1.Adopt dimolybdate salt to mix in the iron position among the Chinese patent CN101121510A, doping is 0.005 ~ 0.015.Adopt lanthanum or actinium compound to mix in the iron position among the Chinese patent CN101150191A, doping is 0.01 ~ 0.05.Utilize the compound LiFePO of oxide of rare earth element y and Ce among the Chinese patent CN1830764A
4, not forming doped compound, content is 0.05 ~ 0.1.
Doping on the oxygen position: the LiFe that proposes a kind of oxygen-containing vacancy among the Chinese patent CN1797823A
1-xM
xPO
4-yNz compound is introduced alloy simultaneously in iron position and oxygen position, and M comprises Li, Na, K, Cu, Ag.The inventor utilizes solid phase method to prepare oxygen place doped LiFePO4 LiFeP (M in Chinese patent CN1772604A
xO
4-x) (0≤x≤2), M comprises itrogenous organic substance, sulfurous organic compound or elemental sulfur, chlorine-containing compound and fluorochemical.
In the doping on the lithium position: the inventor utilizes solid phase method to prepare lithium position doped iron phosphate lithium Li in Chinese patent CN1785799A, Chinese patent CN1785800A
1-xM
xFePO
4, 0＜x≤0.05, dopant ion comprises the compound of the lanthanum except that the radioactivity promethium, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium in Co, Ni, Mn, the lanthanide series.
Doping on phosphate potential: the inventor provides a kind of at Chinese patent CN1785823A and partly replaces the synthetic LiFeP of phosphate potential by B, W, S and Si element
1-xM
xO
4Method, 0＜x≤0.5.Chinese patent CN101037195A utilizes solid phase method to prepare P site doped LiFe (P
1-xM
x) O
4Method, wherein M is Ge, Sn, Se, Te and Bi, 0＜x＜0.5.Adopt dimolybdate salt P site doped among the Chinese patent CN101121510A, doping is 0.005 ~ 0.015.
The present invention proposes to utilize solid phase method to synthesize multi-position doped lithium iron phosphate Li
1-xA
xFe
1-yB
yP
1-zC
zO
4D
δModified compound has improved the basic electrical property of this material, makes it be applicable to industrialization steady production and non-high-purity raw material.
Summary of the invention
The objective of the invention is in order to improve LiFePO
4The basic electrical property of class material makes it be applicable to industrialization steady production and non-high-purity raw material and a kind of multi-position doped lithium iron phosphate positive electrode material preparation method and application thereof is provided.Adopt LiFePO
4In the lattice in the parent position of lithium position, iron position, phosphate potential and oxygen position at least two cases be doped simultaneously, wherein lithium position alloy is the rare earth lanthanide compound, iron position alloy is the compound of transition elements Mn, Co, Ni and rare earth lanthanide, partly replace P elements with compound or the simple substance that contains B, W, S and Si element, oxygen group elements and halogens doped and substituted oxygen position.
The objective of the invention is to be achieved through the following technical solutions:
The invention provides a kind of multi-position doped lithium iron phosphate positive electrode material that is used for secondary lithium battery, with nominal composition formula Li
1-xA
xFe
1-yB
yP
1-zC
zO
4D
δExpression,
Wherein, mix and represent that with A A is a rare earth lanthanide except that the radioactivity promethium in the lithium position, corresponding to the rare earth lanthanide compound, and doping scope 0≤x≤0.05;
Mix and to represent with B in the iron position, B be transition elements Mn, Co, Ni and except that the radioactivity promethium rare earth lanthanide, corresponding to the compound of transition elements Mn, Co, Ni and rare earth lanthanide, doping scope 0≤y≤0.05;
P site dopedly represent that with C C is B, W, S and Si element, corresponding to the compound or the simple substance that contain B, W, S and Si element, doping scope 0≤z≤0.5;
Oxygen place dopedly represent that with D D is oxygen group elements and halogens, corresponding to the compound of oxygen group elements and halogens, doping scope 0≤δ≤2.
At least two can not be 0 simultaneously among x, y, z, the δ.
Mix and make up 6 kinds of combinations that comprise two different cases in each parent position provided by the invention: lithium iron, lithium phosphorus, lithia, iron phosphorus, iron oxygen and phosphorus oxygen; 4 kinds of combinations of three different cases: lithium iron phosphorus, lithium iron oxygen, lithium phosphorus oxygen and iron phosphorus oxygen; 1 kind of combination of four different cases: lithium iron phosphorus oxygen.
Described everybody doping combination does not comprise the only doping type on a case.
Described doping position corresponding element is that one or more corresponding elements mix in this position of mixing simultaneously.
