CN102856545B - Preparation method of micro-nano-grade metal-ion-doped lithium iron phosphate anode material - Google Patents
Preparation method of micro-nano-grade metal-ion-doped lithium iron phosphate anode material Download PDFInfo
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- CN102856545B CN102856545B CN201210335700.7A CN201210335700A CN102856545B CN 102856545 B CN102856545 B CN 102856545B CN 201210335700 A CN201210335700 A CN 201210335700A CN 102856545 B CN102856545 B CN 102856545B
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- Prior art keywords
- lithium
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- iron
- solution
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 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 18
- 239000010405 anode material Substances 0.000 title abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 66
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 47
- 238000002156 mixing Methods 0.000 claims description 40
- 238000005245 sintering Methods 0.000 claims description 37
- 229910052698 phosphorus Inorganic materials 0.000 claims description 30
- 229910052742 iron Inorganic materials 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000005955 Ferric phosphate Substances 0.000 claims description 22
- 229940032958 ferric phosphate Drugs 0.000 claims description 22
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 22
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- -1 Sucrose Fatty Acid Ester Chemical class 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 4
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 4
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 4
- 229920000136 polysorbate Polymers 0.000 claims description 4
- 229950008882 polysorbate Drugs 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- 229930091371 Fructose Natural products 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 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
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 2
- 241001272567 Hominoidea Species 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229930003268 Vitamin C Natural products 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000001913 cellulose Chemical class 0.000 claims description 2
- 229920002678 cellulose Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019154 vitamin C Nutrition 0.000 claims description 2
- 239000011718 vitamin C Substances 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- WFGBXPXOFAFPTO-UHFFFAOYSA-N [P].[Fe].[Li] Chemical compound [P].[Fe].[Li] WFGBXPXOFAFPTO-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000000265 homogenisation Methods 0.000 abstract 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 abstract 1
- 238000001694 spray drying Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 10
- 239000008187 granular material Substances 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 7
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000006245 Carbon black Super-P Substances 0.000 description 5
- XKSGHSJZPRUMJX-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Fe+2].[Co+2].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Fe+2].[Co+2].[Li+] XKSGHSJZPRUMJX-UHFFFAOYSA-K 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000005030 aluminium foil Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- PSPBOBONWVYMPP-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Zn+2] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Zn+2] PSPBOBONWVYMPP-UHFFFAOYSA-K 0.000 description 3
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- 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
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention belongs to the technical field of lithium ion battery anode material preparation, and discloses a preparation method of a micro-nano-grade metal-ion-doped lithium iron phosphate anode material. According to the invention, an accurate iron-phosphorus ratio is realized through a liquid phase homogenization reaction; doping metal ions are added simultaneously during a continuous liquid phase reaction process, such that material conductivity and tap density are improved; during subsequent preparation processes, through accurate controlling over lithium-iron-phosphorus ratio and carbon content, good dispersion, and rapid spray drying, precursor material uniform dispersion and good carbon coating are realized; and under atmosphere protection, the micro-nano-grade metal-ion-doped lithium iron phosphate anode material with narrow particle-size distribution, high tap density, and good fluidity is obtained through a heat treatment of a relatively short time under a relatively low temperature. The preparation method provided by the invention has the advantages of suitability for large-scale productions, simple technology, and low cost. The method has great application value and good application prospect in the respect of preparation of high-power lithium ion batteries applied in fields of solar energy, wind energy, electric vehicles, and the like.
Description
Technical field
The invention belongs to chargeable chemical electric power source electrode technical field of material, particularly the preparation method of micro-nano-scale doped lithium iron phosphate anode material for a kind of high power lithium ion cell.
Background technology
LiFePO 4 (LiFePO
4) be a kind of lithium ion battery novel anode material growing up in recent years.Its raw material source is abundant, and specific capacity is high, has extended cycle life, and environmental pollution is little.At present, power type of new generation or accumulation energy type lithium ion battery have been widely used in.
