CN105990562B - A kind of the nano lithium iron manganese composite material and preparation method and application of core-shell structure - Google Patents
A kind of the nano lithium iron manganese composite material and preparation method and application of core-shell structure Download PDFInfo
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- CN105990562B CN105990562B CN201510072987.2A CN201510072987A CN105990562B CN 105990562 B CN105990562 B CN 105990562B CN 201510072987 A CN201510072987 A CN 201510072987A CN 105990562 B CN105990562 B CN 105990562B
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- 239000002131 composite material Substances 0.000 title claims abstract description 92
- 239000011258 core-shell material Substances 0.000 title claims abstract description 66
- DOCYQLFVSIEPAG-UHFFFAOYSA-N [Mn].[Fe].[Li] Chemical compound [Mn].[Fe].[Li] DOCYQLFVSIEPAG-UHFFFAOYSA-N 0.000 title abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 229910052493 LiFePO4 Inorganic materials 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 21
- 238000005253 cladding Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 66
- 239000011259 mixed solution Substances 0.000 claims description 55
- 239000002904 solvent Substances 0.000 claims description 52
- 239000000725 suspension Substances 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 32
- 239000000654 additive Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 230000000996 additive effect Effects 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000011572 manganese Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 28
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 23
- ZDEWGVLGXAHEIB-UHFFFAOYSA-N [C].[Mn].[Fe].[Li] Chemical compound [C].[Mn].[Fe].[Li] ZDEWGVLGXAHEIB-UHFFFAOYSA-N 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 229910019142 PO4 Inorganic materials 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- 235000011007 phosphoric acid Nutrition 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 150000005846 sugar alcohols Polymers 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- 229930006000 Sucrose Natural products 0.000 description 7
- 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 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 7
- 239000005720 sucrose Substances 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 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 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- -1 purity is high Substances 0.000 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 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052603 melanterite Inorganic materials 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000010450 olivine Substances 0.000 description 4
- 229910052609 olivine Inorganic materials 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 229910016153 LiMn0.9Fe0.1PO4 Inorganic materials 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 3
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 3
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- 239000001116 FEMA 4028 Substances 0.000 description 2
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 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 description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 2
- 229960004853 betadex Drugs 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
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- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 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 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
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- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of nano lithium iron manganese composite materials, specifically, the composite material includes the outer carbon-coating of core-shell structure and the optional cladding core-shell structure, wherein, the core-shell structure includes: (i) core, and the chemical composition of the core is LiMn1‑(x‑a)Fex‑aPO4, wherein 0.05≤a≤x≤0.6；(ii) nucleocapsid, the nucleocapsid are LiFePO4；And the partial size of the composite material is 10-900nm.The invention also discloses the preparation method and application of the composite material.Composite material of the present invention is conducive to improve lithium ion battery chemical property and preparation process strong operability, easily controllable and at low cost.
Description
Technical field
The present invention relates to electrochemical fields, a kind of nano lithium iron manganese composite material more particularly to core-shell structure and
Preparation method and application.
Background technique
Lithium ion battery has operating voltage height, energy density big and environmental-friendly as new generation of green energy system
The features such as, application has had spread over such as electric car, peak load regulation network large-scale energy storage device field.Compared to cathode material
Material, the power density and energy density of positive electrode are all lower, and the superiority and inferiority of performance of lithium ion battery largely all depends on
In positive electrode.The development of positive electrode technology is always one of the main bottleneck of limiting lithium ion cell technology development.
In recent years, the features such as phosphate material is nontoxic since it is at low cost, and chemical property is good, and thermal stability is good,
It has been to be concerned by more and more people.Studying in phosphate material more is LiFePO4, commercialization is had been carried out now, the material
Material is considered as more satisfactory one of the positive electrode of power lithium-ion battery.But due to LiFePO4Working voltage platform
Only 3.4V (vs.Li/Li+), cause its energy density lower.As lithium ion battery applications are in large-scale energy storage device (such as electricity
Electrical automobile etc.) rise, it is also higher and higher to requirement of the lithium ion battery in performance especially in energy density.Therefore, it opens
Hair novel high voltage positive electrode has become the trend of a certainty.Another phosphate material LiMnPO4, theoretical specific capacity
For 170mAhg-1, except with LiFePO4Other than all advantages of material, Mn3+/Mn2+Electrode potential be 4.1V (vs.Li/
Li+), it can metric density and LiFePO4Compared to improving nearly 20%, therefore LiMnPO4Material is also by the extensive pass of people
Note.Although lithium manganese phosphate material has the advantage in energy density and cost, electronic conductivity and lithium ion diffusion speed
Rate is lower, so that non-modified lithium manganese phosphate material is unable to satisfy practical application needs.In order to meet its application demand, just must
It must be modified, to improve its comprehensive electrochemical.The existing generally existing energy consumption of modification technology is high, process conditions are severe
The features such as quarter, the high requirements on the equipment, is unfavorable for controlling production cost.
In conclusion a kind of conducive to raising lithium ion battery chemical property and preparation process there is an urgent need in the art to develop
Strong, the easily controllable and at low cost phosphoric acid salt material of process operability.
Summary of the invention
The purpose of the present invention is to provide a kind of nano lithium iron manganese composite material and preparation methods of core-shell structure
And application.
The first aspect of the present invention, provides a kind of nano lithium iron manganese composite material, and the composite material includes core
The outer carbon-coating of shell structure and the optional cladding core-shell structure,
Wherein, the core-shell structure includes:
(i) core, the chemical composition of the core are LiMn1-(x-a)Fex-aPO4, wherein 0.05≤a≤x≤0.6；With
(ii) nucleocapsid, the nucleocapsid are LiFePO4；
And the partial size of the composite material is 10-900nm.
In another preferred example, the chemical composition of the LiFePO4 is LiFePO4。
In another preferred example, the chemical structure of the core-shell structure of the composite material is formed as shown in formula (I):
aLiFePO4-(1-a)LiMn1-(x-a)Fex-aPO4 (Ⅰ)
In formula, 0.05≤a≤x≤0.5.
In another preferred example, 0.1≤a≤x≤0.5, preferably 0.15≤a≤x≤0.4, more preferably 0.2≤a≤x≤
0.4。
In another preferred example, the composite material includes the outer carbon-coating for coating the core-shell structure.