Described synthetic alloy is compound or the non-stoichiometric compound that meets stoichiometric proportion.
When described synthetic alloy is the non-stoichiometric compound, relates to and do not wait the corresponding defect chemistry equation of electricity price doped and substituted to be:
The Li position:
(+3 valency A)
The Fe position:
(+3 valency A)
The P position:
(+3 valency C)
The doping of described oxygen position is a kind of nominal composition amount, does not represent the actual final doping that enters oxygen lattice position.
The multi-position doped lithium iron phosphate positive electrode preparation methods, synthesis mode comprises:
(1) the solid phase method synthesis mode of an alloy and a batch mixing of parent stock
Lithium position raw material, iron position raw material, phosphate potential raw material and oxygen place doped thing are pressed ((1-x) Li+xA): ((1-y) Fe+yB): ((1-z) P+zC): the molar ratio weighing raw material of D=1:1:1: δ, parent stock and alloy are in ratio batch mixing in solvent of 0≤x≤0.05,0≤y≤0.05,0≤z≤0.5 and 0≤δ≤2, adding ball-milling medium then mixes, 6～12 hours mixing and ball milling time is 40～70 ℃ of oven dry down; Oven dry back powder heats 400～550 ℃ under inert atmosphere or reducing atmosphere, be incubated 2～10 hours and carry out precalcining; Secondary ball milling 6～12 hours, 40～70 ℃ of following oven dry, under inert atmosphere or reducing atmosphere, 550～850 ℃ of secondary clacinings must nominal composition formula be Li then
1-xA
xFe
1-yB
yP
1-zC
zO
4D
δThe multi-position doped lithium iron phosphate powder.
(2) the solid phase method synthesis mode that mixes with the pre-imitation frosted glass that mixes in other parent positions of oxygen place doped thing
Lithium position raw material, iron position raw material and phosphate potential raw material are pressed ((1-x) Li+xA): ((1-y) Fe+yB): the molar ratio weighing raw material of ((1-z) P+zC)=1:1:1, parent stock and alloy are in ratio batch mixing in solvent of 0≤x≤0.05,0≤y≤0.05,0≤z≤0.5, adding ball-milling medium then mixes, 6～12 hours mixing and ball milling time is 40～70 ℃ of oven dry down; Oven dry back powder heats 400～550 ℃ under inert atmosphere or reducing atmosphere, be incubated 2～10 hours and carry out precalcining; Secondary ball milling 6～12 hours, 40～70 ℃ of oven dry down, obtaining composition formula is Li
1-xA
xFe
1-yB
yP
1-zC
zO
4The pre-imitation frosted glass of parent; Again with pre-imitation frosted glass of parent and oxygen place doped thing D, mixed 6～12 hours in 0≤δ≤2 ratio ball millings, 40～70 ℃ of oven dry down, then under inert atmosphere or reducing atmosphere, 550～850 ℃ of secondary clacinings, obtaining nominal composition formula is Li
1-xA
xFe
1-yB
yP
1-zC
zO
4D
δThe multi-position doped lithium iron phosphate powder.
Described mixed solvent is at least a in deionized water, industrial alcohol and the absolute ethyl alcohol.
Be situated between at least a in zirconia ball, alumina balls, agate ball, stainless steel ball and the polyurethane ball of described mixer mill.
Described inert atmosphere or reducing atmosphere are nitrogen, argon gas, at least a in the nitrogen and hydrogen mixture.
Described lithium position raw material is Li
2CO
3, lithium oxalate, at least a among lithium acetate and the LiOH.
The purity of described lithium position raw material comprises technical grade 99.2%, LITHIUM BATTERY 〉=99.5% and high-purity level 〉=99.9%.
Described ferrous salt is a ferrous oxalate, and ferrous acetate is at least a in frerrous chloride, ferrous sulfate, the ferrous phosphate.
Described phosphate comprises ammonium phosphate, diammonium hydrogen phosphate, and ammonium dihydrogen phosphate, at least a in the ferrous phosphate.
Described lithium position alloy is at least a in oxide, hydroxide, chloride, nitrate, sulfate, carbonate, fluoride and the organic salt of the lanthanum except that the radioactivity promethium, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium in the lanthanide series.
Described iron position alloy is at least a in the compound except that the radioactivity promethium in transition elements Mn, Co, Ni compound and the lanthanide series.Transition elements Mn, Co, Ni compound comprise oxide, hydroxide, chloride, nitrate, sulfate, carbonate and the organic salt of transition elements Mn, Co, Ni, and lanthanide compound comprises oxide, hydroxide, chloride, nitrate, sulfate, carbonate, fluoride and the organic salt of the lanthanum except that the radioactivity promethium, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium in the lanthanide series.