Yet, most of business-like LiFePO4s are owing to directly adopting solid phase high-sintering process, at raw material, mix, there is defect in the aspect such as dry, sintering, therefore, the performance of mass production of products is stable not, and consistency is poor in batches, cause material manufacturing cost to increase, add different manufacturers battery preparation technique difference, applying of product is affected, thereby also seriously restricted its large-scale production; In addition, show still Shortcomings of the aspects such as its high rate during charging-discharging, cryogenic property, cause power of battery density, operating characteristics and the scope of application to be also restricted.Therefore, must propose a set of innovative technology route and fundamentally solve the above-mentioned bottleneck problem that LiFePO 4 material exists.
Preparation technology is simple for high temperature solid-state method LiFePO 4 material, but reactant is difficult for mixing, some process using ball milling mixes, sintering time is long, time consumption and energy consumption, synthetic product broad particle distribution, granule size is micro-meter scale, pattern is irregular, and the chemical property of different batches material differs greatly.This is that the control of product composition, purity, crystallization shape, granule size also has great difficulty, causes the batch less stable of product, and whole production process flow process is long because solid phase method is difficult to control accurately lithium, iron, phosphorus ratio, and energy consumption is larger.Existing many patents have carried out improving research to the synthesis technique of LiFePO4 both at home and abroad, but are the improvement on solid phase method basis mostly.Also have and adopt microwave method, hydro thermal method and some liquid phase method synthetic methods, but that these methods are not suitable for extensive preparation, some complex process, some cost is a bit higher.Therefore, the present invention is intended to find a kind of preparation on a large scale, process stabilizing, simple to operate, lower-cost liquid phase homogeneous phase method in conjunction with the process route of solid-phase sintering synthesizing iron lithium phosphate.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of micro-nano doped metal ion lithium iron phosphate positive material, this lithium iron phosphate positive material granularity is 50nm~6 μ m, and doping metals amount is 0.5 ~ 5%, and carbon content is 0.5~5%, and tap density is 1.1 ~ 1.6g/cm
2, the method comprises the following steps:
(1) according to the mol ratio of Fe and doped metal ion sum and P, be that 1:1 weighs source of iron, phosphorus source and doped metal ion compound, by three's water-soluble solution that is mixed with respectively, then source of iron and phosphorus source solution are mixed to get to the mixed solution that Fe and P total concentration are 0.75-2mol/L, doped metal ion amount is 0.01 ~ 0.05 of total mole of doped metal ion and Fe, and the concentration of doped metal ion compound solution is 0.1 ~ 1mol/L; Compound concentration is the alkaline solution of 0.1-3mol/L;
(2) in reactor, add the dispersant of deionized water and the theoretical ferric phosphate quality 0.1% ~ 0.5% generating, even with the speed dispersed with stirring of 200-2000r/min, reaction 0.5-4 hour;
(3) the phosphorus source in step (1) and source of iron mixed solution, doped metal ion compound solution, aqueous slkali are distinguished in the reactor of input step (2), and be uniformly mixed with the speed of 200-2000r/min, reaction 0.5-4 hour, reaction temperature is 15-80 ℃; Wherein the charging rate of phosphorus source and source of iron mixed solution is 2-15ml/min, and doped metal ion compound solution charging rate is 1-10ml/min, and alkaline solution charging rate regulates by the pH of system, and pH control range is 1.5-6.0;
(4) step (3) products therefrom is filtered, with deionized water, wash 3 times, with ethanol, wash 1 time, 80 ℃, dry 4-8 hour; Then, at 350-550 ℃, sintering 4-8 hour obtains the ferric phosphate containing doped metal ion;
(5) by Li, Fe, P three's mol ratio, be (1 ~ 1.05): (0.95 ~ 1): 1 takes respectively ferric phosphate prepared by lithium source and step (4); By ferric phosphate quality 0.5 ~ 5% take carbon source, lithium source, ferric phosphate, carbon source are added in the aqueous solution that contains dispersant, in the blender with stirring, take mixing speed as 200-800r/min dispersion 0.25-2 hour, and be 10%-50% with deionized water adjustment solid content; Wherein the consumption of dispersant is theoretical 0.1% ~ 0.5% of the ferric phosphate quality that generates;
(6) by the mixed material input spray dryer in step (5), spray dry; Control inlet temperature is 180-250 ℃, and outlet temperature is 90-120 ℃;
(7) by step (6) gained dried material sintering temperature under inert gas, be at 400-700 ℃, sintering time is 8-12 hour, obtains micro-nano doped metal ion lithium iron phosphate positive material by sintered products is cooling.
