JP2019061789A - Positive electrode material for non-aqueous electrolyte secondary battery and method for manufacturing the same - Google Patents
Positive electrode material for non-aqueous electrolyte secondary battery and method for manufacturing the same Download PDFInfo
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- JP2019061789A JP2019061789A JP2017183850A JP2017183850A JP2019061789A JP 2019061789 A JP2019061789 A JP 2019061789A JP 2017183850 A JP2017183850 A JP 2017183850A JP 2017183850 A JP2017183850 A JP 2017183850A JP 2019061789 A JP2019061789 A JP 2019061789A
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- transition metal
- metal oxide
- sodium
- lithium
- positive electrode
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000011255 nonaqueous electrolyte Substances 0.000 title abstract description 12
- 238000000034 method Methods 0.000 title description 15
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 160
- 239000011734 sodium Substances 0.000 claims abstract description 78
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 67
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 67
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 52
- 150000003624 transition metals Chemical class 0.000 claims abstract description 52
- 239000000126 substance Substances 0.000 claims abstract description 50
- 150000003388 sodium compounds Chemical class 0.000 claims abstract description 47
- 239000002131 composite material Substances 0.000 claims abstract description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910001415 sodium ion Inorganic materials 0.000 claims description 52
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 51
- 229910052744 lithium Inorganic materials 0.000 claims description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 35
- 150000002642 lithium compounds Chemical class 0.000 claims description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 26
- 229910001416 lithium ion Inorganic materials 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 5
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011572 manganese Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 238000003701 mechanical milling Methods 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
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- 239000000047 product Substances 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- 239000003575 carbonaceous material Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
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- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003823 mortar mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
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- KFAFTZQGYMGWLU-UHFFFAOYSA-N oxo(oxovanadiooxy)vanadium Chemical compound O=[V]O[V]=O KFAFTZQGYMGWLU-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
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- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- ZBNMBCAMIKHDAA-UHFFFAOYSA-N sodium superoxide Chemical compound [Na+].O=O ZBNMBCAMIKHDAA-UHFFFAOYSA-N 0.000 description 1
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- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、希少金属の使用量が少ない非水電解質二次電池用の正極材料およびその製造方法に関する。 The present invention relates to a positive electrode material for a non-aqueous electrolyte secondary battery, which uses a small amount of rare metals, and a method for producing the same.
非水電解質二次電池であるリチウムイオン二次電池は高いエネルギー密度を有する。このため、リチウムイオン二次電池は、携帯電話やノートパソコン等の小型電源の他、電気自動車等の大型電源としても実用化されている。今後もリチウムイオン二次電池の需要の拡大が期待される。リチウムイオン二次電池の正極材料として、コバルト酸リチウム(ＬｉＣｏＯ2)がよく用いられている。この正極材料を構成するコバルトは、希少金属のため原料価格が高い。また、コバルトは南米や中国等に偏在しており、コバルト原料の安定供給に不安がある。 Lithium ion secondary batteries, which are non-aqueous electrolyte secondary batteries, have high energy density. For this reason, the lithium ion secondary battery is put to practical use as a large power source such as an electric car as well as a small power source such as a mobile phone and a notebook computer. Demand for lithium ion secondary batteries is expected to continue to grow in the future. Lithium cobaltate (LiCoO 2 ) is often used as a positive electrode material of a lithium ion secondary battery. Cobalt constituting this positive electrode material is a rare metal and therefore the raw material price is high. In addition, cobalt is ubiquitous in South America, China, etc., and there is concern about the stable supply of cobalt raw materials.
この課題を解決するため、コバルトと同様に資源偏在性が高いリチウムを使用しない次世代二次電池として、ナトリウムイオン二次電池が研究されている。ナトリウムイオン二次電池の電荷担体であるナトリウムは、資源量が豊富で安価な材料である。このため、ナトリウムイオン二次電池の実用化が期待されている。特に、鉄酸ナトリウム(ＮａＦｅＯ2)やマンガン酸ナトリウム(ＮａＭｎＯ2)などは、希少金属を含まないので、ナトリウムイオン二次電池用の正極材料として注目されている。しかしながら、ナトリウムはリチウムと比べて三倍以上の質量数を示すことから、ナトリウムイオン二次電池用正極材料は重量あたりの容量密度がリチウム二次電池用正極材料と比べて小さいという問題がある。 In order to solve this problem, sodium ion secondary batteries are being studied as next-generation secondary batteries that do not use lithium, which has high resource localization like cobalt. Sodium, which is a charge carrier of a sodium ion secondary battery, is a resource-rich and inexpensive material. For this reason, practical use of a sodium ion secondary battery is expected. In particular, sodium ferrate (NaFeO 2) or sodium permanganate (NaMnO 2) Since not contain rare metals, is attracting attention as a positive electrode material for a sodium ion secondary battery. However, since sodium exhibits a mass number three or more times that of lithium, there is a problem that the positive electrode material for a sodium ion secondary battery has a smaller capacity density per weight than the positive electrode material for a lithium secondary battery.
ナトリウムを含有する化合物と遷移金属を含有する化合物をメカニカルミリングで複合化したナトリウムイオン二次電池用正極が非特許文献１に記載されている。このナトリウムイオン二次電池用正極は約２００ｍＡｈ／ｇの高い可逆容量を示すことが、非特許文献１で報告されている。しかしながら、この材料は充放電時の大きな構造変化により充放電サイクル中に容量が劣化するという問題がある。
Non-Patent
本発明は、上記の問題に鑑みてなされたものであり、希少金属の使用量を抑え、三価と四価の間の酸化還元反応が利用できる遷移金属酸化物を用いて、従来よりも高容量で、かつ充放電が安定してできる非水電解質二次電池用の正極材料を提供することを主な目的とする。 The present invention has been made in view of the above problems, and it is possible to use a transition metal oxide which can suppress the use amount of rare metals and can utilize the oxidation-reduction reaction between trivalent and tetravalent, and can be higher than the prior art. The main object of the present invention is to provide a positive electrode material for a non-aqueous electrolyte secondary battery which is stable in capacity and charge and discharge.
本発明者らは、上記目的を達成すべく鋭意研究を重ねてきた。その結果、非特許文献１に記載されたナトリウム正極材料と、充放電によりＮａが挿入脱離可能なＮａＦｅＯ2のようなナトリウム含有遷移金属酸化物正極材料を複合化すると、その複合体はナトリウム正極材料およびナトリウム含有遷移金属酸化物正極材料をそれぞれ単独で充放電した場合と比べて高容量が得られることを見出した。
The present inventors have intensively studied to achieve the above object. As a result, when the sodium positive electrode material described in
本発明の複合体は、酸素を含有するナトリウム化合物と、遷移金属酸化物と、ナトリウム含有遷移金属酸化物とを有し、遷移金属酸化物中の遷移金属の物質量Ａに対するナトリウム化合物中のナトリウムの物質量Ｂの比Ｂ／Ａが１.０〜２.０であり、遷移金属酸化物中の遷移金属の物質量Ａに対するナトリウム含有遷移金属酸化物中の遷移金属の物質量Ｃの比Ｃ／Ａが１.０〜４.０である。本発明のナトリウムイオン二次電池用の正極材料は、本発明の複合体を含有する。また、本発明のナトリウムイオン二次電池は、本発明の正極材料を正極活物質として含む正極と、負極と、電解質とを有する。 The complex of the present invention comprises an oxygen-containing sodium compound, a transition metal oxide, and a sodium-containing transition metal oxide, and the sodium in the sodium compound relative to the mass A of the transition metal in the transition metal oxide The ratio B / A of the substance mass B of B is 1.0 to 2.0, and the ratio C of the substance mass C of the transition metal in the sodium-containing transition metal oxide to the substance mass A of the transition metal in the transition metal oxide / A is 1.0 to 4.0. The positive electrode material for a sodium ion secondary battery of the present invention contains the composite of the present invention. Further, the sodium ion secondary battery of the present invention has a positive electrode containing the positive electrode material of the present invention as a positive electrode active material, a negative electrode, and an electrolyte.
本発明の他の複合体は、酸素を含有するリチウム化合物と、遷移金属酸化物と、リチウム含有遷移金属酸化物とを有し、遷移金属酸化物中の遷移金属の物質量Ａに対するリチウム化合物中のリチウムの物質量Ｄの比Ｄ／Ａが１.０〜２.０であり、遷移金属酸化物中の遷移金属の物質量Ａに対するリチウム含有遷移金属酸化物中の遷移金属の物質量Ｅの比Ｅ／Ａが１.０〜４.０ある。本発明のリチウムイオン二次電池用の正極材料は、本発明の複合体を含有する。また、本発明のリチウムイオン二次電池は、本発明の正極材料を正極活物質として含む正極と、負極と、電解質とを有する。 Another composite of the present invention comprises a lithium compound containing oxygen, a transition metal oxide, and a lithium-containing transition metal oxide, and in the lithium compound relative to the mass A of the transition metal in the transition metal oxide The ratio D / A of the lithium substance mass D is 1.0 to 2.0, and the substance mass E of the transition metal in the lithium-containing transition metal oxide to the substance mass A of the transition metal in the transition metal oxide The ratio E / A is 1.0 to 4.0. The positive electrode material for a lithium ion secondary battery of the present invention contains the composite of the present invention. The lithium ion secondary battery of the present invention has a positive electrode containing the positive electrode material of the present invention as a positive electrode active material, a negative electrode, and an electrolyte.
