CN107482182A - 碳包覆离子掺杂磷酸锰锂电极材料及其制备方法 - Google Patents
碳包覆离子掺杂磷酸锰锂电极材料及其制备方法 Download PDFInfo
- Publication number
- CN107482182A CN107482182A CN201710568748.5A CN201710568748A CN107482182A CN 107482182 A CN107482182 A CN 107482182A CN 201710568748 A CN201710568748 A CN 201710568748A CN 107482182 A CN107482182 A CN 107482182A
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- China
- Prior art keywords
- electrode material
- carbon
- lithium
- manganese
- carbon coating
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- 239000007772 electrode material Substances 0.000 title claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 70
- 238000000576 coating method Methods 0.000 title claims abstract description 31
- 239000011248 coating agent Substances 0.000 title claims abstract description 30
- 150000002500 ions Chemical class 0.000 title claims abstract description 22
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011572 manganese Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 23
- -1 ferrous metal compound Chemical class 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000011247 coating layer Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002270 dispersing agent Substances 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
- 239000002296 pyrolytic carbon Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 238000001465 metallisation Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- 229910000765 intermetallic Inorganic materials 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 claims description 2
- WKCZSFRAGKIIKN-UHFFFAOYSA-N 2-(4-tert-butylphenyl)ethanamine Chemical compound CC(C)(C)C1=CC=C(CCN)C=C1 WKCZSFRAGKIIKN-UHFFFAOYSA-N 0.000 claims description 2
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 claims description 2
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- 239000004375 Dextrin Substances 0.000 claims description 2
- 229920001353 Dextrin Polymers 0.000 claims description 2
- 239000005955 Ferric phosphate Substances 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- 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 2