Above-mentioned source of iron is ferric nitrate, iron chloride, ferric sulfate or ironic citrate.
The above-mentioned phosphorus source of stating is phosphoric acid, ammonium dihydrogen phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate;
Above-mentioned doped metal ion compound is cobalt nitrate, manganese nitrate, zinc nitrate, ammonium molybdate, ammonium tungstate, ammonium titanium fluoride, strontium nitrate, nickel nitrate, magnesium nitrate or zirconium nitrate.
Above-mentioned lithium source is lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium oxalate or lithium sulfate.
Above-mentioned carbon source is one or more in acetylene black, electrically conductive graphite, carbon nano-tube, Graphene, sucrose, glucose, fructose, citric acid, pentaerythrite, vitamin C, polyvinyl alcohol, polyethylene glycol and polyethers.
Alkali compounds in above-mentioned alkaline solution is carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, sodium carbonate, saleratus, potash, NaOH, potassium hydroxide or ammoniacal liquor.
Above-mentioned dispersant is that lauryl sodium sulfate, dodecyl sodium sulfate, APES 10, dioctyl sodium sulfosuccinate, Sucrose Fatty Acid Ester, aliphatic acid sorb are smooth, one or more in polysorbate, polyoxyethylene, polyvinyl alcohol, methyl anyl alcohol, cellulose derivative, fatty acid polyethylene glycol ester.
Reactor described in step (2) is that this reactor can continuous discharge with the stainless steel reactor of chuck, charging aperture, discharging opening, overfall, blender and PH meter.
Lithium source described in step (5) adds with powder or is configured to the aqueous solution and adds.
Inert gas described in step (7) is high pure nitrogen, high-purity argon gas or is that the High Purity Hydrogen of 2% hydrogen is argon-mixed containing volume.
Beneficial effect of the present invention is: use relatively cheap ferric iron to replace divalence source of iron to make raw material, not only reduced production cost, and avoided ferrous iron to be easily oxidized generating the impurity that is difficult to remove and cause product impure; In liquid phase, can realize accurate-metering and the doping of source of iron, phosphorus source and metal ion, iron, phosphorus and metallic atom distribute very evenly and proportion of composing is fixed; In liquid-phase system, add a small amount of dispersant can make source of iron, phosphorus source and doping metals compound fully mix before reaction, product is dispersed; Ferric phosphate, lithium source and carbon source only do not need ball milling just can realize good homogeneous phase to mix, saved the energy, greatly shortened incorporation time, improved production efficiency by stirring; Adopt spray-dired method, wink-dry slurry, avoids segregation in composition dry run, and products obtained therefrom composition is even, in batches good stability; In liquid phase reaction course, realize the even carbon dope of metal ion mixing and granule interior, material tap density and conductivity raising are highly profitable; Precursor material granularity prepared by the method is less, narrow distribution, and therefore, required sintering temperature declines, and sintering time shortens, and has further reduced power consumption.This reaction method technique is simple, is easy to control, can continuous discharge, and production efficiency is high, product quality high conformity, stable electrochemical property, preparation cost is low, and is easy to large-scale continuous production.Micro-nano-scale doped iron lithium phosphate material prepared by the method has good chemical property as anode material for lithium-ion batteries, at room temperature 0.1C multiplying power discharging specific capacity is greater than 155mAh/g, 10C multiplying power discharging specific capacity is greater than 100mAh/g, and cycle performance is good, the positive electrode that is suitable as high power type lithium ion cell is used.
Accompanying drawing explanation
Fig. 1 is scanning electron microscopy (SEM) figure and the X-ray energy spectrum figure (EDS) that mixes cobalt ferric phosphate.
Fig. 2 is the SEM figure that mixes cobalt lithium iron phosphate positive material.
Fig. 3 is the cycle performance curve of mixing the electric discharge of cobalt lithium iron phosphate positive material under different multiplying that room temperature records.
Embodiment
Below in conjunction with drawings and Examples, technical scheme of the present invention is described further.
Embodiment 1
(1) according to the mol ratio of Fe and doped metal ion sum and P, be 1:1, prepare respectively 1mol/L iron nitrate solution and 1mol/L phosphoric acid solution, two solution are mixed, obtain the mixed solution that Fe and P total concentration are 1mol/L, and compound concentration is that 0.5mol/L cobalt nitrate solution and concentration are 3mol/L ammonia spirit.
