CN1208241C - Wet chemistry method for preparing lithium iron phosphate - Google Patents
Wet chemistry method for preparing lithium iron phosphate Download PDFInfo
- Publication number
- CN1208241C CN1208241C CNB031026656A CN03102665A CN1208241C CN 1208241 C CN1208241 C CN 1208241C CN B031026656 A CNB031026656 A CN B031026656A CN 03102665 A CN03102665 A CN 03102665A CN 1208241 C CN1208241 C CN 1208241C
- Authority
- CN
- China
- Prior art keywords
- phosphate
- lithium
- iron
- source compound
- compound containing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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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 22
- 238000007704 wet chemistry method Methods 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000012298 atmosphere Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims abstract description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 19
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000006229 carbon black Substances 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 11
- 239000006258 conductive agent Substances 0.000 claims description 11
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 11
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 5
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 5
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 5
- 235000019800 disodium phosphate Nutrition 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 235000011089 carbon dioxide Nutrition 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 4
- 239000011858 nanopowder Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 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
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract 4
- 229910052493 LiFePO4 Inorganic materials 0.000 abstract 2
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 19
- 229910010710 LiFePO Inorganic materials 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 12
- 235000019241 carbon black Nutrition 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 238000003860 storage Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 238000000295 emission spectrum Methods 0.000 description 8
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000004254 Ammonium phosphate Substances 0.000 description 6
- 235000019289 ammonium phosphates Nutrition 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- -1 Fe (III) compound Chemical class 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000003836 solid-state method Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910009891 LiAc Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000005285 chemical preparation method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention belongs to a wet chemical method of directly obtaining precursors by precipitation reaction to prepare lithium iron phosphate (LiFePO4) of positive material of a lithium ion battery. A compound containing a Li source, a compound containing an iron source, a compound containing a phosphorus source, a compound containing doped elements or electric conducting agent, and the solution or suspension liquid of a precipitation agent are mixed and react for 0.5 to 24 h in a hermetic stirred reactor at the temperature of 5 to 120 DEGC, the reacted mixture is filtered, washed and dried to obtain nanometer precursors, wherein the concentration of the compound containing a Li source, the compound containing an iron source and the compound containing a phosphorus source is from 0.1 to 3.0 mol/L; the nanometer precursors are placed in a high temperature furnace, in a non air or non oxidizing atmosphere, the nanometer precursors are heated at the heating rate of 1 to 30 DEG C /min, are roasted for 5 to 48h at the temperature of 500 to 800 DEGC, and are cooled at the detemperature rate of 1 to 20 DEG C /min, namely cooling in furnace, and the nanometer powder of lithium iron phosphate is prepared. The present invention effectively controls the chemical components, the phase compositions and the particle diameter of LiFePO4, improves the evenness and the electrical conductivity, and improves the electrochemical property, and meanwhile, the present invention reduces the material cost, simplifies the synthesis process, and can be implemented on industry easily.
Description
Technical field
The invention belongs to a kind of preparation method of anode material for lithium-ion batteries, particularly a kind of presoma that directly obtains with precipitin reaction prepares lithium ion battery anode material lithium iron phosphate (LiFePO
4) wet chemical method.
Background technology
In the research of lithium ion battery, has α-NaFeO
2The material of type structure is the focus of research always.These materials comprise LiCoO
2, LiNiO
2, LiMnO
2And LiVO
2Deng.LiCoO
2It is the positive electrode material that present commercialization lithium ion battery uses, it has high theoretical specific storage (274mAh/g) and excellent cycle performance, but its actual specific capacity has only about 140mAh/g, when when charging lithium deviate from amount greater than 55% the time, material structure is destroyed and reduce its cycle performance, in addition, cobalt is lower in natural abundance, and price is more expensive; For LiNiO
2The problem that exists is more, and it also has safety issue except synthetic difficulty and unstable under full-charge state; In recent years, safety issue and the price problem of people in order to solve lithium ion battery is to having the LiMn of spinel structure
2O
4Carried out a large amount of research.LiMn
2O
4Though application can solve LiCoO
2Price problem and LiNiO
2Safety problem, but the capacity attenuation under the high temperature (55 ℃) makes it also have certain distance from practicality.Therefore, the cheap positive electrode material of excellent property is the emphasis of Study on Li-ion batteries using exploitation always.