Described P site doped thing is at least a in boron-containing compound, Tungstenic compound, sulfurous organic compound, sulphur simple substance and the silicon-containing compound.Boron-containing compound comprises boric acid, trimethylborate and boron oxide, Tungstenic compound comprises wolframic acid and ammonium tungstate, sulfur-containing compound comprises thiocarbamide, vulcanized sodium and ammonium sulfide, and silicon-containing compound comprises silica gel, tetraethoxysilane, methyl triethoxysilane and silicochloroform.
Described oxygen place doped thing is at least a in itrogenous organic substance, sulfur-containing compound, sulphur simple substance, chlorine-containing compound and the fluorochemical.Itrogenous organic substance is a urea.Chlorine-containing compound is ammonium chloride, sodium chloride.Fluorochemical is ammonium fluoride, lithium fluoride.
Described multi-position doped lithium iron phosphate positive electrode material is applied to the preparation technology of lithium battery, with multi-position doped lithium iron phosphate powder and conductive carbon black, Kynoar, press (9～16): (0.875～2.2): 1 mass ratio is coated on the collector aluminium flake after grinding evenly, make electrode slice, with the metal lithium sheet is negative pole, to press 1.0mol/L LiPF
6Concentration is dissolved in and is electrolyte in ethyl carbonate that volume ratio is 1:1 and the dimethyl carbonate mixed solvent, and polypropylene microporous film is a barrier film, is assembled into simulation secondary lithium-ion rechargeable battery; The system of discharging and recharging of respective battery is: press the 0.05-0.2C multiplying power at 2.5V-4.2V constant current charge-discharge under voltage.
The invention has the beneficial effects as follows and utilize the solid phase method that is easy to commercially produce, alloy is drawn materials extensively, through the simple stoving process that mixes, by control heat treatment temperature and time, it is good to prepare crystal property, composition is even, multi-position doped type secondary lithium battery LiFePO 4 of anode material powder, and first discharge specific capacity is greater than 100mAh/g under the room temperature.Compare with independent some lattices position doping route, the present invention not only can significantly improve parent basis capacity and cycle electric performance, be applicable to the industrialization steady production simultaneously and adapt to non-high-purity raw material, has wide application prospect at secondary lithium battery, particularly power source commonly used with the cell positive material field.
Adopt multidigit LiFePO4 of the present invention to be applicable to that as the secondary lithium battery of positive electrode various mobile electronic devices maybe need the equipment of mobile driven by energy, fields such as mobile phone, notebook computer, portable video recorder, electronic toy, electric tool, mining light fixture, electric bicycle, electric automobile, hybrid vehicle, automobile starting storage battery, accumulation power supply for example, and be not limited to this.
Embodiment
Below by embodiment, further illustrate outstanding feature of the present invention and marked improvement, only be the present invention is described and never limit the present invention.
Embodiment 1
With 0.0495 mole of pure Lithium Carbonate Li
2CO
3, 0.0005 mole of nine water lanthanum oxalate La
2(C
2O
4)
39H
2O, 0.099 mole of ferrous oxalate Fe (C
2O
4) 2H
2O, 0.001 mole of four water cobalt oxalate Co (C
2O
4) 4H
2O, 0.098 mole of phosphoric acid ammonium dihydrogen NH
4H
2PO
4With 0.002 mole of boric acid H
3BO
3Mix, add in the nylon jar, add the 25ml absolute alcohol, sealing back is that ball-milling medium mixed 60 ℃ of oven dry then 6 hours with the zirconia on planetary ball mill, sieve, under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute heating rates, this temperature insulation 8 hours, be cooled to room temperature with stove, take out pre-imitation frosted glass and add 0.4 mole of thiocarbamide in the nylon jar, add an amount of absolute alcohol, sealing back ball milling 10 hours, 70 ℃ of oven dry, sieve, then under 0.3 liter/minute nitrogen atmosphere, rise to 700 ℃ with 4 ℃/minute heating rates, be incubated 8 hours, cool to room temperature with the furnace, obtaining nominal composition formula is Li
0.99La
0.01Fe
0.99Co
0.01P
0.98B
0.02O
4S
0.4The positive electrode powder.