(2) 0.25g polyvinyl alcohol is dispersed in 100ml deionized water, adds in the 1L stainless steel reactor with chuck and stirring and stir, mixing speed is 200r/min, and controlling chuck circulating water temperature is 25 ℃.
(3) by the mixed solution of iron nitrate solution and phosphoric acid solution with 5ml/min charging rate input reactor, by 0.5mol/L cobalt nitrate solution with 2ml/min charging rate input reactor.Meanwhile, by the ammonia spirit input reactor of 3mol/L, controlling pH is 1.5, regulates the charging rate of ammonia spirit.Adjusting mixing speed is 1500r/min, reacts and within 1.5 hours, starts discharging.By material filtering, with deionized water, wash 3 times, with ethanol, wash 1 time, at 80 ℃, dry 4 hours, then 350 ℃ of sintering 8 hours, obtain mixing cobalt ferric phosphate.
(4) take 50g and mix cobalt ferric phosphate, 14.4g lithium carbonate, 12.6g sucrose and 0.15g polyvinyl alcohol add in blender, add 180ml water, and adjusting solid content is 30%, with the mixing speed of 800r/min, stirs after 0.5 hour and stops stirring.By this material input spray dryer, controlling drying machine inlet temperature is 220 ℃, and 110 ℃ of outlet temperatures are sprayed dry.
(5) gained dried material is placed in to high pure nitrogen sintering furnace, 500 ℃ of sintering of sintering temperature 4 hours are set, 600 ℃ of sintering 6 hours, obtain mixing cobalt lithium iron phosphate positive material.
Utilize and in sem test preparation process, mix cobalt ferric phosphate granule size and pattern, and mix cobalt ferric phosphate with the test of X-ray energy spectrum analytic approach, result as shown in Figure 1.
Utilize sem test to mix cobalt lithium iron phosphate positive material granule size and pattern analytical test material tap density, mix cobalt amount and carbon content.Recording this, to mix cobalt lithium iron phosphate positive material particle size range be 80nm~3 μ m, and mixing cobalt amount is 3.2%, and carbon content of lithium iron phosphate is 4.5%.Material tap density is 1.2g/cm
3, as shown in Figure 2.
This is mixed to the 8:1:1 mixing in mass ratio of cobalt LiFePO 4 material, Super-P conductive carbon black, PVDF binding agent, the NMP of take makes uniform slurry as solvent, then by its blade coating on the aluminium foil of 20 micron thickness, after 120 ℃ of vacuumize, obtain anode pole piece, cut into suitable diameter, take lithium paper tinsel as to electrode, in being full of the glove box of argon gas, be assembled into button cell, with constant current, carry out charge-discharge test, charging/discharging voltage is 2.5-4.2V, specific capacity and the cycle performance of the different discharge-rates of test material.As shown in Figure 3, under 1C multiplying power, average specific discharge capacity is more than 142mAh/g, and under 10C multiplying power, average specific discharge capacity is higher than 110mAh/g.
Embodiment 2
(1) according to the mol ratio of Fe and doped metal ion sum and P, be 1:1, prepare respectively 2mol/L ferric chloride solution and 2mol/L ammonium dihydrogen phosphate, two solution are mixed, obtaining Fe and P total concentration is 2mol/L mixed solution.Prepare 1mol/L ammonium molybdate solution and 2mol/L sal volatile.
(2) by load weighted 0.1g polyethylene glycol and 0.05g polyvinyl alcohol in advance dispersant in 100ml deionized water, add in the 1L stainless steel reactor with chuck and stirring and stir, mixing speed is 600r/min, and controlling chuck circulating water temperature is 15 ℃.
(3) by the mixed solution of ferric chloride solution and ammonium dihydrogen phosphate with 15ml/min charging rate input reactor, by 1mol/L ammonium molybdate solution with 10ml/min charging rate input reactor.Meanwhile, by 2mol/L sal volatile input reactor, controlling pH is 4.0, regulates the charging rate of 2mol/L sal volatile.Adjusting mixing speed is 2000r/min, reacts and within 0.5 hour, starts discharging.By material filtering, with deionized water, wash 3 times, with ethanol, wash 1 time, at 80 ℃, dry 6 hours, then 450 ℃ of sintering 6 hours, obtain mixing molybdophosphate iron.