Since report lithium ion in 1997 can be at olivine-type LiFePO
4In reversible take off embedding after, it just has been subjected to widely paying attention to, and is considered to the anode material for lithium-ion batteries that the utmost point has application potential.LiFePO
4Theoretical capacity is about 170mAh/g, and discharge platform is 3.4V, has good performance and the safety performance followed.But following shortcoming has hindered its practical application: Fe during (1) is synthetic
2+Easily be oxidized to Fe
3+, be difficult to obtain monophasic LiFePO
4(2) lithium ion is at LiFePO
4Middle diffusion difficulty causes the utilization ratio of active material low; (3) LiFePO
4The specific conductivity of itself is low, causes its high-rate discharge ability relatively poor.Existing result of study shows that the following aspects can improve LiFePO
4Performance: (1) adopts inert environments to suppress Fe
2+Oxidation, (2) synthesizing nano-particle improves the middle diffusibility of lithium ion at material, (3) improve specific conductivity by adding conductive agent.
LiFePO
4Synthetic method mainly contain high-temperature solid phase reaction method, hydrothermal method and liquid-phase oxidation reduction method.
High-temperature solid phase reaction method is with FeC
2O
4H
2O, FeAc
2, (NH
4)
2HPO
4And Li
2CO
3Be raw material, respectively at N
2In the atmosphere in 300 ℃ and 500 ℃ of-800 ℃ of prepared in reaction LiFePO
4, as (Optimized LiFePO such as Atsuo Yamada
4For Lithium BatteryCathodes[J] .Journal of The Electrochemical Society, 2001,148 (3): A224-A229) with FeAc
2, (NH
4)
2HPO
4And Li
2CO
3For raw material has synthesized LiFePO
4, and with XRD, BET surface-area measuring technology, M ssbauer spectrum and sreen analysis technical study the influence of synthesis technique to product property.Result of study shows that the product that adopts medium maturing temperature (500 ℃＜T＜600 ℃) and homogeneous phase presoma to obtain at room temperature can reach 95% theoretical capacity.Because temperature is big greater than the particle diameter of 600 ℃ of products, specific surface area is less; Temperature is less than 500 ℃ of Fe that have amorphous or nanometer state
3+Phase.The advantage of pyroprocess is that technology simply, easily realizes industrialization, but reactant is difficult for mixing, and product particle diameter major part is a micron order, and skewness, and pattern is also irregular.
Shoufeng Yang etc. (Hydrothermal synthesis of lithium ironphosphate cathodes[J] .Electrochemistry Communications 20013:505-508) are with divalent iron salt, LiOH and the H of solubility
3PO
4Be raw material, (120 ℃, 5h) synthesized single-phase LiFePO with hydrothermal method
4, median size is about 3 μ m.(LiFePO such as S.Frange
4Synthesis routes for enhanced electrochemicalperformance[J] .Electrochemical and Solid-State Letters, 2002,5 (10) A231-A223) with Fe
3(PO
4)
25H
2O and Li
3PO
4Be raw material, with Hydrothermal Preparation LiFePO
4Compare with high temperature solid-state method, hydrothermal method can directly obtain LiFePO
4, do not need inert atmosphere, also be easy to the crystal formation and the particle diameter of control material; But hydrothermal method needs high-temperature high-pressure apparatus, and it is big that the difficulty of suitability for industrialized production is wanted.
(synthetic route for preparing LiFePO such as Pier Paolo
4Withenhanced electrochemical performance[J] .Journal of theElectrochemical Society, 2002,149 (7) A886-890) use H earlier
2O
2Oxidation of Fe (II) compound FePO
4, again with LiI reduction preparation LiFePO
4, after heat treatment obtain LiFePO
4Crystal.(A novel concept for the synthesis ofan improved LiFePO such as F.Croce
4Lithium batteries cathode[J] .Electrochemical and Solid-State Letters, 2002,5 (3) A47-50) with the xitix LiFePO that reduced Fe (III) compound
4In this class synthetic method, owing to used expensive H
2O
2, reagent such as LiI and xitix, thereby increased the cost of product and the complexity of production technique.
