JP2015032515A - Alkali metal compound with transition metal dissolved therein as solid solution - Google Patents
Alkali metal compound with transition metal dissolved therein as solid solution Download PDFInfo
- Publication number
- JP2015032515A JP2015032515A JP2013162663A JP2013162663A JP2015032515A JP 2015032515 A JP2015032515 A JP 2015032515A JP 2013162663 A JP2013162663 A JP 2013162663A JP 2013162663 A JP2013162663 A JP 2013162663A JP 2015032515 A JP2015032515 A JP 2015032515A
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- JP
- Japan
- Prior art keywords
- transition metal
- alkali metal
- solid solution
- oxide
- metal oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 83
- 239000006104 solid solution Substances 0.000 title claims abstract description 68
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 46
- 150000001339 alkali metal compounds Chemical class 0.000 title abstract description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 58
- 239000013078 crystal Substances 0.000 claims abstract description 26
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 23
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 22
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000007772 electrode material Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 8
- 239000000243 solution Substances 0.000 abstract 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 54
- 239000000843 powder Substances 0.000 description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 40
- 229920000642 polymer Polymers 0.000 description 40
- 238000006056 electrooxidation reaction Methods 0.000 description 28
- 239000000203 mixture Substances 0.000 description 26
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 25
- 229910001947 lithium oxide Inorganic materials 0.000 description 25
- 238000002156 mixing Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 22
- 238000005259 measurement Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 description 16
- 229910000859 α-Fe Inorganic materials 0.000 description 16
- 229910052742 iron Inorganic materials 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 229910000428 cobalt oxide Inorganic materials 0.000 description 11
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 11
- -1 oxides Chemical class 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 229910021389 graphene Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 150000002894 organic compounds Chemical class 0.000 description 8
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- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 239000002134 carbon nanofiber Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
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- 239000007774 positive electrode material Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910010586 LiFeO 2 Inorganic materials 0.000 description 2
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- 239000002033 PVDF binder Substances 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910003472 fullerene Inorganic materials 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 238000010303 mechanochemical reaction Methods 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
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- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
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- 239000003011 anion exchange membrane Substances 0.000 description 1
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- 239000011230 binding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
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- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003010 cation ion exchange membrane Substances 0.000 description 1
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- 235000019425 dextrin Nutrition 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- 239000005486 organic electrolyte Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、遷移金属固溶アルカリ金属化合物に関する。より詳しくは、酸素貯蔵物質や電極材料として利用可能な遷移金属固溶アルカリ金属化合物に関する。 The present invention relates to a transition metal solid solution alkali metal compound. More specifically, the present invention relates to a transition metal solid solution alkali metal compound that can be used as an oxygen storage material or an electrode material.
アルカリ金属化合物は、酸化物、水酸化物、炭酸塩等の種々の化合物が広く知られており、様々な工業分野で広く用いられている。特に近年では、蓄電池やキャパシタ等の蓄電装置の材料としてリチウム化合物の使用量が急速に大きくなる等、その重要性に改めて注目が集まっている。 As the alkali metal compound, various compounds such as oxides, hydroxides and carbonates are widely known, and are widely used in various industrial fields. Particularly in recent years, attention has been renewed on the importance of the use of lithium compounds as materials for power storage devices such as storage batteries and capacitors.
蓄電装置の中で、現在最も広く普及しているのがリチウムイオン電池であり、携帯電話やノートパソコンのバッテリー等として使用されている。しかしながら、リチウムイオン電池は充放電容量が充分とはいえないため、より充放電容量の大きい新たな電池の開発が求められており、近年では、リチウムイオン電池よりも理論容量の大きいリチウム空気電池が注目を集めてきている。リチウム空気電池については、有機系の電解質を用いる方式が報告されている（非特許文献１参照）。 Among power storage devices, the most widely used at present is a lithium ion battery, which is used as a battery for a mobile phone or a notebook computer. However, since the charge / discharge capacity of a lithium ion battery is not sufficient, the development of a new battery having a larger charge / discharge capacity has been demanded. In recent years, a lithium-air battery having a larger theoretical capacity than a lithium ion battery has been demanded. Has attracted attention. A method using an organic electrolyte has been reported for a lithium-air battery (see Non-Patent Document 1).
しかしながら、リチウム空気電池では、充電のためには、４Ｖ程度の高い電圧が必要である。蓄電池の充放電をより容易にするためには、低電圧で充電が可能であるほうが好ましく、より低い容量で充電が可能な電池とすることが求められている。 However, a lithium-air battery requires a high voltage of about 4V for charging. In order to make charge and discharge of the storage battery easier, it is preferable that the battery can be charged with a low voltage, and a battery that can be charged with a lower capacity is required.