In another preferred example, the partial size of the composite material be 20-600nm, preferably 20-400nm, more preferably for
20-200nm。
In another preferred example, the outer carbon-coating with a thickness of 1-15nm, preferably 1-10nm, be more preferably 1-5nm.
In another preferred example, the outer carbon-coating is evenly coated at the kernel periphery.
In another preferred example, the composite material is particle.
In another preferred example, the composite shapes are near-spherical, rodlike, olivine shape.
In another preferred example, the partial size of the core-shell structure is 10-500nm.
In another preferred example, the partial size of the core-shell structure be 20-400nm, preferably 20-300nm, more preferably for
20-200nm。
In another preferred example, the nucleocapsid with a thickness of 1-50nm, preferably 1.5-20nm, be more preferably 2-
15nm。
In another preferred example, the partial size of the core is 5-450nm, preferably 10-300nm, is more preferably 20-
200nm is most preferably 20-150nm.
In another preferred example, the volume ratio of the nucleocapsid and the core is 1:50-1:1, preferably 1:35-1:1,
It is more preferably 1:25-1:3.
In another preferred example, the molar ratio of the nucleocapsid and the core is 1:30-30:1, preferably 1:20-20:
1, it is more preferably 1:15-5:1, is most preferably 1:15-3:1.
In another preferred example, the nucleocapsid is evenly coated at the periphery of the core.
In another preferred example, the shape of the core-shell structure is near-spherical, rodlike, olivine shape.
In another preferred example, the core: nucleocapsid: the thickness ratio of outer carbon-coating is 20-200:1-50:1-15.
In another preferred example, the core: nucleocapsid: the thickness ratio of outer carbon-coating is 50-200:1-30:1-10.
In another preferred example, the mass ratio of the core-shell structure and the outer carbon-coating is 99.5-1:1-99.5, preferably
It is more preferably 95-5:5-95 for 99-1:1-99.
In another preferred example, the core-shell structure and/or the composite material are the sides as described in second aspect of the present invention
Made from method.
The second aspect of the present invention provides a kind of method for preparing composite material described in first aspect present invention, described
Method includes the following steps:
(a) core-shell structure is prepared, comprising:
(a-1) the first mixed solution, the second mixed solution and third mixed solution are provided,
Wherein, first mixed solution is prepared as follows: by manganese source compound, P source compound, and/or source of iron
It closes object to be dissolved in solvent, obtains the first premixed solution；Solvent additive is added in the first premixed solution, it is molten to obtain the first mixing
Liquid；
Second mixed solution is prepared as follows: Fe source compound and P source compound being dissolved in solvent, obtained
Second premixed solution；Solvent additive is added in the second premixed solution, the second mixed solution is obtained；
The third mixed solution is prepared as follows: Li source compound being dissolved in solvent, third mixed solution is obtained；
(a-2) under agitation, by core LiMn1-(x-a)Fex-aPO4Element stoichiometric ratio, third is mixed
Solution is added in the first mixed solution, obtains the 4th suspension；
(a-3) under agitation, the second mixed solution is added in the 4th suspension, obtains the 5th suspension；
(a-4) under agitation, by the stoichiometric ratio of the element of nucleocapsid LiFePO4, third mixed solution is added
In 5th suspension, gained suspension is futher stirred, the 6th suspension is obtained；
In another preferred example, described to refer to " by the stoichiometric ratio of the element of nucleocapsid LiFePO4 " compared to the second mixing
Solution.
(a-5) the 6th suspension is subjected to heating reaction, forms the core-shell structure, i.e. nano lithium iron manganese
Composite material；
(b) carbon-coating optionally outside the core-shell structure outer cladding, comprising:
(b-1) carbon-source cpd is dissolved or dispersed in solvent, obtains the first solution；
(b-2) under agitation, core-shell structure obtained by step (a-5) is added in first solution, to described
After core-shell structure is fully wet out, it is evaporated acquired solution；
(b-3) under an inert atmosphere, sintering step (b-2) products therefrom obtains having outer carbon-coating, first party of the present invention
Nano lithium iron manganese composite material described in face.
In another preferred example, the solvent may be the same or different, and be independently selected from the following group: deionized water, polyalcohols；Compared with
It goodly is deionized water.
In another preferred example, the solvent additive is high boiling solvent.
In another preferred example, 150 DEG C of the boiling point > of the solvent additive, preferably 180 DEG C of >, are more preferably >
200℃。
In another preferred example, the solvent additive mixes 100 DEG C of boiling point > of gained mixed solution with water 1:1, compared with
It goodly is 105 DEG C of >.
In another preferred example, the solvent additive may be the same or different, and be independently selected from the following group: ethylene glycol, tetrem two
Alcohol, glycerine, diglycol, poly alcohol, dimethyl sulfoxide, N,N-dimethylformamide, or combinations thereof.
In another preferred example, also containing surfactant selected from the group below or other additions in first mixed solution
Agent: polyvinylpyrrolidone, citric acid, ascorbic acid, beta-cyclodextrin, cetyl trimethylammonium bromide, sulfonic acid, fatty acid are sweet
Grease, dodecyl benzene sulfonic acid, or combinations thereof.
In another preferred example, the manganese source compound is selected from the group: manganese acetate, manganese sulfate, manganese nitrate, manganous chloride or
A combination thereof.
In another preferred example, the Fe source compound is selected from the group: ferrous acetate, ferrous sulfate, frerrous chloride or its
Combination.
In another preferred example, phosphorus source compound is phosphoric acid, ammonium dihydrogen phosphate or combinations thereof.
In another preferred example, the Li source compound is lithium hydroxide.
In another preferred example, the temperature of the heating reaction is 90-200 DEG C, preferably 100-150 DEG C.
In another preferred example, the time of the heating reaction under the heating temperature is 1-24h, preferably 2-12h.
In another preferred example, the heating reaction carries out under an inert atmosphere, preferably argon-hydrogen mixed atmosphere.
It in another preferred example, further include following steps after step (a-5): filtering and/or washing and/or dry institute
Product is obtained, the core-shell structure is made.
In another preferred example, the carbon-source cpd is selected from the group: conductive black, carbon nanotube, acetylene black, lactose,
Sucrose, glucose, polysaccharide, polyalcohol, poly alcohol or combinations thereof.
In another preferred example, the quality of carbon contained in the carbon-source cpd is the nano lithium iron manganese
The 0.5-25% of composite material quality, preferably 1-10%.
In another preferred example, the quality of the carbon-source cpd is the nano lithium iron manganese composite material quality
1-40%.