- 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 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 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 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 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
- 210000000481 breast Anatomy 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019425 dextrin Nutrition 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 229940032958 ferric phosphate Drugs 0.000 claims description 2
- 229940032950 ferric sulfate Drugs 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 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
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 235000014872 manganese citrate Nutrition 0.000 claims description 2
- 239000011564 manganese citrate Substances 0.000 claims description 2
- 229940097206 manganese citrate Drugs 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 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
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- RZVXOCDCIIFGGH-UHFFFAOYSA-N chromium gold Chemical compound [Cr].[Au] RZVXOCDCIIFGGH-UHFFFAOYSA-N 0.000 claims 1
- 229940056319 ferrosoferric oxide Drugs 0.000 claims 1
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 15
- 238000007599 discharging Methods 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000013590 bulk material Substances 0.000 abstract 1
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 10
- 239000002245 particle Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910015944 LiMn0.8Fe0.2PO4 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- ZEEDCGIEVPGBCZ-UHFFFAOYSA-N [Li].[Mn].P(O)(O)(O)=O Chemical compound [Li].[Mn].P(O)(O)(O)=O ZEEDCGIEVPGBCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
- 229940006116 lithium hydroxide Drugs 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000006104 solid solution Substances 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
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Abstract
本发明提供一种碳包覆离子掺杂磷酸锰锂电极材料及其制备方法,电极材料的化学式为LiMxNyMn1‑x‑yPO4,0.05≤x≤0.25,0.01≤y≤0.10,通过金属元素的有效掺杂和碳原位包覆来提高锂离子电池的大电流充电性能和放电性能。即添加一类氧化还原电位低于Mn3+/Mn2+电位的金属M用于改善其锂离子电池的放电性能;同时添加一类氧化还原电位高于Mn3+/Mn2+电位的金属N用于改善其锂离子电池的充电性能;碳原位包覆磷酸锰锂本体材料,使其表面部分或全部碳层包覆,提高材料的电子电导率。本发明有效的提高了锂离子电池的比容量和大电流充放电性能,在动力和储能锂离子电池领域具有很好的应用前景。
Description
技术领域
本发明涉及锂离子电池领域,具体涉及碳包覆离子掺杂磷酸锰锂电极材料及其制备方法。
背景技术
锂离子电池因其具备能量密度高、循环寿命长、无记忆效应、自放电低、对环境具备友好性等优点,作为最新一代高比能量化学电源已经广泛应用于移动通讯、便携式手提计算机、摄像机、照相机、便携式仪器仪表等领域,也是各国大力研究的电动汽车的首选配套电源,因此发展锂离子电池材料具有重要意义。近年来混合动力车(HEV)和纯电动车(EV)的蓬勃发展,对电池容量和倍率放电性能以及充放电速度等方面都有更高的要求,这就意味着对正极材料有更高的要求。
目前广泛研究的锂离子电池正极材料主要是锂过渡金属氧化物,金属氧化物如层状结构的LiMO2(M=Co Ni Mn)和尖晶石型结构的锰酸锂(LiMn2O4),其中钴酸锂(LiCoO2)成本较高、资源贫乏且毒性大;镍酸锂(LiNiO2)制备困难,热稳定性差;LiMn2O4容量较低,循环稳定性较差。锂离子电池正极材料还有三元材料LiNi1/3Co1/3Mn1/3O2,LiNi1/3Co1/3Mn1/3O2比容量高、价格稍低,但循环寿命不长、存在安全隐患。同时,第一代动力电池磷酸铁锂正极材料也得到应用,其安全性能高,但电压平台仅为3.4V,理论比容量170mAh/g,电池能量密度较低。相比之下,同样具有橄榄型结构的LiMnPO4具有较高的电极电位,比LiFePO4的电极电位高0.7V,满足现有电解液的电压使用范围;同时LiMnPO4具有171mAh/g的理论比容量。如果LiMnPO4的实际容量发挥到与LiFePO4相同的程度,其能量密度将比磷酸铁锂高20%以上;除此之外,我国拥有丰富的锰矿资源,锰源毒性小,价格便宜,对环境友好。因此,LiMnPO4表现出了很强的吸引力,是目前更具发展前景的新型4V锂离子电池正极材料。
但是LiMnPO4仍然存在一定的问题,LiMnPO4中发生跃迁的能隙为2eV,电子导电性很差,属于绝缘体。LiMnPO4电子电导率偏低(<10-10S/cm),致使合成能够可逆充放电的LiMnPO4比较困难,且大电流充放电性能差。针对LiMnPO4电子导电率低和离子迁移率低等特点,研究人员主要采取以下措施来改善和提高材料的性能:(1)颗粒粒径纳米化,减小颗粒粒径以缩短锂离子扩散途径;(2)碳包覆以提高颗粒之间的导电性;(3)金属离子掺杂,提高材料的导电性和倍率性能;(4)合成复合材料。目前金属元素的添加还基本停留在提高材料的离子迁移速率,电子导电性和循环性能。Yamada等通过掺铁的方法合成了Li(MnyFe1-y)PO4材料,并获得4V级容量。Yang等采用固相法制备了LiMn0.95M0.05PO4(M=Mg、V、Fe、Co、Cd),改善了锂离子电池的比容量性能和循环性能。刘爱芳等人采用固相法合成了LiMn0.8Fe0.2PO4/C、LiMn0.8V0.2PO4/C和LiMn0.6Fe0.2V0.2PO4/C 3种复合正极材料,充放电测试表明LiMn0.6Fe0.2V0.2PO4放电倍率为0.1C时,首次放电比容量是118mAh/g。Lee等采用Mg和在Zr共同掺杂形成的LiMn0.88Mg0.1Zr0.04PO4固溶体比单一元素的掺杂表现出更好的电化学活性。专利CN103825029A通过稀土元素Y和过渡元素铁替换部分锰,以及掺杂F替代部分P改性,以提高电子导电率和物质活性,然后在其表面包覆碳黑和碳纳米管混合碳包覆网络,进一步提高导电性能和循环稳定性;专利CN201310308201.3通过掺杂镁提高材料的离子迁移速率和电子导电性;专利CN102931405B通过Ti、Co、Fe、Mg、Al、Cr、Nb中的任意一种金属元素的添加,提高锂离子的扩散速率,进而提高磷酸锰锂材料的放电容量和循环性能。
目前金属元素的掺杂比较随意,主要集中在比容量的提高及循环性能的改善,不能有效的提高LiMnPO4正极材料的充电性能和放电性能。
发明内容
本发明的目的在于提供一种高比容量的金属元素掺杂的LiMnPO4电极材料,同时提高金属元素掺杂的LiMnPO4电极材料的充电性能和放电性能。
为解决上述问题,本发明提供一种碳包覆离子掺杂磷酸锰锂电极材料,其特征在于:电极材料的化学式为LiMxNyMn1-x-yPO4,其中M为M3+/M2+氧化还原电位低于Mn3+/Mn2+的金属;N为N3+/N2+氧化还原电位高于Mn3+/Mn2+的金属;其中0.05≤x≤0.25,0.01≤y≤0.10;电极材料表面部分或全部为碳包覆层。