本発明は、上記現状に鑑みてなされたものであり、従来のリチウム空気電池よりも低い電圧で充電することが可能な蓄電池の実現を可能とする材料を提供することを目的とする。 This invention is made | formed in view of the said present condition, and it aims at providing the material which enables realization of the storage battery which can be charged with a voltage lower than the conventional lithium air battery.
本発明者は、蓄電池の材料について種々検討し、アルカリ金属化合物に着目した。そして、アルカリ金属酸化物の結晶構造内に遷移金属原子が固溶した構造を有する化合物が従来のリチウム空気電池よりも低い電圧で酸化容量が発現し、充電が可能であることを見出し、上記課題をみごとに解決することができることに想到し、本発明に到達したものである。 The inventor of the present invention studied various materials for storage batteries and focused on alkali metal compounds. Then, it has been found that a compound having a structure in which a transition metal atom is dissolved in the crystal structure of an alkali metal oxide exhibits an oxidation capacity at a lower voltage than a conventional lithium-air battery and can be charged. The present inventors have arrived at the present invention by conceiving that the problem can be solved brilliantly.
すなわち本発明は、アルカリ金属原子と遷移金属原子とを含む金属酸化物であって、上記金属酸化物は、アルカリ金属酸化物の結晶構造内に遷移金属原子が固溶した構造を有する遷移金属固溶アルカリ金属酸化物である。
以下に本発明を詳述する。
なお、以下において記載する本発明の個々の好ましい形態を２つ以上組み合わせたものもまた、本発明の好ましい形態である。
That is, the present invention is a metal oxide containing an alkali metal atom and a transition metal atom, wherein the metal oxide has a structure in which a transition metal atom is dissolved in the crystal structure of the alkali metal oxide. It is a dissolved alkali metal oxide.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.
本発明の遷移金属固溶アルカリ金属酸化物（以下、単に本発明の金属酸化物ともいう）は、アルカリ金属酸化物の結晶構造内に遷移金属原子が固溶した構造を有する。
アルカリ金属酸化物の結晶構造内に遷移金属原子が固溶した構造とは、アルカリ金属酸化物の結晶構造内に遷移金属原子がランダムに入りこんだ構造であり、この点において、本発明の金属酸化物は、アルカリ金属酸化物の結晶構造内に遷移金属原子が一定の割合で規則的に配列した複合酸化物とは異なる。複合酸化物の場合、アルカリ金属酸化物の結晶構造内に規則的に配列した遷移金属原子の影響により、結晶構造内にもとのアルカリ金属酸化物の結晶とは全く別の反射面が生まれ、その結果、ＸＲＤパターンはもとのアルカリ金属酸化物とは全く異なるものとなる。これに対し、本発明の金属酸化物は、アモルファス化しつつ、遷移金属原子が固溶する前のアルカリ金属酸化物のＸＲＤパターンを保持している。また、本発明の金属酸化物では、アルカリ金属に対する固溶する遷移金属原子の割合は決まっておらず、任意の割合で固溶し得る点も、複合酸化物とは異なっている。
本発明の金属酸化物は、アルカリ金属酸化物の結晶構造内に遷移金属原子が固溶した構造は、アルカリ金属酸化物の結晶構造内に遷移金属原子がドーピングした構造ともいうことができる。
The transition metal solid solution alkali metal oxide of the present invention (hereinafter also simply referred to as the metal oxide of the present invention) has a structure in which transition metal atoms are dissolved in the crystal structure of the alkali metal oxide.
The structure in which transition metal atoms are dissolved in the crystal structure of the alkali metal oxide is a structure in which transition metal atoms randomly enter the crystal structure of the alkali metal oxide. In this respect, the metal oxidation of the present invention The product is different from a complex oxide in which transition metal atoms are regularly arranged at a certain ratio in the crystal structure of the alkali metal oxide. In the case of complex oxides, the influence of transition metal atoms regularly arranged in the crystal structure of the alkali metal oxide creates a completely different reflective surface from the crystal of the alkali metal oxide in the crystal structure. As a result, the XRD pattern is completely different from the original alkali metal oxide. On the other hand, the metal oxide of the present invention retains the XRD pattern of the alkali metal oxide before the transition metal atom is dissolved, while becoming amorphous. Moreover, in the metal oxide of the present invention, the ratio of the transition metal atom that dissolves in the alkali metal is not determined, and it is different from the composite oxide in that it can be dissolved in an arbitrary ratio.