(4) take 50g and mix molybdophosphate iron, 8.4g lithium hydroxide, 4.6g electrically conductive graphite, 0.2g polyethylene glycol and 0.05g polyvinyl alcohol add in blender, add 570ml water, and adjusting solid content is 10%, with the mixing speed of 500r/min, stirs after 1.5 hours and stops stirring.By this material input spray dryer, controlling drying machine inlet temperature is 180 ℃, and 90 ℃ of outlet temperatures are sprayed dry.
(5) gained dried material is placed in to high-purity argon gas sintering furnace, 400 ℃ of sintering of sintering temperature 6 hours are set, 700 ℃ of sintering 6 hours, obtain mixing molybdophosphate iron lithium anode material.
This mixes molybdophosphate iron lithium anode material granule size and pattern to utilize sem test, test material tap density, mixes molybdenum amount and carbon content.
This is mixed to the 8:1:1 mixing in mass ratio of molybdophosphate iron lithium material, Super-P conductive carbon black, PVDF binding agent, the NMP of take makes uniform slurry as solvent, then by its blade coating on the aluminium foil of 20 micron thickness, after 120 ℃ of vacuumize, obtain anode pole piece, cut into suitable diameter, take lithium paper tinsel as to electrode, in being full of the glove box of argon gas, be assembled into button cell, with constant current, carry out charge-discharge test, charging/discharging voltage is 2.5-4.2V, specific capacity and the cycle performance of the different discharge-rates of test material.
Recording this, to mix molybdophosphate iron lithium anode material particle size range be 50nm~1 μ m, and mixing molybdenum amount is 4.5%, and carbon content of lithium iron phosphate is 0.5%.Material tap density is 1.4g/cm
3.Room temperature records mixes the discharge performance of molybdophosphate iron lithium under different multiplying, and under 1C multiplying power, average specific discharge capacity is more than 140mAh/g, and under 10C multiplying power, average specific discharge capacity is higher than 105mAh/g.
Embodiment 3
(1) according to the mol ratio of Fe and doped metal ion sum and P, be 1:1, prepare respectively 0.5mol/L ferric oxalate solution and 1mol/L phosphoric acid solution, two solution are mixed, obtaining Fe and P total concentration is 0.75mol/L mixed solution.Prepare 0.1mol/L zinc nitrate solution and 0.1mol/L sodium hydroxide solution.
(2) by load weighted 0.05g lauryl sodium sulfate in advance dispersant in 100ml deionized water, add in the 1L stainless steel reactor with chuck and stirring and stir, mixing speed is 800r/min, controlling chuck circulating water temperature is 60 ℃.
(3) by the mixed solution of ferric oxalate solution and phosphoric acid solution with 2ml/min charging rate input reactor, by 0.1mol/L zinc nitrate solution with 1ml/min charging rate input reactor.Meanwhile, by the sodium hydroxide solution input reactor of 0.1mol/L, controlling pH is 5.0, regulates the charging rate of sodium hydroxide solution.Adjusting mixing speed is 600r/min, reacts and within 4 hours, starts discharging.By material filtering, with deionized water, wash 3 times, with ethanol, wash 1 time, at 80 ℃, dry 5 hours, then 550 ℃ of sintering 4 hours, obtain mixing zinc ferric phosphate.
(4) take 50g and mix zinc ferric phosphate, 17.7g lithium oxalate, 29.8g glucose and 0.05g lauryl sodium sulfate add in blender, add 98ml water, and adjusting solid content is 50%, with the mixing speed of 400r/min, stirs after 2.0 hours and stops stirring.By this material input spray dryer, controlling drying machine inlet temperature is 250 ℃, and 120 ℃ of outlet temperatures are sprayed dry.
(5) gained dried material is placed in to high pure nitrogen sintering furnace, 450 ℃ of sintering of sintering temperature 6 hours are set, 650 ℃ of sintering 5 hours, obtain mixing zinc lithium iron phosphate positive material.
This mixes zinc lithium iron phosphate positive material granule size and pattern to utilize sem test, tests this material tap density, mixes zinc amount and carbon content.