本発明の複合体の製造方法は、酸素を含有するナトリウム化合物と、遷移金属酸化物と、ナトリウム含有遷移金属酸化物とを有する複合体の製造方法であって、遷移金属酸化物中の遷移金属の物質量Ａに対するナトリウム化合物中のナトリウの物質量Ｂの比Ｂ／Ａが１.０〜２.０と、遷移金属酸化物中の遷移金属の物質量Ａに対するナトリウム含有遷移金属酸化物中の遷移金属の物質量Ｃの比Ｃ／Ａが１.０〜４.０となるように、ナトリウム化合物と、遷移金属酸化物と、ナトリウム含有遷移金属酸化物とを配合した後、混合することによって複合体を得る。 The method for producing a complex of the present invention is a method for producing a complex having an oxygen-containing sodium compound, a transition metal oxide, and a sodium-containing transition metal oxide, wherein the transition metal in the transition metal oxide is The ratio B / A of the substance mass B of sodium in the sodium compound to the substance mass A of 1.0 to 2.0, and in the sodium-containing transition metal oxide relative to the substance mass A of transition metal in the transition metal oxide By blending the sodium compound, the transition metal oxide, and the sodium-containing transition metal oxide so that the ratio C / A of the substance mass C of the transition metal is 1.0 to 4.0, by mixing Get the complex.
本発明の他の複合体の製造方法は、酸素を含有するリチウム化合物と、遷移金属酸化物と、リチウム含有遷移金属酸化物とを有する複合体の製造方法であって、遷移金属酸化物中の遷移金属の物質量Ａに対するリチウム化合物中のリチウムの物質量Ｄの比Ｄ／Ａが１.０〜２.０と、遷移金属酸化物中の遷移金属の物質量Ａに対するリチウム含有遷移金属酸化物中の遷移金属の物質量Ｅの比Ｅ／Ａが１.０〜４.０となるように、リチウム化合物と、遷移金属酸化物と、リチウム含有遷移金属酸化物とを配合した後、混合することによって複合体を得る。 Another method for producing a composite according to the present invention is a method for producing a composite having an oxygen-containing lithium compound, a transition metal oxide, and a lithium-containing transition metal oxide, wherein the composite is contained in the transition metal oxide. The ratio D / A of the substance mass D of lithium in the lithium compound to the substance mass A of the transition metal is 1.0 to 2.0, and the lithium containing transition metal oxide relative to the substance mass A of the transition metal in the transition metal oxide Mix the lithium compound, the transition metal oxide, and the lithium-containing transition metal oxide so that the ratio E / A of the substance mass E of the transition metal in the mixture is 1.0 to 4.0, and mix them. To obtain a complex.
本発明によれば、従来と比べて非常に高容量で、かつ希少金属の使用量を抑えた非水電解質二次電池用の正極材料が得られる。 According to the present invention, it is possible to obtain a positive electrode material for a non-aqueous electrolyte secondary battery which has a very high capacity and suppresses the use amount of a rare metal as compared with the prior art.
以下、本発明の複合体、複合体の製造方法、正極材料、ナトリウムイオン二次電池、およびリチウムイオン二次電池について、実施形態と実施例に基づいて説明する。なお、重複説明は適宜省略する。また、２つの数値の間に「〜」を記載して数値範囲を表す場合には、この２つの数値も数値範囲に含まれる。 The composite, the composite production method, the positive electrode material, the sodium ion secondary battery, and the lithium ion secondary battery of the present invention will be described below based on embodiments and examples. In addition, duplication explanation is omitted suitably. Moreover, when describing "-" between two numerical values and expressing a numerical range, these two numerical values are also included in a numerical range.
(ナトリウム化合物を含有する複合体)
本発明の第一実施形態に係る複合体は、酸素を含有するナトリウム化合物と、遷移金属酸化物と、ナトリウム含有遷移金属酸化物とを有している。本実施形態の複合体は、酸素を含有するナトリウム化合物と、遷移金属酸化物と、ナトリウム含有遷移金属酸化物との均一混合物または低結晶性の反応物である。
(Complex containing sodium compound)
The complex according to the first embodiment of the present invention includes an oxygen-containing sodium compound, a transition metal oxide, and a sodium-containing transition metal oxide. The complex of the present embodiment is a homogeneous mixture or a low crystalline reactant of an oxygen-containing sodium compound, a transition metal oxide, and a sodium-containing transition metal oxide.
酸素を含有するナトリウム化合物としては、酸化ナトリウム(Ｎａ2Ｏ)、過酸化ナトリウム(Ｎａ2Ｏ2)、超酸化ナトリウム(ＮａＯ2)、水酸化ナトリウム(ＮａＯＨ)、炭酸ナトリウム(Ｎａ2ＣＯ3)、炭酸水素ナトリウム(ＮａＨＣＯ3)などのナトリウム塩等が例示できる。これらの中でも、酸素とナトリウムのみからなるナトリウム化合物と、遷移金属酸化物と、ナトリウム含有遷移金属酸化物とを有する複合体から得られる正極を用いると、ナトリウムイオン二次電池の充放電サイクル特性を向上させることができる。ナトリウムと酸素のみからなるナトリウム化合物としては、過酸化ナトリウムが特に好ましい。 As sodium compounds containing oxygen, sodium oxide (Na 2 O), sodium peroxide (Na 2 O 2 ), sodium superoxide (NaO 2 ), sodium hydroxide (NaOH), sodium carbonate (Na 2 CO 3 ) And sodium salts such as sodium hydrogen carbonate (NaHCO 3 ). Among these, when using a positive electrode obtained from a complex having a sodium compound consisting of only oxygen and sodium, a transition metal oxide, and a transition metal oxide containing sodium, the charge-discharge cycle characteristics of a sodium ion secondary battery can be obtained. It can be improved. Sodium peroxide is particularly preferable as a sodium compound consisting only of sodium and oxygen.
遷移金属酸化物中の遷移金属は、Ｍｎ、Ｃｏ、Ｎｉ、Ｆｅ、Ｖ、およびＣｒの中から選ばれる少なくとも一種であることが好ましい。遷移金属酸化物としては、一酸化マンガン(ＭｎＯ)、三酸化二マンガン(Ｍｎ2Ｏ3)、三酸化四マンガン(Ｍｎ3Ｏ4)、四酸化三コバルト(Ｃｏ3Ｏ4)、一酸化ニッケル(ＮｉＯ)、四酸化三鉄(Ｆｅ3Ｏ4)、三酸化二バナジウム(Ｖ2Ｏ3)、三酸化二クロム(Ｃｒ2Ｏ3)等が例示できる。ナトリウム化合物または遷移金属酸化物は、市販品を使用してもよいし、合成品を使用してもよい。 The transition metal in the transition metal oxide is preferably at least one selected from Mn, Co, Ni, Fe, V, and Cr. As a transition metal oxide, manganese monoxide (MnO), manganese trioxide (Mn 2 O 3 ), tetramanganese trioxide (Mn 3 O 4 ), tricobalt tetraoxide (Co 3 O 4 ), nickel monoxide (NiO), triiron tetraoxide (Fe 3 O 4 ), divanadium trioxide (V 2 O 3 ), dichromium trioxide (Cr 2 O 3 ), and the like can be exemplified. As the sodium compound or transition metal oxide, a commercially available product may be used, or a synthetic product may be used.
遷移金属酸化物は沈殿法により合成することができる。具体的には、遷移金属のイオンを含む水溶液、例えば、硫酸塩、硝酸塩、または塩化物等の水溶液をアルカリ水溶液中に滴下し沈殿物を生成した後、ろ過・乾燥して水分を除去して遷移金属酸化物が得られる。複数の遷移金属を含む酸化物は、複数の遷移金属イオンを含む水溶液をアルカリ水溶液に沈殿させ、ろ過・乾燥することで得ることができる。アルカリ水溶液としては、例えば、水酸化ナトリウム水溶液、炭酸ナトリウム水溶液、水酸化リチウム水溶液、水酸化カリウム水溶液等が挙げられる。これらのアルカリ水溶液は、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Transition metal oxides can be synthesized by precipitation. Specifically, an aqueous solution containing transition metal ions, for example, an aqueous solution of sulfate, nitrate or chloride is dropped into an aqueous alkaline solution to form a precipitate, which is then filtered and dried to remove water. A transition metal oxide is obtained. The oxide containing a plurality of transition metals can be obtained by precipitating an aqueous solution containing a plurality of transition metal ions in an alkaline aqueous solution, filtering and drying. Examples of the aqueous alkali solution include sodium hydroxide aqueous solution, sodium carbonate aqueous solution, lithium hydroxide aqueous solution, potassium hydroxide aqueous solution and the like. These aqueous alkali solutions may be used alone or in combination of two or more.