In the metal oxide of the present invention, the structure in which transition metal atoms are dissolved in the crystal structure of the alkali metal oxide can also be referred to as a structure in which transition metal atoms are doped in the crystal structure of the alkali metal oxide.
本発明の金属酸化物を電極材料として用いた場合に、低い電圧で酸化容量が発現する理由は明らかではないが、以下のように推定される。
アルカリ金属酸化物中に遷移金属原子が固溶した場合、電荷補償による格子欠陥が生じると推察される。アルカリ金属としてリチウム、遷移金属として鉄を用いた場合を例にとると、以下のとおりである。
（１）Ｆｅ／Ｌｉ＝０．２のとき
Ｌｉ２Ｏ ＋ ０．２Ｆｅ２Ｏ３ → １．６（Ｌｉ１．２５Ｆｅ０．２５□０．５）Ｏ
（２）Ｆｅ／Ｌｉ＝０．１のとき
Ｌｉ２Ｏ ＋ ０．１Ｆｅ２Ｏ３ → １．３（Ｌｉ１．５４Ｆｅ０．１５４□０．３１）Ｏ
□：格子欠陥
このようにアルカリ金属酸化物の結晶構造中に、多価金属である遷移金属を固溶させることで格子欠陥が生成し、この格子欠陥によって導電性が向上し低い過電圧で酸化電流が流れる、と推定される。
When the metal oxide of the present invention is used as an electrode material, the reason why the oxidation capacity is developed at a low voltage is not clear, but is estimated as follows.
When transition metal atoms are dissolved in the alkali metal oxide, it is presumed that lattice defects are caused by charge compensation. Taking the case where lithium is used as the alkali metal and iron is used as the transition metal as an example, it is as follows.
(1) When Fe / Li = 0.2, Li 2 O + 0.2Fe 2 O 3 → 1.6 (Li 1.25 Fe 0.25 □ 0.5 ) O
(2) When Fe / Li = 0.1, Li 2 O + 0.1 Fe 2 O 3 → 1.3 (Li 1.54 Fe 0.154 □ 0.31 ) O
□: Lattice defects In this way, lattice defects are generated by dissolving the transition metal, which is a polyvalent metal, in the crystal structure of the alkali metal oxide. The lattice defects improve the conductivity, and the oxidation current is reduced with low overvoltage Is estimated to flow.
本発明の遷移金属固溶アルカリ金属酸化物を構成するアルカリ金属原子としては、アルカリ金属に分類されるいずれの金属の原子であってもよく、１種又は２種以上を用いることができるが、リチウム、ナトリウム、カリウムのいずれかであることが好ましい。より好ましくは、リチウムである。アルカリ金属として、リチウムからなるものを用いると、本発明の金属酸化物が電極材料としてより好適なものとなる。 As an alkali metal atom constituting the transition metal solid solution alkali metal oxide of the present invention, any metal atom classified as an alkali metal may be used, and one or more kinds may be used. It is preferably any of lithium, sodium and potassium. More preferably, it is lithium. When an alkali metal made of lithium is used, the metal oxide of the present invention is more suitable as an electrode material.
本発明の遷移金属固溶アルカリ金属酸化物を構成する遷移金属原子としては、遷移金属に分類されるいずれの金属の原子であってもよく、１種又は２種以上を用いることができるが、第７〜１１族に属する遷移金属元素から選ばれる少なくとも１種の原子であることが好ましい。より好ましくは、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ等の周期表の第７〜１０族の遷移金属原子であり、更に好ましくは、Ｆｅ、Ｃｏのいずれかである。
The transition metal atom constituting the transition metal solid solution alkali metal oxide of the present invention may be any metal atom classified as a transition metal, and one or more kinds may be used. It is preferably at least one atom selected from transition metal elements belonging to
本発明の金属酸化物におけるアルカリ金属原子の数と遷移金属原子の数との比（遷移金属原子数／アルカリ金属原子数）は、０．００００１〜０．６であることが好ましい。このような範囲であると、本発明の金属酸化物が、遷移金属原子が固溶したことによる効果をより充分に発揮することができる。アルカリ金属原子の数と遷移金属原子の数との比は、より好ましくは、０．０００１〜０．４であり、更に好ましくは、０．００１〜０．３である。 The ratio of the number of alkali metal atoms to the number of transition metal atoms (number of transition metal atoms / number of alkali metal atoms) in the metal oxide of the present invention is preferably 0.00001 to 0.6. Within such a range, the metal oxide of the present invention can more fully exhibit the effect of the transition metal atom being dissolved. The ratio of the number of alkali metal atoms to the number of transition metal atoms is more preferably 0.0001 to 0.4, and still more preferably 0.001 to 0.3.