In a word, in existing synthetic method, high temperature solid-state method or can not obtain nanoparticle, or need to use expensive acetate and carbon gel; Though hydrothermal method can be controlled particle diameter, be difficult for realizing industrialization; Oxidation reduction process need be used H
2O
2, reagent such as LiI and xitix, increased the preparation cost of material and the complexity of technology.
Summary of the invention
The present invention is directed to the weak point that aforesaid method exists, be nano iron phosphate lithium as anode material of lithium ion battery (LiFePO
4) a kind of new wet chemical preparation method is provided, control LiFePO effectively
4Chemical Composition, phase composition and particle diameter, improve its homogeneity and conductivity, improve its chemical property.Reduced material cost simultaneously, simplified synthesis technique, made it to be easy in industrial enforcement.
The technical measures that the present invention adopts are: the solution or the suspension that will contain Li source compound, Fe source compound, P source compound, doping element compound, conductive agent and precipitation agent mix, in 5-120 ℃ airtight stirred reactor, reacted 0.5-24 hour, obtain the nanometer presoma after filtering, wash, drying, wherein the concentration of Li source compound, Fe source compound, P source compound is 0.1-3.0mol/L; The mol ratio of Li source compound, Fe source compound, P source compound consumption is: lithium: iron: phosphorus=0.90-1.00: 1.0: 1.0; Described nanometer presoma is put into High Temperature Furnaces Heating Apparatus, in non-air or non-oxidizing atmosphere, with the temperature rise rate heating of 1-30 ℃/min, at 500-800 ℃ of constant temperature calcining 5-48 hour, and, make the lithium iron phosphate nano powder with cooling of the rate of temperature fall of 1-20 ℃/min or furnace cooling.
The present invention has following characteristics: the specific discharge capacity of (1) product can be controlled flexibly by changing processing parameter; (2) Chemical Composition of product, phase composition and even particle size distribution and control easily can directly be synthesized the nano-powder of particle diameter less than 600nm; (3) product is realized mixing easily; (4) conductive agent is evenly distributed in product and control easily; (5) raw material of Shi Yonging all is large Chemicals, and is cheap; (6) preparation technology is simple, flow process is short, easy to control, easily realize industrialization; (7) wet method is synthetic, has realized the mixing at molecular level of lithium, iron and phosphorus.
Key of the present invention be prevent to prepare and charge and discharge process in nanometer powder reunion and grow up and improve LiFePO
4The conductive capability of nanometer powder.The present invention mainly prevents the reunion of nanometer powder by following measure and grows up and improve nanometer LiFePO
4The conductive capability of powder: (1) optimizes the reunion that depositing technology prevents particle in presoma preparation and the drying process; (2) inert particle (as the carbon black of high-ratio surface) that coats one deck high-ratio surface on the surface of presoma prevents the hard aggregation of nanoparticle in the follow-up heat treatment process; (3) at LiFePO
4Nanometer powder surface coats one deck carbon or other material and suppresses in the charge and discharge process nanoparticle generation repolymerization and (4) by conductive agent such as adding carbon black in synthetic or at LiFePO
4In introduce other element and carry out body and mix and improve the conductivity of material.
Embodiment
The present invention comprises that mainly precipitin reaction directly prepares presoma and two steps of pyroprocessing.