温度１０℃〜５０℃、好ましくは２０℃〜３０℃程度で、ｐＨが９〜１４、好ましくは１２〜１４となるように調整したアルカリ水溶液に、遷移金属イオンを含む水溶液を少しずつ添加し、沈殿物を生成させることが好ましい。アルカリ水溶液を２種以上使用する場合、各水溶液は、別途添加してもよいし、同時に添加してもよい。ナトリウム化合物および遷移金属酸化物の形状については特に制限がないが、取り扱い性の観点から、粉末状であることが好ましい。遷移金属酸化物中の遷移金属の物質量Ａに対するナトリウム化合物中のナトリウムの物質量Ｂの比Ｂ／Ａ、すなわち「ナトリウム化合物中のナトリウムのモル量／遷移金属酸化物中の遷移金属のモル量」は１.０〜２.０であることが好ましく、１.３〜１.５であることがさらに好ましい。 An aqueous solution containing transition metal ions is added little by little to an aqueous alkali solution adjusted to have a pH of 9 to 14, preferably 12 to 14 at a temperature of 10 ° C. to 50 ° C., preferably 20 ° C. to 30 ° C. It is preferred to produce a precipitate. When using 2 or more types of alkaline aqueous solution, each aqueous solution may be separately added, and may be added simultaneously. The shape of the sodium compound and the transition metal oxide is not particularly limited, but it is preferably in the form of powder from the viewpoint of handleability. Ratio B / A of substance mass B of sodium in sodium compound to substance mass A of transition metal in transition metal oxide, ie “molar amount of sodium in sodium compound / molar amount of transition metal in transition metal oxide “Is preferably 1.0 to 2.0, and more preferably 1.3 to 1.5.
ナトリウム含有遷移金属酸化物は、Ｔｉ、Ｖ、Ｍｎ、Ｆｅ、ＣｏおよびＮｉの中から選ばれる少なくとも一種を含有することが好ましい。ナトリウム含有遷移金属酸化物としてはＮａＴｉＯ2、ＮａＶＯ2、ＮａＣｒＯ2、ＮａＭｎＯ2、ＮａＦｅＯ2、ＮａＣｏＯ2、ＮａＮｉＯ2、Ｎａ(Ｆｅ1-xＣｏx)Ｏ2、Ｎａ(Ｆｅ1-xＭｎx)Ｏ2、Ｎａ(ＦｅxＭｎyＮｉ1-x-y)Ｏ2、Ｎａ2/3(ＭｎxＣｏyＮｉ1-x-y)Ｏ2等が例示できる。ナトリウム含有遷移金属酸化物は市販品を使用してもよいし、合成品を使用してもよい。 The sodium-containing transition metal oxide preferably contains at least one selected from Ti, V, Mn, Fe, Co and Ni. As sodium-containing transition metal oxides, NaTiO 2 , NaVO 2 , NaCrO 2 , NaMnO 2 , NaFeO 2 , NaFeO 2 , NaCoO 2 , NaNiO 2 , Na (Fe 1-x Co x ) O 2 , Na (Fe 1-x Mn x ) O 2 , Na (Fe x Mn y Ni 1 -xy ) O 2 , Na 2/3 (Mn x Co y Ni 1 -xy ) O 2 and the like can be exemplified. The sodium-containing transition metal oxide may be a commercially available product or a synthetic product.
ナトリウム含有遷移金属酸化物は、焼成法により合成することができる。具体的には、遷移金属酸化物と酸素を含有するナトリウム化合物を均一に混合した後、６００℃〜１０００℃で焼成することで得られる。遷移金属酸化物は市販品を用いてもよいし、前述の方法で作製したものを用いてもよい。酸素を含有するナトリウム化合物は前述と同じものであれば特に制限はない。 The sodium-containing transition metal oxide can be synthesized by a firing method. Specifically, it is obtained by uniformly mixing the transition metal oxide and the sodium compound containing oxygen, and then firing at 600 ° C. to 1000 ° C. As the transition metal oxide, a commercially available product may be used, or one produced by the above-mentioned method may be used. The oxygen-containing sodium compound is not particularly limited as long as it is the same as described above.
遷移金属酸化物中の遷移金属の物質量Ａに対するナトリウム含有遷移金属酸化物中の遷移金属の物質量Ｃの比Ｃ／Ａ、すなわち「ナトリウム含有遷移金属酸化物中の遷移金属のモル量／遷移金属酸化物中の遷移金属のモル量」は１.０〜４.０であることが好ましい。本実施形態の複合体は、非水電解質二次電池用の正極活物質等の正極材料として使用できる。なお、本実施形態の複合体は、ナトリウム化合物と遷移金属酸化物以外に導電性の向上を目的としてカーボンブラック等の炭素系材料や、複合体の表面被覆物質としてフッ化物やリン酸塩などを少量有していてもよい。また、本実施形態の複合体は、リチウム化合物等の他のアルカリ金属化合物を含有していてもよい。 Ratio C / A of the substance mass C of the transition metal in the sodium-containing transition metal oxide to the substance mass A of the transition metal in the transition metal oxide, ie, "molar amount of transition metal / transition in the sodium-containing transition metal oxide The molar amount of transition metal in the metal oxide is preferably 1.0 to 4.0. The composite of the present embodiment can be used as a positive electrode material such as a positive electrode active material for a non-aqueous electrolyte secondary battery. In addition to the sodium compound and the transition metal oxide, the composite of this embodiment is a carbon-based material such as carbon black for the purpose of improving the conductivity, and a fluoride or phosphate as a surface covering material of the complex. You may have a small amount. In addition, the complex of the present embodiment may contain another alkali metal compound such as a lithium compound.
(リチウム化合物を含有する複合体)
本発明の第二実施形態に係る複合体は、酸素を含有するリチウム化合物と、遷移金属酸化物と、リチウム含有遷移金属酸化物とを有している。遷移金属酸化物中の遷移金属の物質量Ａに対するリチウム化合物中のリチウムの物質量Ｄの比Ｄ／Ａ、すなわち「リチウム化合物中のリチウムのモル量／遷移金属酸化物中の遷移金属のモル量」は１.０〜２.０であることが好ましい。また、遷移金属酸化物中の遷移金属の物質量Ａに対するリチウム含有遷移金属酸化物中の遷移金属の物質量Ｅの比Ｅ／Ａ、すなわち「リチウム含有遷移金属酸化物中の遷移金属のモル量／遷移金属酸化物中の遷移金属のモル量」は１.０〜４.０であることが好ましい。リチウム化合物は過酸化リチウムであることが好ましい。
(Complex containing lithium compound)
The composite according to the second embodiment of the present invention includes an oxygen-containing lithium compound, a transition metal oxide, and a lithium-containing transition metal oxide. Ratio D / A of substance D of lithium in lithium compound to substance A of transition metal in transition metal oxide, ie "molar amount of lithium in lithium compound / molar amount of transition metal in transition metal oxide""Is preferably 1.0 to 2.0. In addition, the ratio E / A of the substance mass E of the transition metal in the lithium-containing transition metal oxide to the substance mass A of the transition metal in the transition metal oxide, that is, "the molar amount of the transition metal in the lithium-containing transition metal oxide It is preferable that “molar amount of transition metal in transition metal oxide” be 1.0 to 4.0. The lithium compound is preferably lithium peroxide.
(ナトリウムイオン二次電池用の正極材料)
本発明の実施形態に係るナトリウムイオン二次電池用の正極材料は、第一実施形態の複合体を含有する。この正極材料は高容量で充放電サイクル特性に優れているため、この正極材料を含有する正極を用いたナトリウムイオン二次電池を高容量化することができる。また、このナトリウムイオン二次電池では、充電時におけるナトリウム化合物の酸化分解で発生する酸素と遷移金属酸化物が反応し、高価数の遷移金属酸化物に変化する。その後の放電および充電反応は、遷移金属酸化物とナトリウムイオンの反応により進行する。このように、初期充電反応時に遷移金属酸化物と酸素との反応を利用することによって、電池内部の酸素ガス発生を抑制することができる。
(Positive material for sodium ion secondary battery)
The positive electrode material for a sodium ion secondary battery according to an embodiment of the present invention contains the composite of the first embodiment. Since this positive electrode material has high capacity and excellent charge / discharge cycle characteristics, it is possible to increase the capacity of a sodium ion secondary battery using the positive electrode containing this positive electrode material. In addition, in this sodium ion secondary battery, oxygen generated by the oxidative decomposition of the sodium compound at the time of charge reacts with the transition metal oxide to change to an expensive number of transition metal oxides. The subsequent discharge and charge reactions proceed by the reaction of transition metal oxides and sodium ions. Thus, by utilizing the reaction between the transition metal oxide and oxygen during the initial charge reaction, it is possible to suppress the generation of oxygen gas inside the battery.
