JP6260535B2 - 炭素複合化リン酸マンガン鉄リチウム粒子粉末の製造方法、及び該粒子粉末を用いた非水電解質二次電池の製造方法 - Google Patents
炭素複合化リン酸マンガン鉄リチウム粒子粉末の製造方法、及び該粒子粉末を用いた非水電解質二次電池の製造方法 Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims description 111
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 title claims description 96
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 95
- 229910052799 carbon Inorganic materials 0.000 title claims description 88
- 239000002131 composite material Substances 0.000 title claims description 56
- 239000000843 powder Substances 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 44
- 229910052698 phosphorus Inorganic materials 0.000 claims description 40
- 238000010335 hydrothermal treatment Methods 0.000 claims description 38
- 239000011572 manganese Substances 0.000 claims description 38
- 239000000126 substance Substances 0.000 claims description 34
- 239000011574 phosphorus Substances 0.000 claims description 33
- 229910021293 PO 4 Inorganic materials 0.000 claims description 32
- -1 phosphorus compound Chemical class 0.000 claims description 31
- 150000002642 lithium compounds Chemical class 0.000 claims description 24
- 238000010304 firing Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 13
- 239000010450 olivine Substances 0.000 claims description 12
- 229910052609 olivine Inorganic materials 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 239000007900 aqueous suspension Substances 0.000 claims description 11
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 239000011368 organic material Substances 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 34
- 239000012071 phase Substances 0.000 description 22
- 239000007774 positive electrode material Substances 0.000 description 21
- 239000002994 raw material Substances 0.000 description 21
- 239000002002 slurry Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000012535 impurity Substances 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000010298 pulverizing process Methods 0.000 description 12
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 11
- 229910015645 LiMn Inorganic materials 0.000 description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
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- 230000007547 defect Effects 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
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- 239000002904 solvent Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 230000004580 weight loss Effects 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000003991 Rietveld refinement Methods 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
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- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 238000002076 thermal analysis method Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910017840 NH 3 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 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
- 239000006229 carbon black Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- UCLCELYDHWWXIR-UHFFFAOYSA-N lithium dioxido(dioxo)manganese iron(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Fe+2].[Li+] UCLCELYDHWWXIR-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920006369 KF polymer Polymers 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015944 LiMn0.8Fe0.2PO4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 229910006710 Li—P Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZSBXGIUJOOQZMP-JLNYLFASSA-N Matrine Chemical compound C1CC[C@H]2CN3C(=O)CCC[C@@H]3[C@@H]3[C@H]2N1CCC3 ZSBXGIUJOOQZMP-JLNYLFASSA-N 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 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 1
- 229930006000 Sucrose Natural products 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000004898 kneading Methods 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
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- FEPMHVLSLDOMQC-UHFFFAOYSA-N virginiamycin-S1 Natural products CC1OC(=O)C(C=2C=CC=CC=2)NC(=O)C2CC(=O)CCN2C(=O)C(CC=2C=CC=CC=2)N(C)C(=O)C2CCCN2C(=O)C(CC)NC(=O)C1NC(=O)C1=NC=CC=C1O FEPMHVLSLDOMQC-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
Description
放電 MnPO4+Li++e−→LiMnPO4
VUC(Å3)=11.4×(1−x)+291.21・・・(1)
従って、本発明に係る炭素複合化リン酸マンガン鉄リチウム粒子粉末の単位胞体積の式(1)の単位胞体積VUCに対する割合は、好ましくは99.950%以下である。
本発明に係る炭素複合化リン酸マンガン鉄リチウム粒子粉末は水熱処理と熱処理により製造され、低コストで、環境負荷が小さく製造できる。本発明の製造方法によれば、得られる炭素複合化リン酸マンガン鉄リチウム粒子粉末は結晶性と粒子表面と凝集粒子径が制御されているため、二次電池の正極活物質として用いた場合には、室温、及び低温における電流負荷特性においても高容量が得られ、且つ高温で十分に充放電を繰返し使えると本発明者は推定している。