本发明提供的碳包覆离子掺杂磷酸锰锂电极材料,既提高锂离子电池大电流充电性能又提高其大电流放电性能。主要是通过金属元素的有效掺杂和碳原位包覆电极材料来实现。金属元素的有效掺杂是指:添加一类氧化还原电位低于Mn3+/Mn2+电位的金属用于改善其锂离子电池的放电性能,同时添加一类氧化还原电位高于Mn3+/Mn2+电位的金属用于改善其锂离子电池的充电性能。碳层包覆在活性物质颗粒表面,增加材料的导电率。
上述氧化还原电位低于Mn3+/Mn2+电位的金属元素M选自Fe、Ti、Cr或V中的任意一种或几种的任意组合。
上述氧化还原电位高于Mn3+/Mn2+电位的金属元素N为Ni或Co的一种或两种的任意组合。
上述碳包覆层为无定型碳或石墨化碳。其碳微粒可达纳米级,进一步增大导电面积。
进一步地,碳包覆层的量为电极材料总重量的2-20%。由于碳的密度较低,在电极材料中引入碳时,会使电极材料的振实密度和体积能量密度均有所下降,故在进行碳包覆改性时,碳含量应控制在合理范围内。
本发明还提供一种碳包覆双离子掺杂磷酸锰锂电极材料的制备方法,具体包括以下步骤:
(1)将锂源、锰源、磷源、M源、N源、碳源和分散剂混合均匀,得到电极材料浆料;
(2)将得到的浆料进行干燥处理,得到电极材料粉末;
(3)将得到的电极材料粉末在惰性气氛保护下进行烧结,得到碳包覆离子掺杂磷酸锰锂电极材料粉末。
进一步地,所述锂源选自碳酸锂、氢氧化锂、乙酸锂、硝酸锂、草酸锂或碳酸氢锂中的一种或几种;
所述锰源选自碳酸锰、硫酸锰、乙酸锰、氯化锰、草酸锰、硝酸锰或柠檬酸锰中的一种或几种;
所述磷源选自磷酸、磷酸二氢铵、磷酸氢二铵、磷酸铵和磷酸二氢锂中的一种或几种;
所述M源选自铁金属化合物,钛金属化合物,铬金属化合物或钒金属化合物中的一种或几种;铁金属化合物选自硫酸铁、磷酸铁、草酸亚铁、醋酸亚铁、三氧化二铁、四氧化三铁中的一种或几种;钛金属化合物选自硫酸氧钴、钛酸四丁酯、四氯化钛中的一种或几种;铬金属化合物选自铬酸铵、铬酸钠、铬酸钾、硝酸铬中的一种或几种;钒金属化合物选自偏钒酸铵、偏钒酸钠、偏钒酸钾、正钒酸钠、焦钒酸钠中的一种或几种;
所述N源选自钴金属化合物或镍金属化合物中的一种或两种;钴金属化合物选自硫酸钴、硝酸钴、乙酸钴、氯化钴、氢氧化钴中的一种或几种;镍金属化合物选自硫酸镍、硝酸镍、乙酸镍、氯化镍、氢氧化镍中的一种或几种;
所述碳源为天然石墨、人造石墨、硬碳、有机热解碳和碳纳米导电材料中一种或多种;其中有机热解碳为以聚乙烯醇、丁苯橡胶乳、羧甲基纤维素、聚苯乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、酚醛树脂、环氧树脂、葡萄糖、蔗糖、果糖、纤维素、淀粉或糊精为前驱体,经高温碳化所形成的热解炭;碳纳米导电材料为导电碳黑、碳纳米管、石墨烯、纳米碳纤维或纳米碳微球;
所述分散剂选自去离子水、甲醇、无水乙醇、乙二醇、异丙醇、苯甲醇和丙酮中的一种或几种。
进一步地,在步骤(1)中,控制锂源、锰源、M源、N源、磷源的加入量,使得到的电极材料浆料中锂元素、锰元素、M元素、N元素和磷元素的摩尔比为1:(0.75-0.95):(0.05-0.25):(0.01-0.1):1;分散剂的加入量为电极材料浆料质量的50-80%;控制碳源的加入,使得到的碳包覆层的量为电极材料总重量的2-20%。
进一步地,步骤(2)中所述的干燥处理为压力式喷雾干燥、离心式喷雾干燥、气流式喷雾干燥和真空干燥中的一种。
步骤(3)中所述的烧结处理,是指将电极材料粉末以1-10℃/min的速率升温至300-500℃,恒温5-8小时,然后以1-10℃/min的速率升温至600-800℃,恒温8-20小时。
与现有技术相比,本发明的有益效果在于:
本发明提供一种碳包覆离子掺杂磷酸锰锂电极材料及其制备方法,通过两种不同类型金属元素的有效掺杂和碳原位包覆来提高锂离子电池的大电流充电性能和放电性能,在动力和储能锂离子电池领域具有很好的应用前景。按本发明方法得到的电极材料粒径均匀,晶格规整,使用该电极材料所制备锂电池比容量高。通过在电极材料表面设置碳包覆层,提高材料的电子电导率。
附图说明
图1为LiFe0.25Co0.05Mn0.7PO4不同倍率下(C/20,C/10,C/5,C/2,C,2C)首次充放电曲线谱图;
图2为LiMnPO4不同倍率下(C/20,C/10,C/5,C/2,C,2C)首次充放电曲线谱图;
图3为LiFe0.25Co0.05Mn0.7PO4的SEM图。
具体实施方式
为了更好地理解本发明,下面结合本实施例对本发明进行进一步的阐明。
实施例1
Co和Fe掺杂LiFe0.25Co0.05Mn0.7PO4的制备
(1)按照摩尔比1:0.7:0.05:0.25:1称取乙酸锂、硫酸锰、硝酸钴、硫酸亚铁和磷酸二氢铵;称取碳源,碳源的称取量应保证碳包覆层的量为电极材料总重量的3%;加入去离子水与上述原料进行混合得到电极材料浆料,去离子水的加入量为电极材料浆料的质量的75%;
(2)将得到的电极材料浆料以进气口温度260℃喷雾干燥,得到粉末;