また、第一実施形態の複合体では、ナトリウム化合物の含有量を任意に調整できる。このため、本実施形態の正極材料を含む正極と、初期充放電時に不可逆容量を有する負極材料を含む負極を組み合わせた二次電池を作製する場合、ナトリウム化合物を多く含む第一実施形態の複合体を正極に用いることで、負極の不可逆容量を補償できる。したがって、本実施形態のナトリウムイオン二次電池用の正極材料は、様々な負極を備えるナトリウムイオン二次電池の正極に使用できる。 Moreover, in the complex of the first embodiment, the content of the sodium compound can be arbitrarily adjusted. For this reason, when producing a secondary battery combining the positive electrode including the positive electrode material of the present embodiment and the negative electrode including the negative electrode material having irreversible capacity at the time of initial charge and discharge, the composite of the first embodiment including a large amount of sodium compound. Can be used to compensate for the irreversible capacity of the negative electrode. Therefore, the positive electrode material for the sodium ion secondary battery of this embodiment can be used for the positive electrode of a sodium ion secondary battery provided with various negative electrodes.
なお、複合体の粒子サイズが小さすぎると、比表面積が大きくなり、充放電反応時に電極表面での副反応が起こりやすくなり、良好な電極特性が得られない。また、複合体の粒子サイズが大きすぎると、粒子内のイオンの拡散に時間がかかり、均一に反応しにくくなるため、電極性能が低下する。電極の良好なサイクル特性を得るためには、粒子サイズが１００ｎｍ〜２μｍであることが好ましく、１μｍ程度であることが特に好ましい。粒子サイズは試料のＳＥＭ画像から算出できる。 If the particle size of the composite is too small, the specific surface area increases, side reactions on the electrode surface are likely to occur during charge and discharge reactions, and good electrode characteristics can not be obtained. In addition, when the particle size of the composite is too large, it takes time to diffuse the ions in the particles and it becomes difficult to react uniformly, resulting in a decrease in electrode performance. In order to obtain good cycle characteristics of the electrode, the particle size is preferably 100 nm to 2 μm, and particularly preferably about 1 μm. Particle size can be calculated from SEM images of the sample.
(リチウムイオン二次電池用の正極材料)
本発明の実施形態に係るリチウムイオン二次電池用の正極材料は、第二実施形態の複合体を含有する。この正極材料は高容量で充放電サイクル特性に優れているため、この正極材料を含有する正極を用いたリチウムイオン二次電池を高容量化することができる。また、このリチウムイオン二次電池では、充電時におけるリチウム化合物の酸化分解で発生する酸素と、遷移金属酸化物が反応し、高価数の遷移金属酸化物に変化する。その後の放電および充電反応は、遷移金属酸化物とリチウムイオンの反応により進行する。このように、初期充電反応時に遷移金属酸化物と酸素との反応を利用することによって、電池内部の酸素ガス発生を抑制することができる。
(Positive material for lithium ion secondary battery)
The positive electrode material for a lithium ion secondary battery according to an embodiment of the present invention contains the composite of the second embodiment. Since this positive electrode material has a high capacity and is excellent in charge and discharge cycle characteristics, it is possible to increase the capacity of a lithium ion secondary battery using a positive electrode containing this positive electrode material. In addition, in this lithium ion secondary battery, the transition metal oxide reacts with oxygen generated by the oxidative decomposition of the lithium compound at the time of charge, and changes to an expensive number of transition metal oxides. The subsequent discharge and charge reactions proceed by the reaction of transition metal oxides and lithium ions. Thus, by utilizing the reaction between the transition metal oxide and oxygen during the initial charge reaction, it is possible to suppress the generation of oxygen gas inside the battery.
また、第二実施形態の複合体では、リチウム化合物の含有量を任意に調整できる。このため、本実施形態の正極材料を含む正極と、初期充放電時に不可逆容量を有する負極材料を含む負極を組み合わせた二次電池を作製する場合、リチウム化合物を多く含む第二実施形態の複合体を正極に用いることで、負極の不可逆容量を補償することが可能である。したがって、本実施形態のリチウムイオン二次電池用の正極材料は、様々な負極を備えるリチウムイオン二次電池の正極に使用できる。 Moreover, in the composite of the second embodiment, the content of the lithium compound can be arbitrarily adjusted. For this reason, when producing a secondary battery combining the positive electrode including the positive electrode material of the present embodiment and the negative electrode including the negative electrode material having irreversible capacity at the time of initial charge and discharge, the composite of the second embodiment including a large amount of lithium compound. It is possible to compensate for the irreversible capacity of the negative electrode by using Therefore, the positive electrode material for a lithium ion secondary battery of the present embodiment can be used for the positive electrode of a lithium ion secondary battery provided with various negative electrodes.
(ナトリウム化合物を含有する複合体の製造方法)
本発明の実施形態に係る複合体の製造方法は、酸素を含有するナトリウム化合物と、遷移金属酸化物と、ナトリウム含有遷移金属酸化物とを有する複合体の製造方法である。そして、遷移金属酸化物中の遷移金属の物質量Ａに対するナトリウム化合物中のナトリウの物質量Ｂの比Ｂ／Ａが１.０〜２.０と、遷移金属酸化物中の遷移金属の物質量Ａに対するナトリウム含有遷移金属酸化物中の遷移金属の物質量Ｃの比Ｃ／Ａが１.０〜４.０となるように、ナトリウム化合物と、遷移金属酸化物と、ナトリウム含有遷移金属酸化物とを配合した後、混合することによって複合体を得る。
(Method of producing complex containing sodium compound)
The method of producing a complex according to an embodiment of the present invention is a method of producing a complex having an oxygen-containing sodium compound, a transition metal oxide, and a sodium-containing transition metal oxide. And, the ratio B / A of the substance mass B of the sodium in the sodium compound to the substance mass A of the transition metal in the transition metal oxide is 1.0 to 2.0, and the substance mass of the transition metal in the transition metal oxide A sodium compound, a transition metal oxide, and a sodium-containing transition metal oxide such that a ratio C / A of a substance mass C of transition metal in the sodium-containing transition metal oxide to A is 1.0 to 4.0 And compounding to obtain a complex by mixing.
混合方法としては、乳鉢混合、メカニカルミリング処理、ナトリウム化合物と、遷移金属酸化物と、ナトリウム含有遷移金属酸化物をそれぞれ溶媒中に分散させた後に混合する方法、またはナトリウム化合物と、遷移金属酸化物と、ナトリウム含有遷移金属酸化物を溶媒中で一度に分散させて混合する方法等が採用できる。ナトリウム化合物と、遷移金属酸化物と、ナトリウム含有遷移金属酸化物をそれぞれ溶媒に分散してから混合を行う場合には、分散性の向上と均一な混合の観点から、ナトリウム化合物、遷移金属酸化物、ナトリウム含有遷移金属酸化物、および溶媒の混合物に超音波を照射することがより好ましい。 As a mixing method, mortar mixing, mechanical milling, a method of dispersing a sodium compound, a transition metal oxide, and a transition metal oxide and a sodium-containing transition metal oxide in a solvent and then mixing, or a sodium compound and a transition metal oxide And a method of dispersing and mixing the sodium-containing transition metal oxide at one time in a solvent and the like can be employed. When the sodium compound, the transition metal oxide, and the sodium-containing transition metal oxide are respectively dispersed in a solvent and then mixed, the sodium compound, the transition metal oxide, and the like from the viewpoint of improving the dispersibility and uniform mixing. More preferably, the mixture of sodium-containing transition metal oxide and solvent is irradiated with ultrasonic waves.