The chemical property of gained sample is measured as follows: take by weighing the 0.9g positive powder, add the 0.19g carbon black, the 0.096g Kynoar is made dispersant with absolute ethyl alcohol, supersonic oscillations are mixed 30min, make it fully to mix, after 80 ℃ of dryings, add N-methyl pyrrolidone furnishing slurry, be coated on equably on the collector aluminium foil, after 80 ℃ of dryings, on roll squeezer, flatten, make the anode thin film of the about 200 μ m of thickness.On anode thin film, go out 1cm
2The size disk, after weighing, with it more than 140 ℃ of vacuumize 12h, behind the vacuum tank natural cooling, as backup electrode.Electrolyte adopts 1mol/L LiPF
6Ethyl carbonate EC: dimethyl carbonate DMC (1:1) mixed liquor; Polypropylene microporous film is a barrier film; Metal lithium sheet is as negative pole.Packaged battery in the glove box of argon gas atmosphere, ageing 6 hours charges to 4.2 volts by the speed of 20mA/g (in positive pole), is discharged to 2.5 volts, and discharge curve obtains the discharge voltage plateau of 3.35V first, and reversible specific capacity is about 110mAh/g first.Specific discharge capacity is greater than 110mAh/g after 20 circulations.
Embodiment 2
With 0.1 mole of LITHIUM BATTERY lithium acetate CH
3COOLi, 0.098 mole of frerrous chloride FeCl
2, 0.001 mole of nine water cerium oxalate Ce
2(C
2O
4)
39H
2O, 0.09 mole of phosphoric acid hydrogen, two ammoniums and 0.01 mole of wolframic acid H
2WO
4Mix, add in the nylon jar, add the 75ml absolute alcohol, sealing back on planetary ball mill is that mill is situated between and mixed 5 hours with alumina balls, after 50 ℃ of oven dry of discharging under 0.3 liter/minute argon gas atmosphere, rise to 450 ℃ with 5 ℃/minute heating rates, be incubated 9 hours, cool to room temperature with the furnace, obtain pre-imitation frosted glass, with the industrial alcohol is medium ball milling 9 hours, under 0.3 liter/minute argon gas atmosphere, rise to 720 ℃ after 65 ℃ of oven dry of discharging, be incubated 7 hours with 4 ℃/minute heating rates, cool to room temperature with the furnace, obtaining nominal composition formula is LiFe
0.98Ce
0.02P
0.9W
0.1O
4The positive electrode powder.
Take by weighing the 1.125g positive powder, add the 0.169g carbon black, 0.12g Kynoar, press embodiment 1 method system electrode slice and assembled battery, speed by 30mA/g (in positive pole) charges to 4.2 volts, be discharged to 2.5 volts, discharge curve obtains the stable discharge voltage plateau of 3.35V, reversible specific capacity 108mAh/g first first.Specific discharge capacity remains on more than the 110mAh/g after 20 circulations.
Embodiment 3
With 0.096 mole of lithium hydroxide in industrial grade LiOHH
2O, 0.002 mole of oxalic acid europium Eu
2(C
2O
4)
310H
2O, ferrous, the 0.0024 mole of oxalic acid dihydrate manganese Mn (C of 0.0976 molar acetate
2O
4) 2H
2O, 0.1 mole of phosphoric acid ammonium (NH
4)
3PO
4Mix and add in the nylon jar, add the 70ml industrial alcohol, sealing back is that mill Jie ball milling mixed 7 hours with the stainless steel ball on planetary ball mill, after 50 ℃ of oven dry of discharging under 0.3 liter/minute nitrogen atmosphere, rise to 480 ℃ with 5 ℃/minute heating rates, be incubated 5 hours, cool to room temperature with the furnace, obtaining pre-imitation frosted glass, is medium ball milling 11 hours with the industrial alcohol, after 60 ℃ of oven dry of discharging under 0.3 liter/minute nitrogen atmosphere, rise to 650 ℃ with 4 ℃/minute heating rates, be incubated 4 hours, be cooled to room temperature with stove, obtaining nominal composition formula is Li
0.96Eu
0.04Fe
0.976Mn
0.024PO
4Positive electrode.
Take by weighing the above-mentioned positive electrode powder of 0.9g, add the 0.19g carbon black, the 0.096g Kynoar, press embodiment 1 method system electrode slice and assembled battery, speed by 25mA/g (in positive pole) charges to 4.2 volts, is discharged to 2.5 volts, and reversible first specific discharge capacity is about 117mAh/g.Through 20 circulations, specific discharge capacity remains on more than the 118mAh/g.