(3)将得到的粉末在N2气氛下以5℃/分钟的速率升温350℃,恒温6小时,然后以3℃/分钟的速率升温至680℃,恒温10小时得到电极材料粉末。
其充放电曲线图如图1,与LiMnPO4充放电曲线相比,本实施例制备的LiFe0.25Co0.05Mn0.7PO4的充电和放电性能明显提高。
实施例2
Co和Ti掺杂LiTi0.1Co0.1Mn0.8PO4的制备
(1)按照摩尔比1:0.8:0.1:0.1称取硝酸锂、硝酸锰、硫酸钴、硫酸氧钛和磷酸铵;称取碳源,其中碳源的称取量应保证碳包覆层的量为电极材料总重量的3%;加入乙二醇与上述原料进行混合得到电极材料浆料,乙二醇的加入量为电极材料浆料的质量的75%;
(2)将得到的电极材料浆料以进气口温度240℃喷雾干燥,得到粉末;
(3)将得到的粉末在N2气氛下以5℃/分钟的速率升温350℃,恒温6小时,然后以3℃/分钟的速率升温至680℃,恒温10小时得到电极材料粉末。
实施例3
Ni和Fe掺杂LiFe0.1Ni0.1Mn0.8PO4的制备
(1)按照摩尔比1:0.8:0.1:0.1:0.1称取氢氧化锂、乙酸锰、硫酸镍、草酸亚铁和磷酸氢二铵;称取碳源,其中碳源的称取量应保证碳包覆层的量为电极材料总重量的5%;加入无水乙醇与上述原料混合得到电极材料浆料,无水乙醇的加入量为电极材料浆料的质量的80%;
(2)将得到的电极材料浆料以进气口温度260℃喷雾干燥,得到粉末;
(3)将得到的粉末在N2气氛下以5℃/分钟的速率升温350℃,恒温6小时,然后以3℃/分钟的速率升温至680℃,恒温10小时得到电极材料粉末。
实施例4
Ni和Cr掺杂LiCr0.15Ni0.1Mn0.75PO4的制备
(1)按照摩尔比1:0.75:0.1:0.15:1称取柠檬酸锂、氯化锰、硝酸镍、硝酸铬和磷酸铵;称取碳源,其中碳源的加入量应保证碳包覆层的量为电极材料总重量的8%;加入去离子水与上述原料进行混合得到电极材料浆料,去离子水的加入量为电极材料浆料的质量的80%;
(2)将得到的电极材料浆料以进气口温度240℃喷雾干燥,得到粉末;
(3)将得到的粉末在N2气氛下以5℃/分钟的速率升温350℃,恒温6小时,然后以3℃/分钟的速率升温至680℃,恒温10小时得到电极材料粉末。
对比例
LiMnPO4的制备
(1)按照摩尔比1:1:1称取乙酸锂、硫酸锰和磷酸二氢铵;称取碳源,其中碳源的称取量应保证碳包覆层的量为电极材料总重量的3%;加入去离子水与上述原料进行混合得到电极材料浆料,去离子水的加入量为电极材料浆料的质量的75%;
(2)将得到的电极材料浆料以进气口温度260℃喷雾干燥,得到粉末;
(3)将得到的电极材料粉末在N2气氛下以5℃/分钟的速率升温350℃,恒温6小时,然后以3℃/分钟的速率升温至680℃,恒温10小时得到电极材料粉末。
将上述各实施例与对比例中制备得到的电极材料装配成CR2016型扣式电池进行电化学测试,对比例电极材料在不同倍率(C/20、C/10、C/5、C/2、1C、2C)下充放电,其对应的放电比容量(单位:mAh/g)具体如表1所示。
表1
上述实施例仅仅是较佳的实施例,并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。凡依本发明专利范围的内容所作的等效变化与修饰,都应作为本发明的技术范畴。
Claims (10)
1.一种碳包覆离子掺杂磷酸锰锂电极材料,其特征在于:电极材料的化学式为LiMxNyMn1-x-yPO4,其中M为M3+/M2+氧化还原电位低于Mn3+/Mn2+的金属;N为N3+/N2+氧化还原电位高于Mn3+/Mn2+的金属;其中0.05≤x≤0.25,0.01≤y≤0.10;电极材料表面部分或全部为碳包覆层。
2.如权利要求1所述的一种碳包覆离子掺杂磷酸锰锂电极材料,其特征在于M为Fe、Ti、Cr或V中的一种或多种。
3.如权利要求1所述的一种碳包覆离子掺杂磷酸锰锂电极材料,其特征在于N为Ni或Co的一种或两种。
4.如权利要求1所述的一种碳包覆离子掺杂磷酸锰锂电极材料,其特征在于碳包覆层为无定型碳或石墨化碳。
5.如权利要求1所述的一种碳包覆离子掺杂磷酸锰锂电极材料,其特征在于碳包覆层为电极材料总重量的2-20%。
6.如权利要求1-5任一所述的一种碳包覆离子掺杂磷酸锰锂电极材料的制备方法,其特征在于,具体包括以下步骤:
(1)将锂源、锰源、磷源、M源、N源、碳源和分散剂混合均匀,得到电极材料浆料;
(2)将得到的浆料进行干燥处理,得到电极材料粉末;
(3)将得到的电极材料粉末在惰性气氛保护下进行烧结,得到碳包覆离子掺杂磷酸锰锂电极材料粉末。
7.如权利要求6所述的一种碳包覆离子掺杂磷酸锰锂电极材料的制备方法,其特征在于:
所述锂源选自碳酸锂、氢氧化锂、乙酸锂、硝酸锂、草酸锂或碳酸氢锂中的一种或几种;
所述锰源选自碳酸锰、硫酸锰、乙酸锰、氯化锰、草酸锰、硝酸锰或柠檬酸锰中的一种或几种;
所述磷源选自磷酸、磷酸二氢铵、磷酸氢二铵、磷酸铵和磷酸二氢锂中的一种或几种;