This is mixed to the 8:1:1 mixing in mass ratio of zinc LiFePO 4 material, Super-P conductive carbon black, PVDF binding agent, the NMP of take makes uniform slurry as solvent, then by its blade coating on the aluminium foil of 20 micron thickness, after 120 ℃ of vacuumize, obtain anode pole piece, cut into suitable diameter, take lithium paper tinsel as to electrode, in being full of the glove box of argon gas, be assembled into button cell, with constant current, carry out charge-discharge test, charging/discharging voltage is 2.5-4.2V, specific capacity and the cycle performance of the different discharge-rates of test material.
Recording this, to mix zinc lithium iron phosphate positive material particle size range be 1 μ m~6 μ m, and mixing zinc amount is 0.5%, and carbon content of lithium iron phosphate is 3.5%.Material tap density is 1.1g/cm
3.Under 1C multiplying power, average specific discharge capacity is more than 140mAh/g, and under 10C multiplying power, average specific discharge capacity is higher than 100mAh/g.
Embodiment 4
The step of preparing micro-nano-scale LiFePO4 is as follows:
(1) according to the mol ratio of Fe and doped metal ion sum and P, be 1:1, through stoichiometry accurately, prepare respectively 1mol/L ironic citrate solution and 1mol/L potassium dihydrogen phosphate, two solution are mixed, obtaining Fe and P total concentration is 1mol/L mixed solution.Prepare 0.5mol/L manganese nitrate solution and 0.5mol/L potassium bicarbonate solution.
(2) by load weighted 0.20g polysorbate in advance dispersant in 100ml deionized water, add in the 1L stainless steel reactor with chuck and stirring and stir, mixing speed is 400r/min, controlling chuck circulating water temperature is 80 ℃.
(3) by the mixed solution of 1mol/L ironic citrate solution and 1mol/L potassium dihydrogen phosphate with 2ml/min charging rate input reactor, by 0.5mol/L manganese nitrate solution with 1ml/min charging rate input reactor.Meanwhile, by the potassium bicarbonate solution input reactor of 0.5mol/L, controlling pH is 6.0, regulates the charging rate of potassium bicarbonate solution.Adjusting mixing speed is 1000r/min, reacts and within 3 hours, starts discharging.By material filtering, with deionized water, wash 3 times, with ethanol, wash 1 time, at 80 ℃, dry 7 hours, then 400 ℃ of sintering 6 hours, obtain mixing manganese ferric phosphate.
(4) take 50g and mix manganese ferric phosphate, 19.4g lithium acetate, 31.3g fructose and 0.15g polysorbate add in blender, add 152ml water, and adjusting solid content is 40%, with the mixing speed of 500r/min, stirs after 1.5 hours and stops stirring.By this material input spray dryer, controlling drying machine inlet temperature is 230 ℃, and 110 ℃ of outlet temperatures are sprayed dry.
(5) gained dried material is placed in to hydrogen-argon-mixed (containing the hydrogen of cumulative volume 2%) sintering furnace, 450 ℃ of sintering of sintering temperature 5 hours are set, 700 ℃ of sintering 4 hours, obtain mixing manganese lithium iron phosphate positive material.
This mixes manganese lithium iron phosphate positive material granule size and pattern to utilize sem test, test material tap density, mixes manganese amount and carbon content.
This is mixed to the 8:1:1 mixing in mass ratio of manganese LiFePO 4 material, Super-P conductive carbon black, PVDF binding agent, the NMP of take makes uniform slurry as solvent, then by its blade coating on the aluminium foil of 20 micron thickness, after 120 ℃ of vacuumize, obtain anode pole piece, cut into suitable diameter, take lithium paper tinsel as to electrode, in being full of the glove box of argon gas, be assembled into button cell, with constant current, carry out charge-discharge test, charging/discharging voltage is 2.5-4.2V, specific capacity and the cycle performance of the different discharge-rates of test material.
Recording this, to mix manganese lithium iron phosphate positive material particle size range be 200nm~4 μ m, and mixing manganese amount is 5.0%, and carbon content of lithium iron phosphate is 1.9%.Material tap density is 1.5g/cm
3.Room temperature records mixes the discharge performance of manganese LiFePO4 under different multiplying, and under 1C multiplying power, average specific discharge capacity is more than 140mAh/g, and under 10C multiplying power, average specific discharge capacity is higher than 100mAh/g.