1. precipitin reaction directly prepares the nanometer presoma
The solution or the suspension that will contain Li source compound, Fe source compound, P source compound, doping element compound and precipitation agent mix, and in 5-120 ℃ airtight stirred reactor, react 0.5-24 hour, obtain the nanometer presoma after filtering, wash, drying.The consumption of Li source compound, Fe source compound, P source compound is pressed lithium in the reaction: iron: phosphorus=0.90-1.00: 1.0: 1.0 (mol ratio) determined.The atmosphere of reactor can be air atmosphere or nonoxidizing atmosphere.Li source compound is selected from a kind of in lithium chloride, Lithium Sulphate, Lithium Acetate, lithium nitrate, Quilonum Retard, lithium hydroxide, the lithium oxalate, and the concentration of its lithium is 0.1-3.0mol/L.Fe source compound is selected from a kind of in ferrous sulfate, iron protochloride and the iron acetate, and wherein the concentration of iron is 0.1-3.0mol/L.P source compound is selected from a kind of in phosphoric acid, triammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, Tripotassium phosphate, dipotassium hydrogen phosphate, potassium primary phosphate, tertiary sodium phosphate, Sodium phosphate dibasic, the SODIUM PHOSPHATE, MONOBASIC, and wherein the concentration of phosphorus is 0.1-3.0mol/L.Precipitation agent is selected from a kind of in Quilonum Retard, lithium hydroxide, triammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, Tripotassium phosphate, dipotassium hydrogen phosphate, potassium primary phosphate, tertiary sodium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, ammonia, ammoniacal liquor, volatile salt, bicarbonate of ammonia, yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, sodium hydroxide, potassium hydroxide, urea and the melamine.Wherein, Quilonum Retard and lithium hydroxide are precipitation agent, be again Li source compound, triammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, Tripotassium phosphate, dipotassium hydrogen phosphate, potassium primary phosphate, tertiary sodium phosphate, Sodium phosphate dibasic and SODIUM PHOSPHATE, MONOBASIC are precipitation agent, are again P source compounds.Consumption is 1.0-3.0 a times of theoretical consumption, and the theoretical consumption of precipitation agent is determined by corresponding chemical reaction.The source of the gas that forms nonoxidizing atmosphere is selected from hydrogen, nitrogen, argon gas, carbonic acid gas, carbon monoxide, ammonia.Conductive agent is selected from a kind of in the compounds such as carbon black, metal-powder, steel fiber, sucrose, and its consumption is the 1-20% of iron lithium phosphate quality.Doped element is selected from a kind of in aluminium, boron, magnesium, calcium, hydrogen, sodium, titanium, barium, vanadium, chromium, manganese, cobalt, copper, the zinc, and its consumption is the 0.1-10% of lithium or iron mole number in the iron lithium phosphate.
2. high-temperature heat treatment
The nanometer presoma of step 1 preparation is put into crucible, and crucible placed High Temperature Furnaces Heating Apparatus, in non-air or non-oxidizing atmosphere, temperature rise rate heating with 1-30 ℃/min, at 500-800 ℃ of constant temperature calcining 5-48 hour, and with cooling of the rate of temperature fall of 1-20 ℃/min or furnace cooling, it was complete to make crystalline structure, Chemical Composition, phase composition and even particle size distribution, the lithium iron phosphate nano powder that conductivity is good.The source of the gas that forms nonoxidizing atmosphere or non-air atmosphere is selected from hydrogen, nitrogen, argon gas, carbonic acid gas, carbon monoxide, ammonia.
Further specify method provided by the present invention below by embodiment.
Behind the copperas solution and 10% carbon black thorough mixing of embodiment 1 with the lithium chloride solution of 0.5mol/L and 0.5mol/L, the ammonium phosphate solution that adds the 0.5mol/L of 1.0 times of theoretical amount again, reacted 6 hours down at 25 ℃, filtration, washing and oven dry obtain presoma.In nitrogen atmosphere, after being heated to specified temperature and being incubated the regular hour with the temperature rise rate of 1 ℃/min, cool to presoma with the furnace room temperature.The roasting condition that experiment is adopted sees Table 1.The product of gained shows to be olivine-type LiFePO through X-ray diffraction analysis
4, complete, the product of crystalline structure particle diameter between 400nm-600nm.The composition of product is measured with plasma emission spectrum (ICP), the results are shown in Table 1.With the Experimental cell that is assembled into of the product of gained, with the constant current discharge technical measurement it charge and discharge specific storage and cycle performance, carry out the perseverance discharge at the discharging current of 0.5C, specific discharge capacity sees Table 1 after their first discharge specific capacity and the circulation 40 times.