It in another preferred example, further include following steps before step (b-3): grinding steps (b-2) products therefrom.
In another preferred example, the sintering temperature is 400-800 DEG C, preferably 500-800 DEG C, more preferably 500-700
℃。
In another preferred example, the sintering time under the sintering temperature is 0.5-10h, preferably 1-6h, more preferably
1.5-4h。
In another preferred example, the method has one or more features selected from the group below:
(a) in first mixed solution, the molar ratio of Mn:Fe:P is 1-9:9-0:2-25；
In another preferred example, in first mixed solution, the molar ratio of (Mn+Fe): P is 1-5:5-1.
In another preferred example, in first mixed solution, the amount (calculating by monomer) of the surfactant is
0.2-10 times of amount summation of substance of the manganese source compound, Fe source compound, preferably 0.5-8 times, more preferably for
0.5-3 times.
In another preferred example, in first mixed solution, the volume ratio of the solvent additive and solvent is 1:
2–5:1；Preferably 4:5-5:1；It is more preferably 1:1-3:1.
(b) in second mixed solution, the molar ratio of Fe:P is 1-2:2-1；
In another preferred example, in second mixed solution, the volume ratio of the solvent additive and solvent is 1:
2–5:1；Preferably 4:5-5:1；It is more preferably 1:1-3:1.
(c) in first premixed solution, the amount concentration of metal ion total material are as follows: 0.5mol/L-4mol/L；
(d) in second premixed solution, the amount concentration of metal ion total material are as follows: 0.5mol/L-1.7mol/L；
(e) in the third mixed solution, the amount concentration of metal ion total material are as follows: 0.5mol/L-5mol/L；
(f) in the 6th suspension, the molar ratio of Mn:Fe:P:Li is 1-8:8-1:2-20:2-20.
In another preferred example, in the 6th suspension, solid content 20g/L-180g/L, preferably 25g/L-
120g/L is more preferably 35g/L-90g/L.
The third aspect of the present invention provides nano lithium iron manganese composite material described in a kind of first aspect present invention
Purposes is used to prepare anode material for lithium-ion batteries.
The fourth aspect of the present invention, provides a kind of positive electrode, and the positive electrode includes first aspect present invention institute
Nano lithium iron manganese composite material is stated as positive electrode active materials.
The fifth aspect of the present invention, provides a kind of product, and the product contains nanometer phosphorus described in first aspect present invention
Sour manganese iron lithium composite material or the nano lithium iron manganese composite material described in first aspect present invention are made.
In another preferred example, the product includes battery, preferably lithium ion battery.
The sixth aspect of the present invention, provides a kind of lithium ion battery, including positive electrode, negative electrode material, electrolyte, every
Film and shell, the positive electrode is using positive electrode described in fourth aspect present invention.
It should be understood that above-mentioned each technical characteristic of the invention and having in below (eg embodiment) within the scope of the present invention
It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, In
This no longer tires out one by one states.
Detailed description of the invention
Fig. 1 is the XRD diffraction pattern of the nano lithium iron manganese composite material 1 of core-shell structure prepared by the embodiment of the present invention 1.
Fig. 2 is the SEM picture of the nano lithium iron manganese composite material 1 of core-shell structure prepared by the embodiment of the present invention 1.
Fig. 3 is the TEM photo of the nano lithium iron manganese composite material 1 of core-shell structure prepared by the embodiment of the present invention 1.
Fig. 4 is the charging and discharging curve figure of lithium ion battery 1 prepared by the embodiment of the present invention 2.
Fig. 5 is the charging and discharging curve figure of lithium ion battery 2 prepared by the embodiment of the present invention 4.
Fig. 6 is the curve of double curvature figure of lithium ion battery 2 prepared by the embodiment of the present invention 4.
Fig. 7 is the cyclic curve figure of lithium ion battery 2 prepared by the embodiment of the present invention 4.
Fig. 8 is the XRD diffraction pattern of composite material C1 prepared by comparative example 1 of the present invention.
Specific embodiment
The present inventor's in-depth study by long-term, it has unexpectedly been found that be respectively added to high boiling solvent additive
Bottom liquid 1 (mixed aqueous solution of manganese source compound, P source compound and/or Fe source compound) and/or 2 (Fe source compound of bottom liquid
With the mixed aqueous solution of P source compound) in after, the boiling point of bottom liquid is remarkably improved, so as to use liquid phase method to prepare one kind
The nano lithium iron manganese composite material of core-shell structure.The preparation method is simple for process, low for equipment requirements, cost compared with
It is low.After the nano lithium iron manganese composite material surface coats one layer of carbon material, obtained nano lithium iron manganese-carbon
Composite material quality is stablized, good dispersion, purity is high, and material surface structural stability and electric conductivity enhancing are conducive to improve lithium
The chemical property of ion battery.And the preparation process technique for preparing the nano lithium iron manganese-carbon composite can operate
Property is strong, easily controllable, at low cost, pollution-free, it is easy to accomplish large-scale production.Based on above-mentioned discovery, inventor completes this hair
It is bright.
Term
As used herein, term " nano lithium iron manganese composite material of the present invention ", " nano lithium iron manganese composite wood
Material " or " nano lithium iron manganese " are used interchangeably, and refer both to include core-shell structure and the optional cladding core-shell structure
Outer carbon-coating, wherein the core-shell structure includes:
(i) core, the chemical composition of the core are LiMn1-(x-a)Fex-aPO4, wherein 0.05≤a≤x≤0.6；With
(ii) nucleocapsid, the nucleocapsid are LiFePO4；
And the partial size of the composite material is 10-900nm.
Composite material
The present invention provides a kind of nano lithium iron manganese composite material, the composite material include core-shell structure and optionally
The cladding core-shell structure outer carbon-coating,
Wherein, the core-shell structure includes:
(i) core, the chemical composition of the core are LiMn1-(x-a)Fex-aPO4, wherein 0.05≤a≤x≤0.6；With
(ii) nucleocapsid, the nucleocapsid are LiFePO4；
And the partial size of the composite material is 10-900nm.
In the present invention, the chemical composition of the LiFePO4 is LiFePO4。
In the present invention, the chemical structure of the core-shell structure of the composite material is formed as shown in formula (I):
aLiFePO4-(1-a)LiMn1-(x-a)Fex-aPO4 (Ⅰ)
In formula, 0.05≤a≤x≤0.5.