Embodiment 4
With 0.0495 mole of battery-level lithium carbonate Li
2CO
3, 0.001 mole of praseodymium chloride PrCl
30.1 mole ferrous oxalate, 0.1 mole of phosphoric acid ammonium dihydrogen and 0.15 mole of urea are mixed, add in the nylon jar, add the 25ml absolute alcohol, sealing back on planetary ball mill is that mill is situated between and mixed 6 hours with the agate ball, after 40 ℃ of oven dry of discharging under 0.3 liter/minute argon gas atmosphere, rise to 500 ℃ with 5 ℃/minute heating rates, this temperature insulation 4 hours, be cooled to room temperature with stove, taking out pre-imitation frosted glass is incorporated in the nylon jar, add appropriate amount of deionized water, sealing back ball milling 12 hours, after 70 ℃ of oven dry of discharging under 0.3 liter/minute argon gas atmosphere, rise to 680 ℃ with 4 ℃/minute heating rates, be incubated 11 hours, cool to room temperature with the furnace, obtaining nominal composition formula is Li
0.99Pr
0.01FePO
4N
1.5Positive electrode.
Take by weighing the 0.9g positive powder, add the 0.204g carbon black, 0.096g Kynoar, press embodiment 1 method system electrode slice and assembled battery, speed by 20mA/g (in positive pole) charges to 4.2 volts, be discharged to 2.5 volts, discharge curve obtains the stable discharge voltage plateau of 3.38V first, and reversible specific capacity is about 109mAh/g first.After 20 circulations, specific discharge capacity remains on about 110mAh/g.
Embodiment 5
With 0.05 mole of lithium carbonate, 0.097 mole of ferrous oxalate, 0.003 mole of six water nitric acid nickel (NO
3)
26H
2O and 0.1 mole of phosphoric acid ammonium dihydrogen mix, add in the nylon jar, add the 25ml industrial alcohol, sealing back on planetary ball mill is that mill is situated between and mixed 7 hours with the stainless steel, after 50 ℃ of oven dry of discharging under 0.3 liter/minute nitrogen atmosphere, rise to 550 ℃ with 5 ℃/minute heating rates, this temperature insulation 2 hours, be cooled to room temperature with stove, take out pre-imitation frosted glass and put into the nylon jar with 0.03 mole of ammonium fluoride, add appropriate amount of deionized water, sealing back ball milling 7 hours, after 65 ℃ of oven dry of discharging under 0.3 liter/minute nitrogen atmosphere, rise to 580 ℃ with 4 ℃/minute heating rates, this temperature insulation 10 hours, cool to room temperature with the furnace, obtaining nominal composition formula is LiFe
0.97Ni
0.03PO
4F
0.3Positive electrode.
Take by weighing the 0.3375g positive powder, add the 0.0765g carbon black, 0.036g Kynoar, press embodiment 1 method system electrode slice and assembled battery, speed by 34mA/g (in positive pole) charges to 4.2 volts, be discharged to 2.5 volts, battery discharge curve first obtains the discharge voltage plateau of 3.3V, and reversible specific capacity is about 115mAh/g first.After 20 circulations, specific discharge capacity remains on more than the 112mAh/g.
Embodiment 6
With 0.098 moles of hydrogen lithia LiOHH
2O, 0.001 mole of samarium oxide (Sm
2O
3), the ferrous FeSO of 0.1 mol sulfuric acid
47H
2O, 0.8 mole of phosphoric acid hydrogen, two ammoniums and 0.2 mole of tetraethoxysilane Si (OC
2H
5)
4Mix, add in the nylon jar, add the 30ml absolute alcohol, sealing back on planetary ball mill is that mill is situated between and mixed 5 hours with the zirconia, under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ after 45 ℃ of oven dry of discharging, this temperature insulation 8 hours with 5 ℃/minute heating rates, cool to room temperature with the furnace, take out pre-imitation frosted glass and be incorporated in the nylon jar, add an amount of industrial alcohol, sealing back ball milling 8 hours, after 50 ℃ of oven dry of discharging at 0.3 liter/minute nitrogen and hydrogen mixture atmosphere (nitrogen: hydrogen=9:1, volume ratio) under, rises to 780 ℃, be incubated 7 hours with 4 ℃/minute heating rates, cool to room temperature with the furnace, obtaining nominal composition formula is Li
0.98Sm
0.02FeP
0.8Si
0.2O
4Positive electrode.
Take by weighing the 1.5g positive powder, add the 0.255g carbon black, 0.12g Kynoar, press embodiment 1 method system electrode slice and assembled battery, speed by 10mA/g (in positive pole) charges to 4.2 volts, be discharged to 2.5 volts, the discharge curve first of battery has the discharge voltage plateau of 3.3V, and reversible specific capacity is about 120mAh/g first.After 20 circulations, specific discharge capacity remains on more than the 121mAh/g.