Embodiment 5
The step of preparing micro-nano-scale doped iron lithium phosphate is as follows:
(1) according to the mol ratio of Fe and doped metal ion sum and P, be 1:1, prepare respectively 1mol/L iron nitrate solution and 1mol/L phosphoric acid solution, two solution are mixed, obtaining Fe and P total concentration is 1mol/L mixed solution.Prepare 0.1mol/L ammonium tungstate solution and 2mol/L ammonia spirit.
(2) by load weighted 0.15g pentaerythrite in advance dispersant in 100ml deionized water, add in the 1L stainless steel reactor with chuck and stirring and stir, mixing speed is 700r/min, controlling chuck circulating water temperature is 35 ℃.
(3) by the mixed solution of 1mol/L iron nitrate solution and 1mol/L phosphoric acid solution with 10ml/min charging rate input reactor, by 0.1mol/L ammonium tungstate solution with 5ml/min charging rate input reactor.Meanwhile, by the ammonia spirit input reactor of 2mol/L, controlling pH is 3.0, regulates the charging rate of ammonia spirit.Adjusting mixing speed is 1200r/min, reacts and within 1.2 hours, starts discharging.By material filtering, with deionized water, wash 3 times, with ethanol, wash 1 time, at 80 ℃, dry 8 hours, then 550 ℃ of sintering 4 hours, obtain mixing tungstophosphoric acid iron.
(4) take 50g and mix tungstophosphoric acid iron, 22.8g lithium nitrate, 20.6g polyethylene glycol (molecular weight 4000) and 0.25g pentaerythrite add in blender, add 375ml water, and adjusting solid content is 20%, with the mixing speed of 700r/min, stirs after 1.0 hours and stops stirring.By this material input spray dryer, controlling drying machine inlet temperature is 240 ℃, and 120 ℃ of outlet temperatures are sprayed dry.
(5) gained dried material is placed in to high-purity argon gas sintering furnace, 500 ℃ of sintering of sintering temperature 4 hours are set, 700 ℃ of sintering 4 hours, obtain mixing tungstophosphoric acid iron lithium anode material.
This mixes tungstophosphoric acid iron lithium anode material granule size and pattern to utilize sem test, test material tap density, mixes tungsten amount and carbon content.
This is mixed to the 8:1:1 mixing in mass ratio of tungstophosphoric acid iron lithium material, Super-P conductive carbon black, PVDF binding agent, the NMP of take makes uniform slurry as solvent, then by its blade coating on the aluminium foil of 20 micron thickness, after 120 ℃ of vacuumize, obtain anode pole piece, cut into suitable diameter, take lithium paper tinsel as to electrode, in being full of the glove box of argon gas, be assembled into button cell, with constant current, carry out charge-discharge test, charging/discharging voltage is 2.5-4.2V, specific capacity and the cycle performance of the different discharge-rates of test material.
Recording this, to mix tungstophosphoric acid iron lithium anode material particle size range be 80nm~3 μ m, and mixing tungsten amount is 2.7%, and carbon content of lithium iron phosphate is 1.5%, and material tap density is 1.6g/cm
3.Room temperature records mixes the discharge performance of tungstophosphoric acid iron lithium under different multiplying, and under 1C multiplying power, average specific discharge capacity is more than 145mAh/g, and under 10C multiplying power, average specific discharge capacity is higher than 110mAh/g.