The experiment condition of table 1 embodiment 1 and result
The 40th specific discharge capacity of numbering maturing temperature roasting time product atomic ratio first discharge specific capacity
/℃ /h Li∶Fe∶P /mAh·g-1 /mAh·g-1
1 500 48 1.00∶1.00∶1.00 135.0 125.1
2 600 16 1.02∶1.00∶1.00 145.0 138.2
3 700 8 1.01∶1.00∶1.00 140.0 132.1
4 800 5 0.99∶1.00∶1.00 138.8 126.0
Behind the copperas solution and 10% carbon black (A5) thorough mixing of embodiment 2 with the lithium chloride solution of 0.5mol/L and 0.5mol/L, the ammonium phosphate solution that adds the 0.5mol/L of 1.0 times of theoretical amount again, carry out precipitin reaction under different conditions, filtration, washing and oven dry obtain presoma.Presoma in nitrogen atmosphere, was heated to 600 ℃ of constant temperature calcinings 8 hours with the temperature rise rate of 1 ℃/min, is cooled to room temperature with the rate of temperature fall of 1 ℃/min.The condition of precipitin reaction sees Table 2.The product of gained shows to be olivine-type LiFePO through X-ray diffraction analysis
4, complete, the product of crystalline structure particle diameter between 400nm-600nm.The composition of product is measured with plasma emission spectrum (ICP), the results are shown in Table 2.With the Experimental cell that is assembled into of the product of gained, with the constant current discharge technical measurement it charge and discharge specific storage and cycle performance, carry out the perseverance discharge at the discharging current of 0.5C, specific discharge capacity sees Table 2 after their first discharge specific capacity and the circulation 40 times.
The experiment condition of table 2 embodiment 2 and result
40 specific storagies of numbering temperature of reaction reaction times product atomic ratio specific volume flow control first
/℃ /h Li∶Fe∶P /mAh·g-1 /mAh·g-1
5 5 24 1.02∶1.00∶1.00 138.5 131.0
6 25 6 1.03∶1.00∶1.00 139.2 132.0
7 60 3 1.00∶1.00∶1.00 137.6 131.3
8 120 0.5 0.99∶1.00∶1.00 136.9 130.1
Behind the phosphoric acid solution and iron salt solutions and 10% carbon black thorough mixing of embodiment 3 with 0.5mol/L, add the lithium salt solution of different sorts and concentration again, reacted 3 hours down at 60 ℃, filtration, washing and oven dry obtain presoma.Presoma in nitrogen atmosphere, was heated to 600 ℃ of constant temperature calcinings 8 hours with the temperature rise rate of 10 ℃/min, is cooled to room temperature with the rate of temperature fall of 10 ℃/min.Test used lithium salts and molysite kind and concentration and see Table 3.The product of gained shows to be olivine-type LiFePO through X-ray diffraction analysis
4, complete, the product of crystalline structure particle diameter between 300nm-500nm.The composition of product is measured with plasma emission spectrum (ICP), the results are shown in Table 3.With the Experimental cell that is assembled into of the product of gained, with the constant current discharge technical measurement it charge and discharge specific storage and cycle performance, carry out the perseverance discharge at the discharging current of 0.5C, specific discharge capacity sees Table 3 after their first discharge specific capacity and the circulation 40 times.
The experiment condition of table 3 embodiment 3 and result
Compile 40 specific storagies of lithium salts lithium salt molysite iron salt concentration product atomic ratio specific volume flow control first
Number kind/molL
-1Kind/molL
-1Li: Fe: P/mAhg-1/mAhg-1
9 Li
2SO
4 1.0 FeCl
2 1.0 1.00∶1.00∶1.00 139.0 134.0
10 LiAc 3.0 FeCl
2 0.1 1.00∶1.00∶1.00 139.2 133.0
11 Li
2CO
3 0.5 FeCl
2 2.0 1.02∶1.00∶1.00 138.6 132.3
12 Li
2C
2O
40.5 FeCl
2 3.0 1.00∶1.00∶1.00 138.9 133.1
13 LiOH 0.5 FeAc
2 1.5 1.00∶1.00∶1.00 139.2 134.0
After implementing 4 copperas solutions and 10% carbon black thorough mixing, add the different precipitation agents of doing again, 90 ℃ of reactions 6 hours down, filter, washing and oven dry obtain presoma the lithium chloride solution of 0.5mol/L and 0.5mol/L.Presoma in nitrogen atmosphere, was heated to 600 ℃ of constant temperature calcinings 8 hours with the temperature rise rate of 20 ℃/min, is cooled to room temperature with the rate of temperature fall of 10 ℃/min.The precipitation agent that experiment is adopted sees Table 4.The product of gained shows to be olivine-type LiFePO through X-ray diffraction analysis
4, complete, the product of crystalline structure particle diameter between 200nm-500nm.The composition of product is measured with plasma emission spectrum (ICP), the results are shown in Table 4.With the Experimental cell that is assembled into of the product of gained, with the constant current discharge technical measurement it charge and discharge specific storage and cycle performance, carry out the perseverance discharge at the discharging current of 0.5C, specific discharge capacity sees Table 4 after their first discharge specific capacity and the circulation 40 times.