In another preferred example, 0.1≤a≤x≤0.5, preferably 0.15≤a≤x≤0.4, more preferably 0.2≤a≤x≤
0.4。
In another preferred example, the x-a=0.02-0.3, preferably x-a=0.05-0.2, more preferably x-a=0.05-
0.15。
In another preferred example, the composite material includes the outer carbon-coating for coating the core-shell structure.
In another preferred example, the partial size of the composite material be 20-600nm, preferably 20-400nm, more preferably for
20-200nm。
In another preferred example, the outer carbon-coating with a thickness of 1-15nm, preferably 1-10nm, be more preferably 1-5nm.
In another preferred example, the outer carbon-coating is evenly coated at the kernel periphery.
In another preferred example, the shape of the composite material is not particularly limited, the preferably described composite shapes
For near-spherical, rodlike, olivine shape.
In the present invention, the partial size of the core-shell structure is 10-500nm.
In another preferred example, the partial size of the core-shell structure be 20-400nm, preferably 20-300nm, more preferably for
20-200nm。
In another preferred example, the nucleocapsid with a thickness of 1-50nm, preferably 1.5-20nm, be more preferably 2-
15nm。
In another preferred example, the partial size of the core is 5-450nm, preferably 10-300nm, is more preferably 20-
200nm is most preferably 20-150nm.
In another preferred example, the volume ratio of the nucleocapsid and the core is 1:50-1:1, preferably 1:35-1:1,
It is more preferably 1:25-1:3.
In another preferred example, the molar ratio of the nucleocapsid and the core is 1:30-30:1, preferably 1:20-20:
1, it is more preferably 1:15-5:1, is most preferably 1:15-3:1.
In another preferred example, the nucleocapsid is evenly coated at the periphery of the core.
In the present invention, the shape of the core-shell structure is not particularly limited, it is therefore preferable to near-spherical, rodlike, olivine
Shape.
Specifically, the core: nucleocapsid: the thickness ratio of outer carbon-coating is 20-200:1-50:1-15.
Typically, the core: nucleocapsid: the thickness ratio of outer carbon-coating is 50-200:1-30:1-10.
In the present invention, the mass ratio of the core-shell structure and the outer carbon-coating is not particularly limited, it is therefore preferable to 99.5-
1:1-99.5, preferably 99-1:1-99 are more preferably 95-5:5-95.
In another preferred example, the core-shell structure and/or the composite material are the sides as described in second aspect of the present invention
Made from method.
Solvent additive
By adding high boiling solvent additive in the liquid of bottom, the boiling point of gained bottom liquid can be significantly improved, so as to
To use liquid phase method to prepare nano lithium iron manganese composite material of the present invention.
The solvent additive is not particularly limited, and high boiling solvent commonly used in the art can be used.
In the present invention, 150 DEG C of the boiling point > of the solvent additive, preferably 180 DEG C of > are more preferably > 200
℃。
Specifically, the solvent additive mixes 100 DEG C of boiling point > of gained mixed solution, preferably > with water 1:1
105℃。
In the present invention, the solvent additive may be the same or different.
Typically, the solvent additive includes (but being not limited to): ethylene glycol, tetraethylene glycol, glycerine, a contracting two
Ethylene glycol, poly alcohol, dimethyl sulfoxide, N,N-dimethylformamide, or combinations thereof.
Preparation method
In the present invention, a kind of method for preparing the composite material is provided, described method includes following steps:
(a) core-shell structure is prepared, comprising:
(a-1) the first mixed solution, the second mixed solution and third mixed solution are provided,
Wherein, first mixed solution is prepared as follows: by manganese source compound, P source compound, and/or source of iron
It closes object to be dissolved in solvent, obtains the first premixed solution；Solvent additive is added in the first premixed solution, it is molten to obtain the first mixing
Liquid；
Second mixed solution is prepared as follows: Fe source compound and P source compound being dissolved in solvent, obtained
Second premixed solution；Solvent additive is added in the second premixed solution, the second mixed solution is obtained；
The third mixed solution is prepared as follows: Li source compound being dissolved in solvent, third mixed solution is obtained；
(a-2) under agitation, by core LiMn1-(x-a)Fex-aPO4Element stoichiometric ratio, third is mixed
Solution is added in the first mixed solution, obtains the 4th suspension；
(a-3) under agitation, the second mixed solution is added in the 4th suspension, obtains the 5th suspension；
(a-4) under agitation, (molten compared to the second mixing by the stoichiometric ratio of the element of nucleocapsid LiFePO4
Liquid), third mixed solution is added in the 5th suspension, gained suspension is futher stirred, obtains the 6th suspension；
(a-5) the 6th suspension is subjected to heating reaction, forms the core-shell structure, i.e. nano lithium iron manganese
Composite material；
(b) carbon-coating optionally outside the core-shell structure outer cladding, comprising:
(b-1) carbon-source cpd is dissolved or dispersed in solvent, obtains the first solution；
(b-2) under agitation, core-shell structure obtained by step (a-5) is added in first solution, to described
After core-shell structure is fully wet out, it is evaporated acquired solution；
(b-3) under an inert atmosphere, sintering step (b-2) products therefrom obtains nanometer phosphorus that have outer carbon-coating, described
Sour manganese iron lithium composite material.
In the present invention, the solvent is not particularly limited, and in each solution, the solvent be may be the same or different.
Representative solvent includes (but being not limited to): water or aqueous solvent (including water and polarity or nonpolar organic molten
The mixed solvent of agent, such as the water that mixed proportion is 10-99.999:0.001-90: the mixed solvent of alcohol).
Preferred solvent includes deionized water, polyalcohols, especially deionized water.
In the present invention, surfactant or other additives are also contained in first mixed solution, the surface is living
Property agent or other additives are not particularly limited.
Typically, the surfactant or other additives include (but being not limited to): polyvinylpyrrolidone, lemon
Lemon acid, ascorbic acid, beta-cyclodextrin, cetyl trimethylammonium bromide, sulfonic acid, fatty glyceride, dodecyl benzene sulfonic acid,
Or combinations thereof.
It should be understood that required manganese source compound, Fe source compound, P source compound, lithium source chemical combination in positive electrode of the present invention
Object, carbon-source cpd etc. are not particularly limited, and can select the material of this field routine, or prepared with conventional method, or from
Market is commercially available.