Claims (11)
1. a preparation method for micro-nano doped metal ion lithium iron phosphate positive material, is characterized in that, the method comprises the following steps:
(1) according to the mol ratio of Fe and doped metal ion sum and P, be that 1:1 weighs source of iron, phosphorus source and doped metal ion compound, by three's water-soluble solution that is mixed with respectively, then source of iron and phosphorus source solution are mixed to get to the mixed solution that Fe and P total concentration are 0.75-2mol/L, doped metal ion amount is 0.01 ~ 0.05 of total mole of doped metal ion and Fe, and the concentration of doped metal ion compound solution is 0.1 ~ 1mol/L; Compound concentration is the alkaline solution of 0.1-3mol/L;
(2) in reactor, add the dispersant of deionized water and the theoretical ferric phosphate quality 0.1% ~ 0.5% generating, even with the speed dispersed with stirring of 200-2000r/min, reaction 0.5-4 hour;
(3) the phosphorus source in step (1) and source of iron mixed solution, doped metal ion compound solution, aqueous slkali are distinguished in the reactor of input step (2), and be uniformly mixed with the speed of 200-2000r/min, reaction 0.5-4 hour, reaction temperature is 15-80 ℃; Wherein the charging rate of phosphorus source and source of iron mixed solution is 2-15ml/min, and doped metal ion compound solution charging rate is 1-10ml/min, and alkaline solution charging rate regulates by the pH of system, and pH control range is 1.5-6.0;
(4) step (3) products therefrom is filtered, with deionized water, wash 3 times, with ethanol, wash 1 time, 80 ℃, dry 4-8 hour; Then, at 350-550 ℃, sintering 4-8 hour obtains the ferric phosphate containing doped metal ion;
(5) by Li, Fe, P three's mol ratio, be (1 ~ 1.05): (0.95 ~ 1): 1 takes respectively ferric phosphate prepared by lithium source and step (4); By ferric phosphate quality 0.5 ~ 5% take carbon source, lithium source, ferric phosphate, carbon source are added in the aqueous solution that contains dispersant, in the blender with stirring, take mixing speed as 200-800r/min dispersion 0.25-2 hour, and be 10%-50% with deionized water adjustment solid content; Wherein the consumption of dispersant is theoretical 0.1% ~ 0.5% of the ferric phosphate quality that generates;
(6) by the mixed material input spray dryer in step (5), spray dry; Control inlet temperature is 180-250 ℃, and outlet temperature is 90-120 ℃;
(7) by step (6) gained dried material sintering temperature under inert gas, be at 400-700 ℃, sintering time is 8-12 hour, obtains micro-nano doped metal ion lithium iron phosphate positive material by sintered products is cooling.
2. preparation method according to claim 1, is characterized in that, described source of iron is ferric nitrate, iron chloride, ferric sulfate or ironic citrate.
3. preparation method according to claim 1, is characterized in that, described phosphorus source is phosphoric acid, ammonium dihydrogen phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate.
4. preparation method according to claim 1, is characterized in that, described doped metal ion compound is cobalt nitrate, manganese nitrate, zinc nitrate, ammonium molybdate, ammonium tungstate, ammonium titanium fluoride, strontium nitrate, nickel nitrate, magnesium nitrate or zirconium nitrate.
5. preparation method according to claim 1, is characterized in that, described lithium source is lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium oxalate or lithium sulfate.
6. preparation method according to claim 1, it is characterized in that, described carbon source is one or more in acetylene black, electrically conductive graphite, carbon nano-tube, Graphene, sucrose, glucose, fructose, citric acid, pentaerythrite, vitamin C, polyvinyl alcohol, polyethylene glycol and polyethers.
7. preparation method according to claim 1, is characterized in that, the alkali compounds in described alkaline solution is carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, sodium carbonate, saleratus, potash, NaOH, potassium hydroxide or ammoniacal liquor.
8. preparation method according to claim 1, it is characterized in that, described dispersant is that lauryl sodium sulfate, dodecyl sodium sulfate, APES 10, dioctyl sodium sulfosuccinate, Sucrose Fatty Acid Ester, aliphatic acid sorb are smooth, one or more in polysorbate, polyoxyethylene, polyvinyl alcohol, methyl anyl alcohol, cellulose derivative, fatty acid polyethylene glycol ester.
9. preparation method according to claim 1, is characterized in that, reactor described in step (2) is that this reactor can continuous discharge with the stainless steel reactor of chuck, charging aperture, discharging opening, overfall, blender and PH meter.
10. preparation method according to claim 1, is characterized in that, lithium source described in step (5) adds with powder or is configured to the aqueous solution and adds.
11. preparation methods according to claim 1, is characterized in that, inert gas described in step (7) is high pure nitrogen, high-purity argon gas or is that the High Purity Hydrogen of 2% hydrogen is argon-mixed containing volume.
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CN101112979B (en) * | 2007-06-27 | 2010-05-19 | 广州市鹏辉电池有限公司 | Solid-phase method for preparation of high-density spherical-like ferric phosphate lithium |
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