The experiment condition of table 4 embodiment 4 and result
The 40th specific discharge capacity of numbering precipitation agent kind precipitation agent consumption product atomic ratio first discharge specific capacity
/ times Li: Fe: P/mAhg-1/mAhg-1
14 tertiary sodium phosphates 1.5 1.00: 1.00: 1.00 138.0 133.0
15 Tripotassium phosphates 1.5 1.00: 1.00: 1.00 139.0 134.5
16 bicarbonate of ammonia 2.0 0.98: 1.00: 1.00 138.0 132.0
17 yellow soda ash 2.0 0.99: 1.00: 1.00 138.5 133.7
18 salt of wormwood 2.0 0.99: 1.00: 1.00 138.2 132.2
19 sodium hydroxide 1.0 1.00: 1.00: 1.00 138.0 131.5
20 urea 5.0 0.99: 1.00: 1.00 139.2 133.3
21 melamines 4.0 0.99: 1.00: 1.00 137.8 132.7
Behind the copperas solution and 10% carbon black thorough mixing of embodiment 5 with the lithium chloride solution of 0.5mol/L and 0.5mol/L, the ammonium phosphate solution that adds the 0.5mol/L of 1.0 times of theoretical amount again, reacted 6 hours down at 90 ℃, filtration, washing and oven dry obtain presoma.Presoma in different atmosphere, is heated to 600 ℃ of constant temperature calcinings 8 hours with the temperature rise rate of 5 ℃/min, cools to room temperature with the furnace.The atmosphere that experiment is adopted sees Table 5.The product of gained shows to be olivine-type LiFePO through X-ray diffraction analysis
4, complete, the product of crystalline structure particle diameter between 400nm-500nm.The composition of product is measured with plasma emission spectrum (ICP), the results are shown in Table 5.With the Experimental cell that is assembled into of the product of gained, with the constant current discharge technical measurement it charge and discharge specific storage and cycle performance, the discharging current 0.5 carries out the perseverance discharge, specific discharge capacity sees Table 5 after their first discharge specific capacity and the circulation 40 times.
The experiment condition of table 5 embodiment 5 and result
Numbering atmosphere kind atmosphere is formed the 40th specific discharge capacity of product atomic ratio first discharge specific capacity
/ volume ratio Li: Fe: P/mAhg-1/mAhg-1
22 argon gas 1.0 1.00: 1.00: 1.00 139.0 135.2
23 carbonic acid gas 1.0 1.01: 1.00: 1.00 138.0 132.1
24 ammonias 1.0 1.00: 1.00: 1.00 138.0 133.0
25 nitrogen+hydrogen 0.5: 0.5 1.00: 1.00: 1.00 135.0 127.7
26 nitrogen+hydrogen 0.8: 0.2 0.98: 1.00: 1.00 133.2 126.2
27 nitrogen+carbon monoxide 0.4: 0.6 1.00: 1.00: 1.00 134.0 137.0
28 nitrogen+carbon monoxide 0.3: 0.7 1.00: 1.00: 1.00 132.2 125.3
Embodiment 6 mixes the copperas solution of 0.5mol/L lithium chloride solution, 0.5mol/L and the ammonium phosphate solution of 0.5mol/L with different conductive agents, reacted 3 hours down at 25 ℃, filter, wash and oven dry, obtain presoma, with presoma in nitrogen atmosphere, with the heating of the temperature rise rate of 5 ℃/min,, cool to room temperature with the furnace 600 ℃ of constant temperature calcinings 8 hours.The conductive agent that experiment is adopted sees Table 6.The product of gained shows to be olivine-type LiFePO through X-ray diffraction analysis
4, complete, the product of crystalline structure particle diameter between 400nm-500nm.The composition of product is measured with plasma emission spectrum (ICP), the results are shown in Table 6.With the Experimental cell that is assembled into of the product of gained, with the constant current discharge technical measurement it charge and discharge specific storage and cycle performance, carry out the perseverance discharge at the discharging current of 0.5C, specific discharge capacity sees Table 6 after their first discharge specific capacity and the circulation 40 times.