これらの混合方法の中でも、メカニカルミリング処理が好ましい。ナトリウム化合物と、遷移金属酸化物と、ナトリウム含有遷移金属酸化物を、より均一に混合できるからである。メカニカルミリング装置としては、例えば、ボールミル、振動ミル、ターボミル、およびディスクミル等を用いることができる。これらの中でもボールミルを用いた混合が好ましい。混合時の雰囲気は特に制限がなく、例えば、ＡｒやＮ2等の不活性ガス雰囲気、または大気雰囲気等が採用できるが、酸化ナトリウムなどの大気中で反応性が高い原料を用いる場合には、不活性ガス雰囲気でナトリウム化合物と、遷移金属酸化物と、ナトリウム含有遷移金属酸化物を混合することが好ましい。 Among these mixing methods, mechanical milling is preferred. This is because the sodium compound, the transition metal oxide, and the sodium-containing transition metal oxide can be mixed more uniformly. As a mechanical milling device, for example, a ball mill, a vibration mill, a turbo mill, and a disc mill can be used. Among these, mixing using a ball mill is preferable. The atmosphere at the time of mixing is not particularly limited, and, for example, an inert gas atmosphere such as Ar or N 2 or an air atmosphere can be employed, but when using a material having high reactivity in the atmosphere such as sodium oxide, It is preferable to mix the sodium compound, the transition metal oxide, and the sodium-containing transition metal oxide in an inert gas atmosphere.
遷移金属酸化物の結晶子サイズは５０ｎｍ〜９０ｎｍであることが好ましく、複合体の粒子サイズが１００ｎｍ〜２μｍであることが好ましい。遷移金属酸化物の結晶子サイズは、ＸＲＤ測定の遷移金属酸化物構造に帰属される回折ピークの半価幅から、Ｓｃｈｅｒｒｅｒの式に基づいて算出できる。ナトリウム化合物は過酸化ナトリウムであることが好ましい。遷移金属酸化物中の遷移金属は、Ｍｎ、Ｃｏ、Ｎｉ、Ｆｅ、Ｖ、およびＣｒから選ばれる少なくとも一種であることが好ましい。ナトリウム含有遷移金属酸化物は、Ｍｎ、Ｃｏ、Ｎｉ、およびＦｅから選ばれる少なくとも一種を含有することが好ましい。 The crystallite size of the transition metal oxide is preferably 50 nm to 90 nm, and the particle size of the complex is preferably 100 nm to 2 μm. The crystallite size of the transition metal oxide can be calculated from the half value width of the diffraction peak attributed to the transition metal oxide structure in XRD measurement, based on the Scherrer equation. The sodium compound is preferably sodium peroxide. The transition metal in the transition metal oxide is preferably at least one selected from Mn, Co, Ni, Fe, V, and Cr. The sodium-containing transition metal oxide preferably contains at least one selected from Mn, Co, Ni, and Fe.
(リチウム化合物を含有する複合体の製造方法)
本発明の他の実施形態に係る複合体の製造方法は、酸素を含有するリチウム化合物と、遷移金属酸化物と、リチウム含有遷移金属酸化物とを有する複合体の製造方法である。そして、遷移金属酸化物中の遷移金属の物質量Ａに対するリチウム化合物中のリチウムの物質量Ｄの比Ｄ／Ａが１.０〜２.０と、遷移金属酸化物中の遷移金属の物質量Ａに対するリチウム含有遷移金属酸化物中の遷移金属の物質量Ｅの比Ｅ／Ａが１.０〜４.０となるように、リチウム化合物と、遷移金属酸化物と、リチウム含有遷移金属酸化物とを配合した後、混合することによって複合体を得る。
(Method of producing complex containing lithium compound)
The method for producing a composite according to another embodiment of the present invention is a method for producing a composite having an oxygen-containing lithium compound, a transition metal oxide, and a lithium-containing transition metal oxide. And, the ratio D / A of the substance mass D of lithium in the lithium compound to the substance mass A of transition metal in the transition metal oxide is 1.0 to 2.0, and the substance mass of transition metal in the transition metal oxide The lithium compound, the transition metal oxide, and the lithium-containing transition metal oxide such that the ratio E / A of the substance mass E of the transition metal in the lithium-containing transition metal oxide to A is 1.0 to 4.0 And compounding to obtain a complex by mixing.
リチウム化合物と、遷移金属酸化物と、リチウム含有遷移金属酸化物の混合は、ナトリウム化合物と、遷移金属酸化物と、ナトリウム含有遷移金属酸化物の混合と同様の方法で行うことができる。なお、遷移金属酸化物の結晶子サイズは５０ｎｍ〜９０ｎｍであることが好ましく、複合体の粒子サイズが１００ｎｍ〜２μｍであることが好ましい。リチウム化合物は過酸化リチウムであることが好ましい。遷移金属酸化物中の遷移金属は、Ｍｎ、Ｃｏ、Ｎｉ、Ｆｅ、Ｖ、およびＣｒの中から選択される少なくとも一種であることが好ましい。リチウム含有遷移金属酸化物は、Ｍｎ、Ｃｏ、Ｎｉ、およびＦｅから選ばれる少なくとも一種を含有することが好ましい。 The mixing of the lithium compound, the transition metal oxide, and the lithium-containing transition metal oxide can be performed in the same manner as the mixing of the sodium compound, the transition metal oxide, and the sodium-containing transition metal oxide. The crystallite size of the transition metal oxide is preferably 50 nm to 90 nm, and the particle size of the complex is preferably 100 nm to 2 μm. The lithium compound is preferably lithium peroxide. The transition metal in the transition metal oxide is preferably at least one selected from Mn, Co, Ni, Fe, V, and Cr. The lithium-containing transition metal oxide preferably contains at least one selected from Mn, Co, Ni, and Fe.
(ナトリウムイオン二次電池)
本発明の実施形態に係るナトリウムイオン二次電池は、本実施形態のナトリウムイオン二次電池の正極材料を正極活物質として含む正極と、負極と、電解質と、セパレータを備えている。このナトリウムイオン二次電池は、例えば、非水電解質ナトリウムイオン二次電池、全固体型ナトリウムイオン二次電池、または金属ナトリウムイオン二次電池等である。これらのナトリウムイオン二次電池の基本的な構造は、本実施形態のナトリウムイオン二次電池用の正極材料を正極活物質として用いることを除いて、公知のナトリウムイオン二次電池の構造と同様とすることができる。本実施形態のナトリウムイオン二次電池の形状についても特に限定がなく、円筒型や角型等の形状が採用できる。
(Sodium ion secondary battery)
The sodium ion secondary battery according to the embodiment of the present invention includes a positive electrode including the positive electrode material of the sodium ion secondary battery of the present embodiment as a positive electrode active material, a negative electrode, an electrolyte, and a separator. The sodium ion secondary battery is, for example, a non-aqueous electrolyte sodium ion secondary battery, an all solid sodium ion secondary battery, or a metal sodium ion secondary battery. The basic structure of these sodium ion secondary batteries is the same as that of a known sodium ion secondary battery except that the positive electrode material for the sodium ion secondary battery of this embodiment is used as a positive electrode active material. can do. The shape of the sodium ion secondary battery of the present embodiment is also not particularly limited, and a shape such as a cylindrical shape or a square shape can be adopted.
負極は、ナトリウムを含有する負極材料を負極活物質として含んでいてもよいし、ナトリウムを含有しない負極活物質から構成されていてもよい。負極活物質としては、例えば、難焼結性炭素、ナトリウム金属、スズ、またはこれらを含む合金等、ナトリウムと反応する物質を用いることができる。必要に応じて導電剤やバインダー等を用いて、Ａｌ、Ｃｕ、Ｎｉ、ステンレス、またはカーボン等からなる負極集電体にこれらの負極活物質を担持させることで、負極が作製できる。セパレータは、例えば、ポリエチレンやポリプロピレン等のポリオレフィン樹脂、フッ素樹脂、ナイロン、芳香族アラミド、または無機ガラス等の材質から構成される。セパレータは、多孔質膜、不織布、または織布等の形態の材料を用いることができる。 The negative electrode may contain a negative electrode material containing sodium as a negative electrode active material, or may be composed of a negative electrode active material not containing sodium. As the negative electrode active material, for example, a material that reacts with sodium, such as poorly sinterable carbon, sodium metal, tin, or an alloy containing any of these, can be used. A negative electrode can be produced by supporting these negative electrode active materials on a negative electrode current collector made of Al, Cu, Ni, stainless steel, carbon or the like using a conductive agent, a binder or the like as necessary. The separator is made of, for example, a material such as a polyolefin resin such as polyethylene or polypropylene, a fluorine resin, nylon, an aromatic aramid, or an inorganic glass. The separator can use a material in the form of a porous membrane, a non-woven fabric, or a woven fabric.