Embodiment 7
With 0.1 moles of hydrogen lithia, 0.1 mole ferrous oxalate, 0.09 mole of phosphoric acid ammonium, 0.01 mole simple substance sublimed sulfur S mixes, add in the nylon jar, add the 25ml absolute alcohol, sealing back on planetary ball mill is that mill is situated between and mixed 7 hours with the aluminium oxide, after 60 ℃ of oven dry of discharging under 0.3 liter/minute argon gas atmosphere, rise to 500 ℃ with 5 ℃/minute heating rates, this temperature insulation 3 hours, be cooled to room temperature with stove, take out pre-imitation frosted glass and put into the nylon jar with 0.08 mole of ammonium chloride, add appropriate amount of deionized water, sealing back ball milling 10 hours, after 70 ℃ of oven dry of discharging under 0.3 liter/minute argon gas atmosphere, rise to 650 ℃ with 4 ℃/minute heating rates, this temperature insulation 6 hours, cool to room temperature with the furnace, obtaining nominal composition formula is Li FeP
0.9S
0.1O
4Cl
0.8The positive electrode powder.
Take by weighing the 0.33g positive powder, add the 0.028g carbon black, 0.032g Kynoar, press embodiment 1 method system electrode slice and assembled battery, speed by 20mA/g (in positive pole) charges to 4.2 volts, be discharged to 2.5 volts, the discharge curve first of battery has the stable discharge voltage plateau of 3.35V, and reversible specific capacity is about 125mAh/g first.After 20 circulations, specific discharge capacity remains on more than the 118mAh/g.
Embodiment 8
With 0.0485 mole of lithium carbonate, 0.0015 mole of oxalic acid europium Eu
2(C
2O
4)
310H
2O, 0.098 mole of ferrous oxalate, 0.002 mole of dysprosium chloride DyCl
3, 0.07 mole of phosphoric acid hydrogen, two ammonium (NH
4)
2HPO
4With 0.03 mole of trimethylborate (CH
3O)
3B mixes, add in the nylon jar, add the 25ml absolute alcohol, sealing back serves as that mill is situated between and mixed 6 hours with the polyurethane ball on planetary ball mill, after 40 ℃ of oven dry of discharging under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute heating rates,, be cooled to room temperature with stove this temperature insulation 8 hours, take out pre-imitation frosted glass and put into the nylon jar, add an amount of absolute alcohol, sealing back ball milling 6 hours, after 40 ℃ of oven dry of discharging under 0.3 liter/minute nitrogen atmosphere, rise to 800 ℃ with 4 ℃/minute heating rates, be incubated 4 hours, cool to room temperature with the furnace, obtaining nominal composition formula is Li
0.97Eu
0.03Fe
0.98Dy
0.02P
0.7B
0.3O
4The positive electrode powder.
Take by weighing the 0.97g positive powder, add the 0.104g carbon black, 0.096g Kynoar, press embodiment 1 method system electrode slice and assembled battery, speed by 20mA/g (in positive pole) charges to 4.2 volts, be discharged to 2.5 volts, the discharge curve first of battery has the discharge voltage plateau of the inclination of 3.3V, and reversible specific capacity is about 101mAh/g first.After 20 circulations, specific discharge capacity remains on more than the 100mAh/g.
Embodiment 9
With 0.095 molar nitric acid lithium, 0.005 molar nitric acid lutetium Lu (NO
3)
3, 0.098 mole of frerrous chloride, 0.002 mole of CoCL2 CoCl
26H
2O and 0.1 mole of phosphoric acid ammonium dihydrogen mix, add in the nylon jar, add the 55ml industrial alcohol, sealing back on planetary ball mill is that mill is situated between and mixed 7 hours with the agate ball, after 55 ℃ of oven dry of discharging under 0.3 liter/minute nitrogen atmosphere, rise to 550 ℃ with 5 ℃/minute heating rates, be incubated 2 hours, be cooled to room temperature with stove, take out pre-imitation frosted glass and add 0.04 mole of thiocarbamide in the nylon jar, add an amount of industrial alcohol, sealing back ball milling 6 hours, after 65 ℃ of oven dry of discharging under 0.3 liter/minute nitrogen atmosphere, rise to 850 ℃ with 4 ℃/minute heating rates, this temperature insulation 2 hours, cool to room temperature with the furnace, obtaining nominal composition formula is Li
0.95Lu
0.05Fe
0.98Co
0.02PO
4S
0.4The positive electrode powder.
Take by weighing the 0.537g positive powder, add the 0.066g carbon black, the 0.036g Kynoar, press embodiment 1 method system electrode slice and assembled battery, speed in 34mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 110mAh/g of battery.Through 20 circulations, specific discharge capacity remains on more than the 105mAh/g.