Typically, the manganese source compound includes (but being not limited to): manganese acetate, manganese sulfate, manganese nitrate, manganous chloride
Or combinations thereof.
Typically, the Fe source compound include (but being not limited to): ferrous acetate, ferrous sulfate, frerrous chloride or
A combination thereof.
Typically, phosphorus source compound includes (but being not limited to): phosphoric acid, ammonium dihydrogen phosphate or combinations thereof.
Typically, the Li source compound includes (but being not limited to): lithium hydroxide.
Typically, the temperature of the heating reaction is 90-200 DEG C, preferably 100-150 DEG C.
Typically, the time of the heating reaction under the heating temperature is 1-24h, preferably 2-12h.
In another preferred example, the heating reaction carries out under an inert atmosphere, preferably argon-hydrogen mixed atmosphere.
It in another preferred example, further include following steps after step (a-5): filtering and/or washing and/or dry institute
Product is obtained, the core-shell structure is made.
Typically, the carbon-source cpd includes (but being not limited to): conductive black, carbon nanotube, acetylene black, cream
Sugar, sucrose, glucose, polysaccharide, polyalcohol, poly alcohol or combinations thereof.
In another preferred example, the quality of carbon contained in the carbon-source cpd is the nano lithium iron manganese
The 0.5-25% of composite material quality, preferably 1-10%.
In another preferred example, the quality of the carbon-source cpd is the nano lithium iron manganese composite material quality
1-40%.
It in another preferred example, further include following steps before step (b-3): grinding steps (b-2) products therefrom.
In another preferred example, the sintering temperature is 400-800 DEG C, preferably 500-800 DEG C, more preferably 500-700
℃。
In another preferred example, the sintering time under the sintering temperature is 0.5-10h, preferably 1-6h, more preferably
1.5-4h。
In the present invention, the method has one or more features selected from the group below:
(a) in first mixed solution, the molar ratio of Mn:Fe:P is 1-9:9-0:2-25；
In another preferred example, in first mixed solution, the molar ratio of (Mn+Fe): P is 1-5:5-1.
In another preferred example, in first mixed solution, the amount (calculating by monomer) of the surfactant is
0.2-10 times of amount summation of substance of the manganese source compound, Fe source compound, preferably 0.5-8 times, more preferably for
0.5-3 times.
In another preferred example, in first mixed solution, the volume ratio of the solvent additive and solvent is 1:
2–5:1；Preferably 4:5-5:1；It is more preferably 1:1-3:1.
(b) in second mixed solution, the molar ratio of Fe:P is 1-2:2-1；
In another preferred example, in second mixed solution, the volume ratio of the solvent additive and solvent is 1:
2–5:1；Preferably 4:5-5:1；It is more preferably 1:1-3:1.
(c) in first premixed solution, the amount concentration of metal ion total material are as follows: 0.5mol/L-4mol/L；
(d) in second premixed solution, the amount concentration of metal ion total material are as follows: 0.5mol/L-1.7mol/L；
(e) in the third mixed solution, the amount concentration of metal ion total material are as follows: 0.5mol/L-5mol/L；
(f) in the 6th suspension, the molar ratio of Mn:Fe:P:Li is 1-8:8-1:2-20:2-20.
In another preferred example, in the 6th suspension, solid content 20g/L-180g/L, preferably 25g/L-
120g/L is more preferably 35g/L-90g/L.
Using
The present invention also provides a kind of purposes of nano lithium iron manganese composite material, that is, are used to prepare lithium-ion electric
Pond positive electrode.
The positive electrode includes the nano lithium iron manganese composite material as positive electrode active materials.
The present invention also provides a kind of product, the product contains the nano lithium iron manganese composite material or by described
Nano lithium iron manganese composite material is made.
Typically, the product includes battery, preferably lithium ion battery.
The lithium ion battery includes positive electrode, negative electrode material, electrolyte, diaphragm and shell.
In lithium ion battery of the present invention, other than positive electrode active materials of the present invention, other materials include negative electrode material,
Diaphragm, electrolyte, conductive agent and binder etc. are not particularly limited, and are referred to state of the art and are carried out selection ability
The existing material in domain.
In a preferred example, the anode of the lithium ion battery also contains conductive agent and binder.
In another preferred example, the conductive agent is selected from: conductive black, acetylene black, activated carbon.
In another preferred example, the binder is Kynoar.
In a preferred example, the battery further includes diaphragm and shell.
Typically, the diaphragm includes (but being not limited to): polypropylene diaphragm, polyethylene diagrams, polypropylene-polyethylene
Diaphragm or fibreglass diaphragm.
Typically, the negative electrode material include (but being not limited to): natural graphite, electrographite, carbonaceous mesophase spherules,
Silicon carbide, metal lithium sheet or sodium piece.
Compared with prior art, the present invention has following major advantage:
(1) using deionized water as reaction dissolvent, a certain amount of solvent additive is added as adjuvant, using multistage mixing
Mode realizes the simple liquid phase synthesis of LiFePO4 cladding nano lithium iron manganese in combination with the inhibition of surfactant.
(2) the nano lithium iron manganese material of the core-shell structure obtained by, inner nuclear material (iron manganese phosphate for lithium or manganese phosphate
Lithium) crystal structure is close with sheathing material (LiFePO4) crystal structure, and structural compatibility is good, is conducive to material and follows in charge and discharge
Stable structure is kept during ring.
(3) nano lithium iron manganese of the core-shell structure obtained by-carbon composite quality is stablized, good dispersion, purity
Height, material surface structural stability and electric conductivity enhancing are conducive to the chemical property for improving lithium ion battery, and preparation process
Process operability is strong, easily controllable, at low cost, pollution-free, it is easy to accomplish large-scale production.
(4) nano lithium iron manganese-carbon composite of the core-shell structure prepared using the method, LiFePO4 are uniform
Be coated on nano lithium iron manganese surface, obtained iron manganese phosphate for lithium base anode material discharge capacity with higher, preferably
High rate performance and cycle performance.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are calculated by weight.
Unless otherwise defined, it anticipates known to all professional and scientific terms as used herein and one skilled in the art
Justice is identical.In addition, any method similar to or equal to what is recorded and material can be applied to the method for the present invention.Wen Zhong
The preferred implement methods and materials are for illustrative purposes only.