The experiment condition of table 6 embodiment 6 and result
The 40th specific discharge capacity of numbering conductive agent kind conductive agent consumption product atomic ratio first discharge specific capacity
/％ Li∶Fe∶P /mAh·g-1 /mAh·g-1
29 carbon blacks 0.0 1.00: 1.00: 1.00 100.0 89.0
30 carbon blacks 5.0 1.00: 1.00: 1.00 130.0 124.0
31 carbon blacks 20.0 1.00: 1.00: 1.00 142.0 136.0
32 sucrose 15.0 1.00: 1.00: 1.00 145.0 135.0
33 bronze medal fibers 2.0 1.00: 1.00: 1.00 143.2 136.2
34 Stainless Steel Fibres 3.0 1.00: 1.00: 1.00 144.0 138.0
35 silver powder 1.0 1.00: 1.00: 1.00 142.0 136.3
36 aluminium powders 7.0 1.00: 1.00: 1.00 143.5 135.8
Behind copperas solution, 0.5mol/L lithium chloride solution and the different doping element compounds or the mixing of its solution of embodiment 7 with 0.5mol/L, the ammonium phosphate solution and the thorough mixing that add 0.5mol/L again, reacted 3 hours down at 25 ℃, filter, wash and dry and obtain presoma, with presoma in nitrogen atmosphere, with the heating of the temperature rise rate of 5 ℃/min,, cool to room temperature with the furnace 600 ℃ of constant temperature calcinings 8 hours.The doped element that experiment is adopted sees Table 7.The product of gained shows to be olivine-type LiFePO through X-ray diffraction analysis
4, complete, the product of crystalline structure particle diameter between 400nm-500nm.The composition of product is measured with plasma emission spectrum (ICP), the results are shown in Table 7.With the Experimental cell that is assembled into of the product of gained, with the constant current discharge technical measurement it charge and discharge specific storage and cycle performance, carry out the perseverance discharge at the discharging current of 0.5C, specific discharge capacity sees Table 7 after their first discharge specific capacity and the circulation 40 times.
The experiment condition of table 7 embodiment 7 and result
Compile the 40th specific discharge capacity of dopant species hotchpotch consumption product atomic ratio first discharge specific capacity
Number/the atomic ratio % Li of iron: doped element: F: P/mAhg-1/mAhg-1
37 manganous sulfates 10.0 1.00: 0.10: 0.90: 1.00 146.7 140.0
38 Tai-Ace S 150 1.0 1.00: 0.01: 0.99: 1.00 143.2 136.6
39 calcium chloride 3.0 1.00: 0.03: 0.97: 1.00 142.0 135.0
40 boron trioxides 5.0 1.00: 0.05: 0.95: 1.00 144.0 139.5
41 Vanadium Pentoxide in FLAKESs 7.0 1.00: 0.07: 0.93: 1.00 147.0 141.5
Embodiment 8 mixes the copperas solution of 0.5mol/L lithium chloride solution, 0.5mol/L and the ammonium phosphate solution of 0.5mol/L, reacted 3 hours down at 25 ℃, obtain presoma after filtering, wash and drying, with presoma in nitrogen atmosphere, temperature rise rate heating with 1 ℃/min, 600 ℃ of constant temperature calcinings 8 hours, furnace cooling.Cooled product was handled 1.5 hours down at 50 ℃ with 0.1mol/L hydrochloric acid, and the product of gained is indicated as olivine-type LiFePO through X-ray diffraction analysis
4, complete, the particle diameter of crystalline structure is about 400nm.The composition of product is determined as Li: H: Fe: P=0.97 with plasma emission spectrum (ICP): 0.03: 1.0: 1.0 (atomic ratio), the content of H is about 3%.The Experimental cell that is assembled into the product of gained, with the constant current discharge technical measurement it charge and discharge specific storage and cycle performance, when the discharging current of 0.5C carried out the perseverance discharge, first discharge specific capacity was 142.5mAh/g, and circulating, specific discharge capacity is 136.7mAh/g after 40 times.