Embodiment 10
With 0.098 molar acetate lithium CH
3COOLi, 0.002 mole of thulium chloride TmCl
3, 0.1 mole of ferrous oxalate, 0.094 mole of phosphoric acid ammonium (NH
4)
3PO
4, 0.001 mole of ammonium tungstate N
5H
37W
6O
24H
2O mixes, add in the nylon jar, add the 55ml industrial alcohol, sealing back on planetary ball mill is that mill is situated between and mixed 7 hours with the stainless steel ball, after 50 ℃ of oven dry of discharging under 0.3 liter/minute decomposed ammonia atmosphere, rise to 480 ℃ with 5 ℃/minute heating rates,, be cooled to room temperature with stove this temperature insulation 5 hours, take out pre-imitation frosted glass and add 0.05 mole of urea in the polyester jar, add an amount of absolute alcohol, sealing back ball milling 6 hours, after 40 ℃ of oven dry of discharging under 0.3 liter/minute nitrogen atmosphere, rise to 680 ℃ with 4 ℃/minute heating rates, be incubated 8 hours, be cooled to room temperature with stove, obtaining nominal composition formula is Li
0.98Tm
0.02FeP
0.94W
0.06O4N
0.5The positive electrode powder.
Take by weighing the 1.02g positive powder, add the 0.184g carbon black, 0.096g Kynoar, press embodiment 1 method system electrode slice and assembled battery, speed by 34mA/g (in positive pole) charges to 4.2 volts, be discharged to 2.5 volts, the discharge curve first of battery has the stable discharge voltage plateau of 3.37V, and reversible specific capacity is about 117mAh/g first.After 20 circulations, specific discharge capacity remains on about 115mAh/g.
Embodiment 11
With 0.05 mole of lithium carbonate, 0.098 mole of frerrous chloride FeCl
2, 0.002 mole of six water manganese nitrate Mn (NO
3)
26H
2O and 0.075 mole of phosphoric acid ammonium, 0.025 mole of silica gel and 0.15 mole of urea are mixed, add in the nylon jar, add the 100ml deionized water, sealing back serves as that mill is situated between and mixed 6 hours with the polyurethane ball on planetary ball mill, after 70 ℃ of oven dry of discharging under 0.3 liter/minute nitrogen atmosphere, rise to 420 ℃ with 5 ℃/minute heating rates,, be cooled to room temperature with stove this temperature insulation 8 hours.Take out pre-imitation frosted glass, add an amount of industrial alcohol, sealing back ball milling 6 hours, under 0.3 liter/minute nitrogen atmosphere, rise to 750 ℃ after 60 ℃ of oven dry of discharging, this temperature insulation 6 hours with 4 ℃/minute heating rates, be cooled to room temperature with stove, obtaining nominal composition formula is LiFe
0.98Mn
0.02P
0.75Si
0.25O
4N
1.5The positive electrode powder.
Take by weighing the 0.49g positive powder, add the 0.068g carbon black, 0.032g Kynoar, press embodiment 1 method system electrode slice and assembled battery, speed by 20mA/g (in positive pole) charges to 4.2 volts, be discharged to 2.5 volts, the discharge curve first of battery has the stable discharge voltage plateau of 3.38V, and reversible specific capacity is about 118mAh/g first.After 20 circulations, specific discharge capacity remains on more than the 113mAh/g.
Embodiment 12
With 0.0275 mole of lithium carbonate, 0.005 mol sulfuric acid cerium Ce (SO
4)
22H
2O and 0.04 mole of lithium fluoride, 0.098 mole of ferrous oxalate, 0.001 molar nitric acid gadolinium Gd (NO
3)
3, 0.001 mole of manganese carbonate MnCO
3, 0.08 mole of phosphoric acid ammonium dihydrogen, 0.01 mole of boric acid H
3BO
3, 0.01 mole of wolframic acid H
2WO
4Mix, add in the nylon jar, add the 100ml absolute alcohol, sealing back on planetary ball mill is that mill is situated between and mixed 11 hours with the stainless steel ball, after 40 ℃ of oven dry of discharging under 0.3 liter/minute nitrogen atmosphere, rise to 480 ℃ with 5 ℃/minute heating rates, be incubated 5 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with the absolute alcohol is medium ball milling 5 hours, under 0.3 liter/minute decomposed ammonia atmosphere, rise to 680 ℃ after 40 ℃ of oven dry of discharging, be incubated 8 hours with 4 ℃/minute heating rates, be cooled to room temperature with stove, obtaining nominal composition formula is Li
0.95Ce
0.05Fe
0.98Gd
0.01Mn
0.01P
0.8B
0.1W
0.1O
4F
0.4The positive electrode powder.
Take by weighing 0.96g positive electrode powder, add the 0.16g carbon black, the 0.096g Kynoar, press embodiment 1 method system electrode slice and assembled battery, speed in 10mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 137mAh/g of battery.Through 20 circulations, specific discharge capacity remains on more than the 130mAh/g.