Embodiment 1
Prepare core-shell structure 1
The first step, by 7.571g Manganous sulfate monohydrate (MnSO4·H2O), 1.557g green vitriol (FeSO4·
7H2O), 3.42mL phosphoric acid (H3PO4, 85wt%) and 6.216g polyvinylpyrrolidone (PVP) be dissolved in 28mL deionized water,
Obtain solution α.Take 1.557g green vitriol (FeSO4·7H2O), 0.38mL phosphoric acid (H3PO4, 85wt%) and it is dissolved in 3mL
In deionized water, solution β is obtained.Be separately added into solution α and β 88mL and 10mL dimethyl sulfoxide (DMSO) solution a and
Solution b.Take mono- hydronium(ion) lithia (LiOHH of 7g2O it) is dissolved in 67mL deionized water, obtains solution c.
60mL solution c is added in solution a second step, and stirring obtains suspension d.
Solution b is added drop-wise in suspension d by third step, and stirring obtains suspension e.
Surplus solution c is added in suspension e by the 4th step, and after dripping, stirring obtains suspension f.
Suspension f is placed in 130 DEG C of oil bath pans by the 5th step under inert atmosphere protection, and keeps the temperature 6 hours.It has reacted
It is reaction solution is cooling and filter after, it is three times with deionized water/ethanol wash, finally 12 hours dry in 80 DEG C of baking ovens, it obtains
To the core-shell structure 1.
As a result
Component detection is carried out to the core-shell structure 1 prepared by embodiment 1.
Its component is detected using German BrukerD8advance-X x ray diffractometer x type (XRD), as a result such as Fig. 1
It is shown.Wherein, abscissa is 2 θ of angle, unit are as follows: degree (o)；Ordinate is diffracted intensity, unit are as follows: any unit (a.u.).
As shown in Figure 1, what is showed in XRD diffraction spectra is iron manganese phosphate for lithium characteristic peak (*), free from admixture peak.
The nucleocapsid using Hitachi, Japan FESEM S-4800 type field emission scanning electron microscope prepared by embodiment 1
Structure 1 carries out Shape measure, as a result as shown in Figure 2.As shown in Figure 2, nano lithium iron manganese composite material prepared by the present invention
For the rodlike discrete particles of nanoscale, soilless sticking.
The nano manganese phosphate iron using the Tecnai F20 type transmission electron microscope that FEI Co., the U.S. produces prepared by embodiment 1
Lithium composite material carries out object and is mutually distributed detection, as a result as shown in Figure 3.From the figure 3, it may be seen that nano lithium iron manganese prepared by the present invention
Composite material is a kind of core-shell structure, outer layer LiFePO4Layer, kernel LiMn0.9Fe0.1PO4, the molecular formula of composite material
For 0.1LiFePO4-0.9LiMn0.9Fe0.1PO4。
By Fig. 1, Fig. 2 and Fig. 3 it is found that preparation method provided by the invention is successfully prepared for the nanometer with core-shell structure
Iron manganese phosphate for lithium, the core of material are LiMn0.9Fe0.1PO4, nucleocapsid LiFePO4, purity with higher and lesser particle
Size.
Embodiment 2
Prepare lithium ion battery 1
The nano lithium iron manganese 1 of core-shell structure prepared by embodiment 1 is coated on Al foil collector, and electrode is made
Piece.It is anode with the electrode obtained piece, metal lithium sheet does cathode and is assembled into battery 1.
As a result
The chemical property of battery 1 obtained by test under blue electric battery test system.
Charge-discharge performance of the battery 1 under 0.1C multiplying power is as shown in Figure 4.As shown in Figure 4, it is made using the embodiment of the present invention 1
0.1C first discharge specific capacity is 41mAh/g, electrification to the battery 1 of standby nano lithium iron manganese composite material assembling at room temperature
It is poor to learn performance.
Embodiment 3
Prepare nano lithium iron manganese-carbon composite 1
It takes 0.792g sucrose to be dissolved in 10mL deionized water, nano lithium iron manganese sample 3g obtained by embodiment 1 is added
Enter into sucrose solution and stir, heat and be evaporated after nano lithium iron manganese sample particle is fully wet out, by gained sample
Grinding is placed in tube furnace is heated 2 hours with 600 DEG C, and is passed through 5%H2- 95%Ar atmosphere protection obtains multi-layer core-shell knot
Nano lithium iron manganese-carbon composite 1 of structure.
As a result
Object is carried out to nano lithium iron manganese-carbon composite 1 prepared by embodiment 3 and is mutually distributed detection.
The results show that nano lithium iron manganese-the carbon composite 1 has multi-layer core-shell structure, innermost layer is
LiMn0.9Fe0.1PO4, secondary outer layer is LiFePO4Layer, outermost layer is carbon coating layer, purity with higher and lesser particle ruler
It is very little.
Embodiment 4
Prepare lithium ion battery 2
Nano lithium iron manganese prepared by embodiment 3-carbon composite 0.4g and conductive carbon black 0.05g, binder
(PVDF) 0.05g is mixed evenly, and it is in that appropriateness is thick that appropriate NMP, which is added, to mixture, is stirred 3-4h, is coated onto Al foil collection
It on fluid, is placed in 120 DEG C of vacuum drying ovens after drying 10h, is cut into the disk that diameter is 14mm.It is anode with the electrode obtained piece,
Metal lithium sheet is that cathode is assembled into battery 2.
As a result
The chemical property of battery 2 is tested under blue electric battery test system, Fig. 5 is head of the battery 2 under 0.1C multiplying power
Secondary charge-discharge performance figure, Fig. 6 are discharge performance figure of the battery 2 under different multiplying, and Fig. 7 is the following under 0.5C multiplying power of battery 2
Ring performance map.
By Fig. 5, Fig. 6 and Fig. 7 it is found that 1 group of nano lithium iron manganese-carbon composite prepared with the embodiment of the present invention 3
0.1C first discharge specific capacity reaches 155mAh/g to the battery 2 of dress at room temperature, the electric discharge under the big multiplying power of 5C, 10C and 20C
Capacity is respectively up to 118mAh/g, 105mAh/g and 80mAh/g；100 weeks capacity of 0.5C normal temperature circulation are unattenuated, and it is very good to have
Cyclical stability.