非水電解質ナトリウムイオン二次電池では、正極活物質である本実施形態のナトリウムイオン二次電池の正極材料、導電剤、およびバインダーを混合した正極合剤を、Ａｌ、ステンレス、またはカーボンクロス等の正極集電体に担持させることで、正極が作製できる。導電剤としては、例えば、黒鉛、コークス類、カーボンブラック、または針状カーボン等の炭素材料を用いることができる。非水電解質ナトリウムイオン二次電池の電解質は非水溶媒系の電解液である。この電解液の溶媒としては、カーボネート類、エーテル類、ニトリル類、含硫黄化合物等の公知の非水溶媒系二次電池の電解液の溶媒を用いることができる。 In a non-aqueous electrolyte sodium ion secondary battery, the positive electrode material mixture of the positive electrode material of the sodium ion secondary battery of the present embodiment, which is a positive electrode active material, a conductive agent, and a binder, such as Al, stainless steel or carbon cloth The positive electrode can be manufactured by supporting the positive electrode current collector. As a conductive agent, carbon materials, such as graphite, cokes, carbon black, or needle-like carbon, can be used, for example. The electrolyte of the non-aqueous electrolyte sodium ion secondary battery is a non-aqueous solvent-based electrolyte. As a solvent of this electrolyte solution, the solvent of electrolyte solution of well-known nonaqueous solvent type secondary batteries, such as carbonates, ethers, nitriles, and a sulfur-containing compound, can be used.
全固体型ナトリウムイオン二次電池では、正極活物質としての本実施形態のナトリウムイオン二次電池の正極材料、導電剤、バインダー、および固体電解質等を含む正極合剤を、Ｔｉ、Ａｌ、Ｎｉ、ステンレス等の正極集電体に担持させることで、正極が作製できる。導電剤としては、非水電解質ナトリウムイオン二次電池の場合と同様に、例えば、黒鉛、コークス類、カーボンブラック、または針状カーボン等の炭素材料を用いることができる。全固体型ナトリウムイオン二次電池の固体電解質としては、例えば、ポリエチレンオキサイド系の高分子化合物、ポリオルガノシロキサン鎖およびポリオキシアルキレン鎖の少なくとも一方を含む高分子化合物等のポリマー系固体電解質、硫化物系固体電解質、または酸化物系固体電解質等を用いることができる。 In the all-solid-state sodium ion secondary battery, a positive electrode mixture containing the positive electrode material of the sodium ion secondary battery of the present embodiment as a positive electrode active material, a conductive agent, a binder, a solid electrolyte and the like, Ti, Al, Ni, The positive electrode can be manufactured by supporting it on a positive electrode current collector such as stainless steel. As the conductive agent, a carbon material such as, for example, graphite, cokes, carbon black, or needle-like carbon can be used as in the case of the non-aqueous electrolyte sodium ion secondary battery. Examples of solid electrolytes of all solid sodium ion secondary batteries include polymer based solid electrolytes such as polyethylene oxide type polymer compounds, polymer compounds containing at least one of polyorganosiloxane chain and polyoxyalkylene chain, sulfide Based solid electrolytes or oxide based solid electrolytes can be used.
(リチウムイオン二次電池)
本発明の実施形態に係るリチウムイオン二次電池は、本実施形態のリチウムイオン二次電池の正極材料を正極活物質として含む正極と、負極と、電解質とを有する。このリチウムイオン二次電池の基本的な構造は、正極活物質を除いて、公知のリチウムイオン二次電池の構造と同様とすることができる。
(Lithium ion secondary battery)
The lithium ion secondary battery according to the embodiment of the present invention has a positive electrode including the positive electrode material of the lithium ion secondary battery of the present embodiment as a positive electrode active material, a negative electrode, and an electrolyte. The basic structure of this lithium ion secondary battery can be the same as that of a known lithium ion secondary battery except for the positive electrode active material.
以下、実施例を示して本発明を具体的に説明するが、本発明はこれらの実施例のみに限定されない。 EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.
合成例１：遷移金属酸化物の作製
複合体を構成する遷移金属酸化物を以下の方法により作製した。市販の硫酸マンガン(ＭｎＳＯ4)を蒸留水に溶かして、濃度１Ｍの硫酸マンガン水溶液を得た。濃度１Ｍの水酸化ナトリウム水溶液にこの硫酸マンガン水溶液を少しずつ添加し、沈殿物を生成させた。沈殿物が中性になるまで蒸留水で洗浄し、その後、大気中にて８０℃で乾燥させて酸化マンガン(Ｍｎ3Ｏ4)を得た。
Synthesis Example 1: Preparation of Transition Metal Oxide A transition metal oxide constituting a complex was prepared by the following method. Commercially available manganese sulfate (MnSO 4 ) was dissolved in distilled water to obtain a 1 M aqueous solution of manganese sulfate. The manganese sulfate aqueous solution was added little by little to a 1 M aqueous sodium hydroxide solution to form a precipitate. The precipitate was washed with distilled water until it became neutral, and then dried at 80 ° C. in the atmosphere to obtain manganese oxide (Mn 3 O 4 ).
同様の方法で、硫酸鉄(ＦｅＳＯ4)、硫酸コバルト(ＣｏＳＯ4)、硫酸ニッケル(ＮｉＳＯ4)、およびこれらの硫酸塩のいずれかを２種類以上含む混合物から、酸化マンガン(Ｍｎ3Ｏ4)、酸化コバルト(Ｃｏ3Ｏ4)、(Ｆｅ0.5Ｃｏ0.5)3Ｏ4、(Ｆｅ0.5Ｍｎ0.5)3Ｏ4、(Ｆｅ0.7Ｍｎ0.15Ｎｉ0.15)3Ｏ4、および(Ｍｎ0.667Ｎｉ0.167Ｃｏ0.166)3Ｏ4をそれぞれ作製した。 Manganese oxide (Mn 3 O 4 ) from a mixture containing two or more of iron sulfate (FeSO 4 ), cobalt sulfate (CoSO 4 ), nickel sulfate (NiSO 4 ), and any of these sulfates in a similar manner Cobalt oxide (Co 3 O 4 ), (Fe 0.5 Co 0.5 ) 3 O 4 , (Fe 0.5 Mn 0.5 ) 3 O 4 , (Fe 0.7 Mn 0.15 Ni 0.15 ) 3 O 4 , and (Mn 0.667 Ni 0.167 Co 0.166 ) 3 O 4 was prepared respectively.
合成例２：ナトリウム含有遷移金属酸化物とリチウム含有遷移金属酸化物の作製
酸素を含有するナトリウム化合物またはリチウム化合物と、合成例１で得られた遷移金属酸化物を、遷移金属とナトリウムまたはリチウムとの混合比(いわゆるモル比)が０.５〜２.０：１となるように混合した。その混合物を大気中で６００℃〜１０００℃で１０時間〜２０時間熱処理して、ナトリウム含有遷移金属酸化物またはリチウム含有遷移金属酸化物を得た。
Synthesis Example 2 Preparation of a Sodium-Containing Transition Metal Oxide and a Lithium-Containing Transition Metal Oxide An oxygen-containing sodium compound or lithium compound, the transition metal oxide obtained in Synthesis Example 1, a transition metal and sodium or lithium The mixture ratio (so-called molar ratio) was mixed so as to be 0.5 to 2.0: 1. The mixture was heat-treated in air at 600 ° C. to 1000 ° C. for 10 hours to 20 hours to obtain a sodium-containing transition metal oxide or a lithium-containing transition metal oxide.
実施例１−１〜実施例９：複合体の作製
混合比が表１に記載された値となるように、ナトリウム化合物またはリチウム化合物と、上記で作製した遷移金属酸化物と、ナトリウム含有遷移金属酸化物またはリチウム含有遷移金属酸化物を配合した。表１のモル比は、ナトリウム化合物またはリチウム化合物：遷移金属酸化物：ナトリウム含有遷移金属酸化物またはナトリウム含有遷移金属酸化物を示している。また、表１のナトリウム含有遷移金属酸化物またはリチウム含有遷移金属酸化物の組成式は、合成例２の仕込比に基づいている。
Examples 1-1 to 9: Preparation of a Complex A sodium compound or a lithium compound, the transition metal oxide prepared above, and a sodium-containing transition metal such that the mixing ratio becomes a value described in Table 1 An oxide or lithium-containing transition metal oxide was blended. The molar ratios in Table 1 indicate sodium compounds or lithium compounds: transition metal oxides: sodium containing transition metal oxides or sodium containing transition metal oxides. The composition formula of the sodium-containing transition metal oxide or lithium-containing transition metal oxide in Table 1 is based on the charge ratio of Synthesis Example 2.