所述M源选自铁金属化合物,钛金属化合物,铬金属化合物或钒金属化合物中的一种或几种;铁金属化合物选自硫酸铁、磷酸铁、草酸亚铁、醋酸亚铁、三氧化二铁、四氧化三铁中的一种或几种;钛金属化合物选自硫酸氧钛、钛酸四丁酯、四氯化钛中的一种或几种;铬金属化合物选自铬酸铵、铬酸钠、铬酸钾、硝酸铬中的一种或几种;钒金属化合物选自偏钒酸铵、偏钒酸钠、偏钒酸钾、正钒酸钠、焦钒酸钠中的一种或几种;
所述N源选自钴金属化合物或镍金属化合物中的一种或两种;钴金属化合物选自硫酸钴、硝酸钴、乙酸钴、氯化钴、氢氧化钴中的一种或几种;镍金属化合物选自硫酸镍、硝酸镍、乙酸镍、氯化镍、氢氧化镍中的一种或几种;
所述碳源为天然石墨、人造石墨、硬碳、有机热解碳和碳纳米导电材料中一种或多种;其中有机热解碳为以聚乙烯醇、丁苯橡胶乳、羧甲基纤维素、聚苯乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、酚醛树脂、环氧树脂、葡萄糖、蔗糖、果糖、纤维素、淀粉或糊精为前驱体,经高温碳化所形成的热解炭;碳纳米导电材料为导电碳黑、碳纳米管、石墨烯、纳米碳纤维或纳米碳微球;
所述分散剂选自去离子水、甲醇、无水乙醇、乙二醇、异丙醇、苯甲醇和丙酮中的一种或几种。
8.如权利要求6所述的一种碳包覆离子掺杂磷酸锰锂电极材料的制备方法,其特征在于,在步骤(1)中,控制锂源、锰源、M源、N源、磷源的加入量,使得到的电极材料浆料中锂元素、锰元素、M元素、N元素和磷元素的摩尔比为1:(0.75-0.95):(0.05-0.25):(0.01-0.1):1;分散剂的加入量为电极材料浆料质量的50-80%;控制碳源的加入,使得到的碳包覆层的量为电极材料总重量的2-20%。
9.如权利要求6所述的一种碳包覆离子掺杂磷酸锰锂电极材料的制备方法,其特征在于,步骤(2)中所述的干燥处理为压力式喷雾干燥、离心式喷雾干燥、气流式喷雾干燥和真空干燥中的一种。
10.如权利要求6所述的一种碳包覆离子掺杂磷酸锰锂电极材料的制备方法,其特征在于,步骤(3)中所述的烧结处理,是指将电极材料粉末以1-10℃/min的速率升温至300-500℃,恒温5-8小时,然后以1-10℃/min的速率升温至600-800℃,恒温8-20小时。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103474656A (zh) * | 2013-07-22 | 2013-12-25 | 浙江瓦力新能源科技有限公司 | 一种以磷酸锰制备金属掺杂磷酸锰锂/碳复合材料的方法 |
CN103515594A (zh) * | 2012-06-26 | 2014-01-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | 碳包覆的磷酸锰锂/磷酸铁锂核壳结构材料及其制备方法 |
CN103904324A (zh) * | 2012-12-28 | 2014-07-02 | 河南科隆集团有限公司 | 锂离子电池用多元磷酸锰锂正极材料及其制备方法 |
CN104425820A (zh) * | 2013-09-09 | 2015-03-18 | 北京国能电池科技有限公司 | 磷酸铁锰锂材料、其制备方法及锂离子电池正极材料 |
CN106058225A (zh) * | 2016-08-19 | 2016-10-26 | 中航锂电(洛阳)有限公司 | 核壳结构LiMn1‑xFexPO4正极材料及其制备方法、锂离子电池 |
-
2017
- 2017-07-13 CN CN201710568748.5A patent/CN107482182B/zh not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103515594A (zh) * | 2012-06-26 | 2014-01-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | 碳包覆的磷酸锰锂/磷酸铁锂核壳结构材料及其制备方法 |
CN103904324A (zh) * | 2012-12-28 | 2014-07-02 | 河南科隆集团有限公司 | 锂离子电池用多元磷酸锰锂正极材料及其制备方法 |
CN103474656A (zh) * | 2013-07-22 | 2013-12-25 | 浙江瓦力新能源科技有限公司 | 一种以磷酸锰制备金属掺杂磷酸锰锂/碳复合材料的方法 |
CN104425820A (zh) * | 2013-09-09 | 2015-03-18 | 北京国能电池科技有限公司 | 磷酸铁锰锂材料、其制备方法及锂离子电池正极材料 |
CN106058225A (zh) * | 2016-08-19 | 2016-10-26 | 中航锂电(洛阳)有限公司 | 核壳结构LiMn1‑xFexPO4正极材料及其制备方法、锂离子电池 |
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