Embodiment 5
Prepare nano lithium iron manganese-carbon composite 2
The first step, by 44.8mmol Manganous sulfate monohydrate (MnSO4·H2O), 5.6mmol green vitriol
(FeSO4·7H2O), 3.42mL phosphoric acid (H3PO4, 85wt%) and 56mmol cetyl trimethylammonium bromide (CTAB) be dissolved in
In 28mL deionized water, solution α is obtained.Take 5.6mmol green vitriol (FeSO4·7H2O), 0.38mL phosphoric acid
(H3PO4, 85wt%) and it is dissolved in 3mL deionized water, obtain solution β.88mL and 10mL mono- contracting two is separately added into solution α and β
Ethylene glycol (DEG) obtains solution a and solution b.Take mono- hydronium(ion) lithia (LiOHH of 6.8g2O it) is dissolved in 67mL deionized water,
Obtain solution c.
60mL solution c is added in solution a second step, and stirring obtains suspension d.
Solution b is added drop-wise in suspension d by third step, and stirring obtains suspension e.
Surplus solution c is added in suspension e by the 4th step, and after dripping, stirring obtains suspension f.
Suspension f is placed in 120 DEG C of oil bath pans by the 5th step under inert atmosphere protection, and keeps the temperature 6 hours.It has reacted
It is reaction solution is cooling and filter after, it is three times with deionized water/ethanol wash, finally 12 hours dry in 80 DEG C of baking ovens, it obtains
To nano lithium iron manganese composite material 2, molecular formula 0.1LiFePO4-0.9LiMn0.9Fe0.1PO4。
6th step takes 0.396g sucrose to be dissolved in 10mL deionized water, by above-mentioned 2 sample of nano lithium iron manganese composite material
3g is added in sucrose solution and stirs, and heats and steams after 2 sample particle of nano lithium iron manganese composite material is fully wet out
It is dry, the grinding of gained sample is placed in tube furnace and is heated 3.5 hours with 700 DEG C, and is passed through 5%H2- 95%Ar atmosphere protection,
Obtain nano lithium iron manganese-carbon composite 2.
As a result
With the battery of nano lithium iron manganese-carbon composite 2 manufactured in the present embodiment assembling, 0.1C is for the first time at room temperature
Specific discharge capacity reaches 158mAh/g；Discharge capacity under the big multiplying power of 5C, 10C and 20C respectively up to 115mAh/g,
101mAh/g and 83mAh/g；100 weeks capacity of 0.5C normal temperature circulation are unattenuated, have extraordinary cyclical stability.
Embodiment 6
Prepare nano lithium iron manganese-carbon composite 3
The first step, by 28mmol Manganous sulfate monohydrate (MnSO4·H2O), 1.9mL and phosphoric acid (H3PO4, 85wt%) and it is dissolved in
In 16mL deionized water, solution α is obtained.Take 28mmol green vitriol (FeSO4·7H2O), 1.9mL phosphoric acid (H3PO4,
It 85wt%) is dissolved in 16mL deionized water, obtains solution β.49mL diglycol (DEG) is separately added into solution α and β
Obtain solution a and solution b.Take mono- hydronium(ion) lithia (LiOHH of 6.8g2O it) is dissolved in 67mL deionized water, obtains solution c.
33.5mL solution c is added in solution a second step, and stirring obtains suspension d.
Solution b is added drop-wise in suspension d by third step, and stirring obtains suspension e.
Surplus solution c is added in suspension e by the 4th step, and after dripping, stirring obtains suspension f.
Suspension f is placed in 130 DEG C of oil bath pans by the 5th step under inert atmosphere protection, and keeps the temperature 4 hours.It has reacted
It is reaction solution is cooling and filter after, it is three times with deionized water/ethanol wash, finally 12 hours dry in 80 DEG C of baking ovens, it obtains
To nano lithium iron manganese composite material 3, molecular formula 0.5LiFePO4-0.5LiMnPO4。
6th step takes 0.426g glucose to be dissolved in 10mL deionized water, by above-mentioned 3 sample of nano lithium iron manganese composite material
Product 3g is added in sucrose solution and stirs, and heats after 3 sample particle of nano lithium iron manganese composite material is fully wet out
It is evaporated, the grinding of gained sample is placed in tube furnace and is heated 2 hours with 600 DEG C, and is passed through 5%H2- 95%Ar atmosphere protection,
Obtain nano lithium iron manganese-carbon composite 3.
As a result
With the battery of nano lithium iron manganese-carbon composite 3 manufactured in the present embodiment assembling, 0.1C is for the first time at room temperature
Specific discharge capacity reaches 152mAh/g；Discharge capacity under the big multiplying power of 5C, 10C and 20C respectively up to 116mAh/g,
100mAh/g and 75mAh/g；100 weeks capacity of 0.5C normal temperature circulation are unattenuated, have extraordinary cyclical stability.
Comparative example 1
Prepare nano lithium iron manganese-carbon composite C1
With embodiment 1 and 3, difference is: not adding solvent additive.
As a result
The composite wood using German BrukerD8advance-X x ray diffractometer x type (XRD) prepared by comparative example 1 of the present invention
Expect that C1 carries out XRD detection, test results are shown in figure 8 for gained.As shown in Figure 8, composite material C1 and not formed iron manganese phosphate for lithium
Crystal structure.
Comparative example 2
Solid phase method prepares the iron manganese phosphate for lithium composite material of outer carbon-coating cladding
In the prior art, with Mn (NO3)2·4H2O、Fe(NO3)3·9H2O and H3PO4 is raw material, uses NH4OH adjusts PH
Value, first prepares presoma Mn0.85Fe0.15PO4-FePO4, then with Li2CO3And after carbon source mixing, under argon-hydrogen mixing gas shielded