その後、遊星型ボールミルを用いて、５００ｒｐｍ、１４時間〜１６時間のメカニカルミリング処理によって乾式混合した。メカニカルミリング処理は、容量８０ｍＬのＺｒＯ2製ポットとＺｒＯ2ボールを使用し、Ａｒ雰囲気で行った。複合体を構成するナトリウム化合物またはリチウム化合物と、遷移金属酸化物と、ナトリウム含有遷移金属酸化物またはナトリウム含有遷移金属酸化物の種類も表１に記載した。 Thereafter, dry mixing was performed by mechanical milling at 500 rpm for 14 hours to 16 hours using a planetary ball mill. Mechanical milling process, using a ZrO 2 pot and ZrO 2 balls of capacity 80mL, was carried out in an Ar atmosphere. The types of sodium compounds or lithium compounds, transition metal oxides, and sodium-containing transition metal oxides or sodium-containing transition metal oxides constituting the complex are also described in Table 1.
実験例１：複合体のＸＲＤ測定
実施例１−１で得られた複合体について、波長０.１５４０５ｎｍのＣｕ−Ｋα線を用いたＸＲＤ測定を行った。その結果を図１に示す。また、この複合体のＳＥＭ画像を図２に示す。詳細な結晶構造の決定に至ってはいないが、結晶性が非常に低く、また、原料相とは異なるピークが観測されており、実施例１−１で得られた複合体は、原料のＮａ2Ｏ2と、Ｍｎ3Ｏ4と、Ｎａ2/3(Ｍｎ2/3Ｎｉ1/6Ｃｏ1/6)Ｏ2が複合化過程において反応して得られた反応物であると考えられる。
Experimental Example 1: XRD Measurement of Complex The complex obtained in Example 1-1 was subjected to XRD measurement using a Cu-Kα ray having a wavelength of 0.15405 nm. The results are shown in FIG. Moreover, the SEM image of this complex is shown in FIG. Although the determination of the detailed crystal structure has not been made, the crystallinity is very low, and a peak different from the raw material phase is observed, and the complex obtained in Example 1-1 is the raw material Na 2 It is considered to be a reactant obtained by reacting O 2 , Mn 3 O 4 and Na 2/3 (Mn 2/3 Ni 1/6 Co 1/6 ) O 2 in the complexing process.
実験例２：電気化学セルの充放電試験(実施例１−１〜実施例６)
実施例１−１で得られた複合体を用いて、下記の方法で電気化学セル(コインセルＣＲ２０３２)を作製し、充放電試験を行った。活物質である複合体８４質量％、アセチレンブラック(ＡＢ)８質量％、およびＰＴＦＥバインダー８質量％を混合した合剤を調製し、アルミニウムメッシュに密着接合させ、加熱処理(減圧中、２２０℃、１０時間以上)して正極を得た。試験電極計算容量の約５０倍の容量を有する金属ナトリウム箔を対極として用いた。また、ポリプロピレン微多孔膜をセパレータとして用いた。そして、エチレンカーボネート(ＥＣ)とジエチルカーボネート(ＤＥＣ)の混合液(ＥＣ：ＤＥＣ＝１：１(容量％比))にＮａＰＦ6を溶解したもの(１ｍｏｌ／Ｌ)を電解液として用いた。
Experimental Example 2: Charge / Discharge Test of Electrochemical Cell (Examples 1-1 to 6)
Using the composite obtained in Example 1-1, an electrochemical cell (coin cell CR2032) was produced by the following method, and a charge / discharge test was performed. A mixture comprising 84% by mass of the active material composite, 8% by mass of acetylene black (AB) and 8% by mass of PTFE binder is prepared, closely bonded to an aluminum mesh, and heat-treated (at 220 ° C. under reduced pressure). The positive electrode was obtained after 10 hours). A metallic sodium foil having a capacity of about 50 times the test electrode calculated capacity was used as a counter electrode. In addition, a microporous polypropylene membrane was used as a separator. Then, a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) obtained by dissolving a NaPF 6 a (1 mol / L) was used as an electrolyte solution (EC:: DEC = 1 1 ( % by volume ratio)).
カットオフ電位１.５Ｖ〜４.５Ｖの範囲で、電流密度を１０ｍＡ／ｇとして充放電試験を行った。その結果を図３に示す。なお、図３から図１６には、複合体の組成分と混合比、および複合体作製時のメカニカルミリング処理が記載されている。図３に示すように、実施例１−１で得られた複合体を用いた正極は、初期充電容量２０７ｍＡｈ／ｇおよび初期放電容量２４４ｍＡｈ／ｇを示し、Ｎａ2Ｏ2とＭｎ3Ｏ4複合体を用いた正極の初期特性(初期充電容量：１７４ｍＡｈ／ｇ、初期放電容量：１９４ｍＡｈ／ｇ)、およびＮａ2/3(Ｍｎ2/3Ｎｉ1/6Ｃｏ1/6)Ｏ2を用いた正極の初期特性(初期充電容量：１４９ｍＡｈ／ｇ、初期放電容量：２１６ｍＡｈ／ｇ)と比べて、極めて高い初期特性を示した。また、この正極の初期容量に対する２０サイクル後の放電容量維持率(表１では単に「維持率」)は８０％であった。 The charge / discharge test was performed at a current density of 10 mA / g at a cutoff potential of 1.5 V to 4.5 V. The results are shown in FIG. 3 to 16 show the composition and mixing ratio of the complex, and the mechanical milling process at the time of preparation of the complex. As shown in FIG. 3, the positive electrode using the composite obtained in Example 1-1 exhibits an initial charge capacity of 207 mAh / g and an initial discharge capacity of 244 mAh / g, and the Na 2 O 2 and Mn 3 O 4 composite is used. Initial characteristics (initial charge capacity: 174 mAh / g, initial discharge capacity: 194 mAh / g), and Na 2/3 (Mn 2/3 Ni 1/6 Co 1/6 ) O 2 Compared to the initial characteristics of the positive electrode (initial charge capacity: 149 mAh / g, initial discharge capacity: 216 mAh / g), extremely high initial characteristics were exhibited. In addition, the discharge capacity retention ratio after 20 cycles with respect to the initial capacity of the positive electrode (simply, "maintenance ratio" in Table 1) was 80%.
実施例１−２から実施例６で得られた複合体から作製した正極についても同様に充放電試験を行った。その結果を図４から図１２にそれぞれに示す。図４から図１２に示す充放電曲線をもとに初期容量充電容量と初期放電容量を決定した。その結果を表１に示す。表１に示すように、ナトリウム含有遷移金属酸化物がＭｎを含む正極で良好な電極特性が得られ、ＭｎとＣｏを含む正極でより良好な電極特性が得られることがわかった。また、高い放電容量とサイクル安定性を得るためには、ナトリウム化合物：遷移金属酸化物：ナトリウム含有遷移金属酸化物は、１.３〜１.５：１：２であることが好ましいことがわかった。 The charge / discharge test was similarly conducted on the positive electrodes produced from the composites obtained in Examples 1-2 to 6. The results are shown in FIGS. 4 to 12 respectively. The initial capacity charge capacity and the initial discharge capacity were determined based on the charge and discharge curves shown in FIGS. 4 to 12. The results are shown in Table 1. As shown in Table 1, it was found that good electrode characteristics were obtained with the positive electrode containing sodium-containing transition metal oxide Mn, and better electrode characteristics were obtained with the positive electrode containing Mn and Co. In addition, in order to obtain high discharge capacity and cycle stability, it is found that the sodium compound: transition metal oxide: sodium-containing transition metal oxide is preferably 1.3 to 1.5: 1: 2. The
実験例３：ナトリウムイオン全電池の充放電試験
実施例１−１で得られた複合体を正極として用いて、下記の方法でナトリウムイオン全電池(１.５ｍＡｈ)のコインセル(ＣＲ２０３２)を作製し、充放電試験を行った。ハードカーボン９０質量％、ＡＢ５質量％、およびポリフッ化ビニリデン(ＰＶｄＦ)５質量％を混合してスラリー状の合剤を調製し、厚さ１０μｍの銅箔上に塗布・乾燥した後、ロールプレスにより銅箔と塗膜とを密着接合させ、加熱処理(減圧中、１５０℃、５時間以上)して負極を得た。電解液は実験例２と同じものを用いた。カットオフ電位１.５Ｖ〜４.２Ｖの範囲で充放電を行い、ナトリウムイオン電池として機能することを確認した。その結果を図１３に示す。
Experimental Example 3: Charge / Discharge Test of Sodium Ion Full Battery Using the composite obtained in Example 1-1 as a positive electrode, a coin cell (CR2032) of a sodium ion full battery (1.5 mAh) was produced by the following method. , Charge and discharge test was done. 90% by mass of hard carbon, 5% by mass of AB, and 5% by mass of polyvinylidene fluoride (PVdF) are mixed to prepare a slurry-like mixture, which is coated on a copper foil of 10 μm thickness and dried, and then roll pressed The copper foil and the coating were closely bonded and heat treated (under reduced pressure, at 150 ° C. for 5 hours or more) to obtain a negative electrode. The same electrolytic solution as in Experimental Example 2 was used. It charged / discharged in the range of 1.5V-4.2V of cutoff potential, and confirmed that it functions as a sodium ion battery. The results are shown in FIG.