F. Izumi and T. Ikeda, Mater. Sci. Forum, 2000, Vol.321−324, p.198.
遷移金属の物質収支が各工程で100%とした場合、約88g(約0.56mol)のLiMn0.8Fe0.2PO4ができるように原料を計量した。遷移金属が5.6mol/Lとなるよう、MnSO4、FeSO4、H3PO4、NH4OH、及び純水を混合し、室温での中和反応によりNH4MnPO4とNH4FePO4を得た。沈殿物を濾別し、純水で洗浄した後、LiOH・H2O、H3PO4、及びアスコルビン酸の溶液を加え、mol比がLi:Mn:Fe:P=1.05:0.8:0.2:1.05となる原料仕込み比に調整された水系スラリーを得た。スラリー中の主結晶相はNH4MnPO4であった。該スラリーをボールミルで混合し、凝集粒子を粉砕して粒度を調整した。
実施例1と同仕様で得られた水熱処理、水洗後のリン酸マンガン鉄リチウム粒子含有ケーキに対し、その後の工程において、表1記載のリチウム化合物及び/又はリン化合物と炭素源を変えた他は実施例1と同様に、乾燥、粉砕・分級、焼成、及び粉砕・分級を行い、リン酸マンガン鉄リチウム粒子粉末を得た。表2、3に評価結果を示す。
実施例1と同仕様での水熱処理、水洗後のリン酸マンガン鉄リチウム粒子含有ケーキを乾燥後、表1記載のリチウム化合物及び/又はリン化合物と炭素源を用いて、乾燥物に対し、7.5wt%の水を加えて、コーヒーミルで混合を行った。それ以降の処理は、実施例1記載の方法で行いリン酸マンガン鉄リチウム粒子粉末を得た。表2、3に評価結果を示す。
実施例1に記載の原料仕込み比に対し、Mn:Fe=85:15と変えた他は実施例1と同様の水熱反応用前駆体処理、水熱処理、及び水洗を行ってケーキを得た。評価用に水洗後のサンプルの一部を抜取り、105℃で一晩乾燥したものは、XRD回折パターンのRietveld解析でLi1−αMn0.85Fe0.15P1−βO4−δ(0≦α、β≦0.2)と4.3wt%の不純物相Li3PO4とを含むものであることが判明した。その組成比はICP測定でLi:Mn:Fe:P=0.98:0.85:0.15:0.96であり、5.4wt%重量減少が熱分析で確認できたため、該反応率を94.6wt%とした。
実施例1に記載の原料仕込み比に対し、Mn:Fe=100:0と変えた他は実施例1と同様の水熱反応用前駆体処理、水熱処理、及び水洗を行ってケーキを得た。評価用に水洗後のサンプルの一部を抜取り、105℃で一晩乾燥したものは、XRD回折パターンのRietveld解析で3.0wt%の不純物相Li3PO4とLi1−αMnP1−βO4−δ(0≦α、β≦0.2)と判明した。その組成比はICP測定でLi:Mn:Fe:P=0.98:1.00:0.0:0.96であり、4.8wt%重量減少が熱分析で確認できたため、該反応率を95.2wt%とした。
実施例1と同仕様で得られた水熱反応、水洗後のリン酸マンガン鉄リチウム粒子含有ケーキに対し、表1記載のリチウム化合物及び/又はリン化合物と炭素源を変えた他は実施例4と同様に、該ケーキを乾燥後、リチウム化合物及び/又はリン化合物と炭素源と水を混合、再乾燥、粉砕・分級、焼成、及び粉砕・分級を行いリン酸マンガン鉄リチウム粒子粉末を得た。表2、3に評価結果を示す。
実施例1と同仕様で得られた水熱反応、水洗後のリン酸マンガン鉄リチウム粒子含有ケーキに対し、表1記載のリチウム化合物及び/又はリン化合物と炭素源を変えた他は実施例1と同様に、ケーキ解膠後、混合、乾燥、粉砕・分級、焼成、及び粉砕・分級を行い、リン酸マンガン鉄リチウム粒子粉末を得た。表2、3に評価結果を示す。
実施例1と同様にして第二工程で得られた焼成用前駆体混合粉末に対し、焼成を他の例よりも100℃高い800℃で行い、粉砕・分級を行い、リン酸マンガン鉄リチウム粒子粉末を得た。表2、3に評価結果を示す。
Claims (5)
- オリビン型構造の炭素複合化リン酸マンガン鉄リチウム(Mn:Fe=0.98:0.02〜0.50:0.50mol比)粒子粉末の製造方法において、水熱処理によって生成されたオリビン型構造のリン酸マンガン鉄リチウムとリチウム化合物及び/又はリン化合物と、有機物とを含む水系懸濁液又は含水物を得る第一工程、第一工程で得られた水系懸濁液又は含水物を乾燥して焼成用前駆体混合粉末を得る第二工程、第二工程で得られた焼成用前駆体混合粉末を焼成する第三工程からなる炭素複合化リン酸マンガン鉄リチウム粒子粉末の製造方法であって、第一工程における水系懸濁液又は含水物がmol比で0.98≦Li/(Mn+Fe)≦1.20、0.98≦P/(Mn+Fe)≦1.20、P≦Liを満たし、且つ、リチウム化合物及び/又はリン化合物の60wt%以上がLiH 2 PO 4 であり、前記有機物が水熱処理後のリン酸マンガン鉄リチウムに対して1〜20wt%であるオリビン型構造の炭素複合化リン酸マンガン鉄リチウム粒子粉末の製造方法。
- 炭素複合化リン酸マンガン鉄リチウム粒子粉末の製造方法の第一工程において、有機物が水可溶性の有機物である請求項1に記載の製造方法。
- 炭素複合化リン酸マンガン鉄リチウム粒子粉末の製造方法の第一工程において、有機物がヒドロキシ基(−OH)又はカルボキシル基(−COOH)を含む多価アルコール、糖、又は有機酸に属する有機物である請求項1又は2に記載の製造方法。
- 炭素複合化リン酸マンガン鉄リチウム粒子粉末の製造方法の第二工程における乾燥温度が40℃〜250℃である請求項1〜3のいずれかに記載の製造方法。
- 請求項1〜4のいずれかに記載された製造方法によって得られる炭素複合化リン酸マンガン鉄リチウム粒子粉末を用いて作製した非水電解質二次電池の製造方法。
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