700 DEG C of high temperature sintering 15h, obtain target product.
Compared with the present invention, there are following features for comparative example 2:
1) need to react at high temperature the long period, energy consumption is big, and the present invention due to solvent additive use can compared with
Target product can be obtained in the time for reacting shorter at a temperature of low；
2) products therefrom partial size is micron order (5 μm of >), and present invention gained target product is nanoscale, therefore institute of the present invention
Obtaining product subsequent machining operations has more selectivity, can directly use, can also be further prepared into different-grain diameter
Particle reuses；
3) preparation method is related to presoma and Li2CO3Two phase reaction, this be easy to cause Elemental redistribution uneven, difficult
To obtain the product of stoichiometric ratio, and the process is readily incorporated impurity.And element needed for target product is reacting in the present invention
It is initial just all in the form of reaction raw materials while being added in reaction solution, therefore be easier to also to be more likely to obtain Elemental redistribution equal
Product that is even and meeting stoichiometric ratio；
It 4) is 90mAh/g with the 5C multiplying power discharging capacity of the lithium ion battery of the assembling of product obtained by comparative example 2, and with
The 5C multiplying power discharging capacity of the lithium ion battery of the assembling of product obtained by the present invention is 118mAh/g, it can be seen that using the present invention
The 5C multiplying power discharging capacity of the lithium ion battery of obtained product assembling can be improved about 31%；
5) lithium ion battery assembled with product obtained by the present invention is unattenuated in 100 weeks capacity of 0.5C normal temperature circulation, tool
There is extraordinary cyclical stability；And with product obtained by comparative example 2 assembling lithium ion battery 0.5C normal temperature circulation≤
50 weeks.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To make various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (4)
1. a kind of method for preparing composite material, the composite material includes core-shell structure and the outer carbon for coating the core-shell structure
Layer, wherein the core-shell structure includes: (i) core, and the chemical composition of the core is LiMn1-(x-a)Fex-aPO4,
In 0.05≤a≤x≤0.6；(ii) shell, the shell are LiFePO4；And the partial size of the composite material is 20-
200nm；The outer carbon-coating with a thickness of 1-15nm；The core: shell: the thickness ratio of outer carbon-coating is 20-200:1-50:1-15；
It is characterized in that, described method includes following steps: (a) preparing core-shell structure, comprising: it is molten that (a-1) provides the first mixing
Liquid, the second mixed solution and third mixed solution, wherein first mixed solution is prepared as follows: by manganese source compound,
P source compound, and/or Fe source compound are dissolved in solvent, obtain the first premixed solution；It is pre- that solvent additive is added first
In miscible fluid, the first mixed solution is obtained；Second mixed solution is prepared as follows: by Fe source compound and phosphorus source chemical combination
Object is dissolved in solvent, obtains the second premixed solution；Solvent additive is added in the second premixed solution, it is molten to obtain the second mixing
Liquid；The solvent is deionized water；The solvent additive is high boiling solvent；150 DEG C of the boiling point > of the solvent additive；
The third mixed solution is prepared as follows: Li source compound being dissolved in solvent, third mixed solution is obtained； (a-2)
Under agitation, by core LiMn1-(x-a)Fex-aPO4Element stoichiometric ratio, by third mixed solution be added first
In mixed solution, the 4th suspension is obtained；(a-3) under agitation, the second mixed solution is added in the 4th suspension,
Obtain the 5th suspension；(a-4) under agitation, by the stoichiometric ratio of the element of shell LiFePO4, third is mixed
Solution is added in the 5th suspension, futher stirs gained suspension, obtains the 6th suspension；(a-5) the described 6th is hanged
Turbid carries out heating reaction, forms the core-shell structure；(b) carbon-coating outside the core-shell structure outer cladding, comprising: (b-
1) carbon-source cpd is dissolved or dispersed in solvent, obtains the first solution；(b-2) under agitation, by step (a-
5) gained core-shell structure is added in first solution, after the core-shell structure is fully wet out, is evaporated acquired solution；
(b-3) under an inert atmosphere, sintering step (b-2) products therefrom, obtains the composite material.
2. the method as described in claim 1, which is characterized in that the method has one or more features selected from the group below:
(a) in first mixed solution, the molar ratio of Mn:Fe:P is 1-9:9-0:2-25；(b) molten in second mixing
In liquid, the molar ratio of Fe:P is 1-2:2-1；(c) in first premixed solution, the amount concentration of metal ion total material
Are as follows: 0.5mol/L-4mol/L；(d) in second premixed solution, the amount concentration of metal ion total material are as follows: 0.5mol/
L-1.7mol/L；(e) in the third mixed solution, the amount concentration of metal ion total material are as follows: 0.5mol/L-5mol/
L；(f) in the 6th suspension, the molar ratio of Mn:Fe:P:Li is 1-8:8-1:2-20:2-20.
3. the method as described in claim 1, which is characterized in that the chemical structure composition of the core-shell structure of the composite material is such as
Shown in formula (I): aLiFePO4-(1-a)LiMn1-(x-a)Fex-aPO4 (I) in formula, 0.05≤a≤x≤0.5.
4. the method as described in claim 1, which is characterized in that the partial size of the core-shell structure is 10-200nm.
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| CN106340639B (en) * | 2016-10-28 | 2019-07-12 | 合肥国轩高科动力能源有限公司 | A kind of hud typed iron manganese phosphate for lithium composite positive pole and preparation method thereof of lithium iron phosphate/carbon cladding |
| CN107359342B (en) * | 2017-07-27 | 2019-12-24 | 泓辰电池材料有限公司 | Lithium ferromanganese phosphate particles and lithium ferromanganese phosphate powder |
| CN109428066A (en) * | 2017-08-30 | 2019-03-05 | 中国科学院宁波材料技术与工程研究所 | Core-shell material and preparation method thereof, lithium ion battery negative material and lithium ion battery |
| CN111613786B (en) * | 2020-05-29 | 2023-03-28 | 东莞东阳光科研发有限公司 | Composite material and preparation method thereof |
| CN112242514A (en) * | 2020-11-20 | 2021-01-19 | 深圳澳睿新能源科技有限公司 | Method for preparing anode material of lithium ion battery |
| CN113921769A (en) * | 2021-08-18 | 2022-01-11 | 浙江南都电源动力股份有限公司 | Composite positive pole piece and preparation method and application thereof |
| CN114512649A (en) * | 2022-02-08 | 2022-05-17 | 江苏中兴派能电池有限公司 | Composite lithium manganese iron phosphate cathode material, preparation method and application thereof |
| CN115043387B (en) * | 2022-06-28 | 2023-07-07 | 广东邦普循环科技有限公司 | Preparation method of ammonium ferromanganese phosphate, lithium ferromanganese phosphate and application thereof |
| GB2624951A (en) * | 2022-06-28 | 2024-06-05 | Guangdong Brunp Recycling Technology Co Ltd | Preparation method for ammonium manganese iron phosphate, and lithium manganese iron phosphate and use thereof |
| CN115020702A (en) * | 2022-07-12 | 2022-09-06 | 东莞凯德新能源有限公司 | Lithium ion battery, positive electrode material with core-shell structure and preparation method of positive electrode material |
| CN117133920B (en) * | 2023-10-25 | 2023-12-29 | 成都仪隆电子有限公司 | Modified lithium iron manganese phosphate anode material and preparation method and application thereof |
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