実験例４：リチウムイオン二次電池の充放電試験(実施例７〜実施例９)
実施例７から実施例９で得られた複合体を用いて、実験例２と同様にして正極を作製した。リチウム金属を対極として、カットオフ電位１.５〜４.８Ｖの範囲で充放電試験を行った結果を図１４から図１６に示す。リチウム含有遷移金属酸化物としてＬｉ0.5ＭｎＯ2を用いた複合体(実施例８)では初期充電容量１６９ｍＡｈ／ｇ、初期放電容量３８２ｍＡｈ／ｇを示し、２０サイクル後の放電容量維持率は８２％であった。実施例７から実施例９で得られた複合体は、リチウムイオン二次電池用の正極材料として利用できることがわかった。
Experimental Example 4: Charge / Discharge Test of Lithium Ion Secondary Battery (Examples 7 to 9)
Using the composite obtained in Example 7 to Example 9, a positive electrode was produced in the same manner as in Experimental Example 2. 14 to 16 show the results of the charge / discharge test with a cut-off potential of 1.5 to 4.8 V using lithium metal as the counter electrode. The composite (Example 8) using Li 0.5 MnO 2 as the lithium-containing transition metal oxide shows an initial charge capacity of 169 mAh / g, an initial discharge capacity of 382 mAh / g, and a discharge capacity retention ratio of 20% after 20 cycles there were. It was found that the composite obtained in Example 7 to Example 9 can be used as a positive electrode material for a lithium ion secondary battery.
本発明の複合体は、非水電解質二次電池用の正極活物質などに利用できる。 The composite of the present invention can be used as a positive electrode active material for non-aqueous electrolyte secondary batteries.
Claims (15)
前記遷移金属酸化物中の遷移金属の物質量Ａに対する前記ナトリウム化合物中のナトリウムの物質量Ｂの比Ｂ／Ａが１.０〜２.０であり、
前記遷移金属酸化物中の遷移金属の物質量Ａに対する前記ナトリウム含有遷移金属酸化物中の遷移金属の物質量Ｃの比Ｃ／Ａが１.０〜４.０である複合体。 A complex comprising an oxygen-containing sodium compound, a transition metal oxide, and a sodium-containing transition metal oxide,
The ratio B / A of the substance mass B of sodium in the sodium compound to the substance mass A of transition metal in the transition metal oxide is 1.0 to 2.0,
A composite wherein the ratio C / A of the substance mass C of the transition metal in the sodium-containing transition metal oxide to the substance mass A of the transition metal in the transition metal oxide is 1.0 to 4.0.
前記ナトリウム含有遷移金属酸化物が、Ｍｎ、Ｃｏ、Ｎｉ、およびＦｅの中から選ばれる少なくとも一種を含有する複合体。 In claim 1,
A complex in which the sodium-containing transition metal oxide contains at least one selected from Mn, Co, Ni, and Fe.
前記酸素を含有するナトリウム化合物が過酸化ナトリウムであり、
前記ナトリウム含有遷移金属酸化物がＭｎを含有する複合体。 In claim 1 or 2,
The oxygen-containing sodium compound is sodium peroxide,
A complex wherein the sodium-containing transition metal oxide contains Mn.
前記遷移金属酸化物中の遷移金属の物質量Ａに対する前記リチウム化合物中のリチウムの物質量Ｄの比Ｄ／Ａが１.０〜２.０であり、
前記遷移金属酸化物中の遷移金属の物質量Ａに対する前記リチウム含有遷移金属酸化物中の遷移金属の物質量Ｅの比Ｅ／Ａが１.０〜４.０ある複合体。 A complex comprising an oxygen-containing lithium compound, a transition metal oxide, and a lithium-containing transition metal oxide,
The ratio D / A of the substance mass D of lithium in the lithium compound to the substance mass A of transition metal in the transition metal oxide is 1.0 to 2.0,
A composite having a ratio E / A of the substance mass E of the transition metal in the lithium-containing transition metal oxide to the substance mass A of the transition metal in the transition metal oxide of 1.0 to 4.0.
前記リチウム化合物が過酸化リチウムである複合体。 In claim 6,
A complex wherein the lithium compound is lithium peroxide.
前記遷移金属酸化物中の遷移金属の物質量Ａに対する前記ナトリウム化合物中のナトリウの物質量Ｂの比Ｂ／Ａが１.０〜２.０と、前記遷移金属酸化物中の遷移金属の物質量Ａに対する前記ナトリウム含有遷移金属酸化物中の遷移金属の物質量Ｃの比Ｃ／Ａが１.０〜４.０となるように、前記ナトリウム化合物と、前記遷移金属酸化物と、前記ナトリウム含有遷移金属酸化物とを配合した後、混合することによって前記複合体を得る複合体の製造方法。 A method for producing a complex having an oxygen-containing sodium compound, a transition metal oxide, and a sodium-containing transition metal oxide,
The ratio B / A of the substance mass B of the sodium in the sodium compound to the substance mass A of the transition metal in the transition metal oxide is 1.0 to 2.0, and the substance of the transition metal in the transition metal oxide The sodium compound, the transition metal oxide, and the sodium such that the ratio C / A of the substance mass C of the transition metal in the sodium-containing transition metal oxide to the amount A is 1.0 to 4.0 A method for producing a composite, wherein the composite is obtained by blending with the contained transition metal oxide and then mixing.
前記酸素を含有するナトリウム化合物が過酸化ナトリウムである複合体の製造方法。 In claim 10,
The method for producing a complex, wherein the oxygen-containing sodium compound is sodium peroxide.
前記ナトリウム含有遷移金属酸化物が、Ｍｎ、Ｃｏ、Ｎｉ、およびＦｅの中から選ばれる少なくとも一種を含有する複合体の製造方法。 In claim 10 or 11,
The method for producing a complex, wherein the sodium-containing transition metal oxide contains at least one selected from Mn, Co, Ni, and Fe.
前記遷移金属酸化物中の遷移金属の物質量Ａに対する前記リチウム化合物中のリチウムの物質量Ｄの比Ｄ／Ａが１.０〜２.０と、前記遷移金属酸化物中の遷移金属の物質量Ａに対する前記リチウム含有遷移金属酸化物中の遷移金属の物質量Ｅの比Ｅ／Ａが１.０〜４.０となるように、前記リチウム化合物と、前記遷移金属酸化物と、前記リチウム含有遷移金属酸化物とを配合した後、混合することによって前記複合体を得る複合体の製造方法。 A method for producing a complex having an oxygen-containing lithium compound, a transition metal oxide, and a lithium-containing transition metal oxide,
The ratio D / A of the substance mass D of lithium in the lithium compound to the substance mass A of transition metal in the transition metal oxide is 1.0 to 2.0, and the substance of the transition metal in the transition metal oxide The lithium compound, the transition metal oxide, and the lithium such that the ratio E / A of the substance mass E of the transition metal in the lithium-containing transition metal oxide to the amount A is 1.0 to 4.0 A method for producing a composite, wherein the composite is obtained by blending with the contained transition metal oxide and then mixing.
前記酸素を含有するリチウム化合物が過酸化リチウムである複合体の製造方法。 In claim 13,
The manufacturing method of the complex whose lithium compound containing said oxygen is a lithium peroxide.
前記リチウム含有遷移金属酸化物が、Ｍｎ、Ｃｏ、Ｎｉ、およびＦｅの中から選ばれる少なくとも一種を含有する複合体の製造方法。 In claim 13 or 14,
The method for producing a complex, wherein the lithium-containing transition metal oxide contains at least one selected from Mn, Co, Ni, and Fe.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005276612A (en) * | 2004-03-24 | 2005-10-06 | Sanyo Electric Co Ltd | Positive electrode for nonaqueous electrolyte battery, its manufacturing method, battery using it, and manufacturing method of battery |
| JP2015053244A (en) * | 2012-10-22 | 2015-03-19 | 国立大学法人 東京大学 | Battery |
-
2017
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005276612A (en) * | 2004-03-24 | 2005-10-06 | Sanyo Electric Co Ltd | Positive electrode for nonaqueous electrolyte battery, its manufacturing method, battery using it, and manufacturing method of battery |
| JP2015053244A (en) * | 2012-10-22 | 2015-03-19 | 国立大学法人 東京大学 | Battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114824191A (en) * | 2022-03-11 | 2022-07-29 | 江苏理工学院 | NaMnO 2 @NaV 2 O 5 Composite material and preparation method and application thereof |
| CN114824191B (en) * | 2022-03-11 | 2023-07-11 | 江苏理工学院 | NaMnO 2 @NaV 2 O 5 Composite material and preparation method and application thereof |
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