Claims (8)
1. wet chemical method for preparing iron lithium phosphate, it is characterized in that the solution or the suspension that will contain Li source compound, Fe source compound, P source compound, doping element compound, conductive agent and precipitation agent mix, in 5-120 ℃ airtight stirred reactor, reacted 0.5-24 hour, obtain the nanometer presoma after filtering, wash, drying, wherein the concentration of Li source compound, Fe source compound, P source compound is 0.1-3.0mol/L; The mol ratio of Li source compound, Fe source compound, P source compound consumption is: lithium: iron: phosphorus=0.90-1.00: 1.0: 1.0; Described nanometer presoma is put into High Temperature Furnaces Heating Apparatus, in non-air or non-oxidizing atmosphere, with the temperature rise rate heating of 1-30 ℃/min, at 500-800 ℃ of constant temperature calcining 5-48 hour, and, make the lithium iron phosphate nano powder with cooling of the rate of temperature fall of 1-20 ℃/min or furnace cooling.
2. the wet chemical method of preparation iron lithium phosphate according to claim 1 is characterized in that described Li source compound is selected from a kind of in lithium chloride, Lithium Sulphate, Lithium Acetate, lithium nitrate, Quilonum Retard, lithium hydroxide, the lithium oxalate.
3. the wet chemical method of preparation iron lithium phosphate according to claim 1 and 2 is characterized in that described Fe source compound is selected from a kind of in ferrous sulfate, iron protochloride and the iron acetate.
4. the wet chemical method of preparation iron lithium phosphate according to claim 1 and 2 is characterized in that described P source compound is selected from a kind of in phosphoric acid, triammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, Tripotassium phosphate, dipotassium hydrogen phosphate, potassium primary phosphate, tertiary sodium phosphate, Sodium phosphate dibasic, the SODIUM PHOSPHATE, MONOBASIC.
5. the wet chemical method of preparation iron lithium phosphate according to claim 1 and 2, it is characterized in that described precipitation agent is selected from Quilonum Retard, lithium hydroxide, triammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, Tripotassium phosphate, dipotassium hydrogen phosphate, potassium primary phosphate, tertiary sodium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, ammonia, ammoniacal liquor, volatile salt, bicarbonate of ammonia, yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, sodium hydroxide, potassium hydroxide, a kind of in urea and the melamine, the consumption of precipitation agent serve as reasons corresponding chemical reaction decision theoretical consumption 1.0-3.0 doubly.
6. it is a kind of or its mixture in hydrogen, nitrogen, argon gas, carbonic acid gas, carbon monoxide, the ammonia that the wet chemical method of preparation iron lithium phosphate according to claim 1 and 2, the source of the gas that it is characterized in that described formation nonoxidizing atmosphere are selected from.
7. the wet chemical method of preparation iron lithium phosphate according to claim 1 and 2 is characterized in that described conductive agent is selected from a kind of in carbon black, metal-powder, steel fiber, the sucrose, and its consumption is the 1-20% of iron lithium phosphate quality.
8. the wet chemical method of preparation iron lithium phosphate according to claim 1 and 2, it is characterized in that described doped element is selected from a kind of in aluminium, boron, magnesium, calcium, hydrogen, sodium, titanium, barium, vanadium, chromium, manganese, cobalt, copper, the zinc, its consumption is the 0.1-10% of lithium or iron mole number in the iron lithium phosphate.
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| CN101777649A (en) * | 2010-03-15 | 2010-07-14 | 彩虹集团公司 | Preparation method of lithium iron phosphate of positive electrode material of lithium ion battery |
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