Claims (4)
1. multi-position doped lithium iron phosphate positive electrode material, this positive electrode is with nominal composition formula Li
1-xA
xFe
1-yB
yP
1-zC
zO
4D
δExpression, one or more elements mix in same doping position; It is characterized in that its doping is to adopt LiFePO
4In the lattice in lithium position, iron position, phosphate potential and the oxygen position a plurality of parents position be doped simultaneously, wherein lithium position alloy is at least a in the rare earth lanthanide compound; Described rare earth lanthanide compound comprises oxide, hydroxide, chloride, nitrate, sulfate, carbonate, fluoride and the organic salt of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium in the lanthanide series except that the radioactivity promethium; Iron position alloy is at least a in the compound except that the radioactivity promethium in transition elements Mn, Co, Ni compound and the lanthanide series, and described transition elements Mn, Co, Ni compound comprise in oxide, hydroxide, chloride, nitrate, sulfate, carbonate and the organic salt of transition elements Mn, Co, Ni at least a;
Mix and represent that with A A is a rare earth lanthanide except that the radioactivity promethium in the lithium position, corresponding to above-mentioned lithium position alloy, doping scope 0≤x≤0.05;
Mix and represent that with B B is transition elements Mn, Co, Ni and at least a in the rare earth lanthanide except that the radioactivity promethium, corresponding to above-mentioned iron position alloy, doping scope 0≤y≤0.05 in the iron position;
P site dopedly represent that with C C is at least a in B, W, S and the Si element, corresponding to the compound or the simple substance that contain B, W, S and Si element, doping scope 0≤z≤0.5;
Oxygen place dopedly represent that with D D is at least a in oxygen group elements and the halogens, corresponding to the compound of oxygen group elements and halogens, doping scope 0≤δ≤2;
And at least two can not be 0 simultaneously among x, y, z, the δ.
2. according to the described multi-position doped lithium iron phosphate positive electrode material of claim 1, it is characterized in that, described alloy is compound or the non-stoichiometric compound that meets stoichiometric proportion, when described synthesizing blender thing is the non-stoichiometric compound, relates to and do not wait the corresponding defect chemistry equation of electricity price doped and substituted to be:
The Li position:
The Fe position:
The P position:
The doping of above-mentioned oxygen position is a kind of nominal composition amount, does not represent the actual final doping that enters oxygen lattice position.
3. described multi-position doped lithium iron phosphate positive electrode preparation methods of claim 1, adopt the solid phase method synthesis mode of an alloy and a batch mixing of parent stock synthetic, alloy and parent stock are added ball-milling medium to be mixed, 6～12 hours mixing and ball milling time is 40～70 ℃ of oven dry down; Oven dry back powder heats 400～550 ℃ under inert atmosphere or reducing atmosphere, be incubated 2～10 hours and carry out precalcining; Secondary ball milling 6～12 hours, 40～70 ℃ of following oven dry, under inert atmosphere or reducing atmosphere, 550～850 ℃ of secondary clacinings must nominal composition formula be Li then
1-xA
xFe
1-yB
yP
1-zC
zO
4D
δThe multi-position doped lithium iron phosphate powder; It is characterized in that, lithium position raw material, iron position raw material, phosphate potential raw material and oxygen place doped thing are pressed ((1-x) Li+xA): ((1-y) Fe+yB): ((1-z) P+zC): the molar ratio weighing raw material of D=1: 1: 1: δ, parent stock and alloy are in ratio batch mixing in solvent of 0≤x≤0.05,0≤y≤0.05,0≤z≤0.5 and 0≤δ≤2.
4. according to the described multi-position doped lithium iron phosphate positive electrode preparation methods of claim 3, it is characterized in that the raw material of described each parent position is:
Described lithium position raw material is Li
2CO
3, lithium oxalate, at least a among lithium acetate and the LiOH, the purity of its raw material comprises technical grade 99.2%, LITHIUM BATTERY 〉=99.5% and high-purity level 〉=99.9%;
Described iron position raw material is at least a in ferrous oxalate, ferrous acetate, frerrous chloride, ferrous sulfate, the ferrous phosphate;
Described phosphate potential raw material is an ammonium phosphate, diammonium hydrogen phosphate, and ammonium dihydrogen phosphate, at least a in the ferrous phosphate;
Described oxygen place doped thing is at least a in itrogenous organic substance, sulfur-containing compound, sulphur simple substance, chlorine-containing compound and the fluorochemical; Wherein itrogenous organic substance is a urea; Chlorine-containing compound is ammonium chloride, sodium chloride; Fluorochemical is ammonium fluoride, lithium fluoride.
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