本発明の遷移金属固溶アルカリ金属酸化物は、下記式（１）；
［Ａ２−ｘＢｘ］Ｏ （１）
（式中、Ａは、アルカリ金属原子を表す。Ｂは、遷移金属原子を表す。ｘは、０＜ｘ＜２の数を表す。）で表されるものであることが好ましい。本発明の遷移金属固溶アルカリ金属酸化物は、逆蛍石構造のアルカリ金属酸化物のアルカリ金属サイトが遷移金属原子で置換された構造のものであることが好ましく、そのような構造の金属酸化物は、上記式（１）で表すことができる。
The transition metal solid solution alkali metal oxide of the present invention has the following formula (1):
[A 2-x B x] O (1)
(Wherein, A represents an alkali metal atom, B represents a transition metal atom, and x represents a number of 0 <x <2). The transition metal solid-solution alkali metal oxide of the present invention preferably has a structure in which the alkali metal site of the alkali metal oxide having a reverse fluorite structure is substituted with a transition metal atom. A thing can be represented by the said Formula (1).
上記式（１）においてＡで表されるアルカリ金属原子、Ｂで表される遷移金属原子は、１種の原子であってもよく、２種以上の原子であってもよい。Ａで表されるアルカリ金属原子、Ｂで表される遷移金属原子の具体例及び好ましい原子は、上述したアルカリ金属原子や遷移金属原子の具体例及び好ましい原子と同様である。
上記式（１）におけるｘは、０．００００２〜０．７５であることが好ましい。より好ましくは、０．０００２〜０．５７であり、更に好ましくは０．００２〜０．４６である。
In the above formula (1), the alkali metal atom represented by A and the transition metal atom represented by B may be one kind of atom or two or more kinds of atoms. Specific examples and preferred atoms of the alkali metal atom represented by A and transition metal atom represented by B are the same as the above-described specific examples and preferred atoms of the alkali metal atom and transition metal atom.
X in the above formula (1) is preferably 0.00002 to 0.75. More preferably, it is 0.0002-0.57, More preferably, it is 0.002-0.46.
本発明はまた、アルカリ金属酸化物の結晶構造内に遷移金属原子が固溶した構造を有する遷移金属固溶アルカリ金属酸化物を製造する方法であって、上記製造方法は、メカノケミカル処理によりアルカリ金属酸化物の結晶構造内に遷移金属原子を固溶させる工程を含む遷移金属固溶アルカリ金属酸化物の製造方法でもある。
このような製造方法が本発明の遷移金属固溶アルカリ金属酸化物を製造する方法として簡便であり好ましい。
本発明の遷移金属固溶アルカリ金属酸化物の製造方法は、メカノケミカル処理によりアルカリ金属酸化物の結晶構造内に遷移金属原子を固溶させる工程（以下においては、メカノケミカル処理工程ともいう）を含む限り、その他の工程を含んでいてもよい。
The present invention is also a method for producing a transition metal solid-solution alkali metal oxide having a structure in which transition metal atoms are dissolved in the crystal structure of the alkali metal oxide, wherein the production method comprises an alkali by mechanochemical treatment. It is also a method for producing a transition metal solid solution alkali metal oxide including a step of dissolving a transition metal atom in the crystal structure of the metal oxide.
Such a production method is simple and preferable as a method for producing the transition metal solid-solution alkali metal oxide of the present invention.
The method for producing a transition metal solid-solution alkali metal oxide of the present invention comprises a step of dissolving a transition metal atom in the crystal structure of the alkali metal oxide by a mechanochemical treatment (hereinafter also referred to as a mechanochemical treatment step). Other steps may be included as long as they are included.
上記メカノケミカル処理の具体的な方法は、メカノケミカル反応を起こす方法であれば特に制限されず、遊星ボールミル処理、ビーズミル処理、ボールミル処理やカッターミル処理、ディスクミル処理、スタンプミル処理、ハンマーミル処理、ジェットミル処理等のメカノケミカル反応を起こしうるミリング操作のいずれか１つ又は複数の方法が挙げられる。これらの中でも、メカノケミカル処理を充分に行う点から、遊星ボールミル処理が特に好ましい。 The specific method of the mechanochemical treatment is not particularly limited as long as it causes a mechanochemical reaction. Planetary ball mill treatment, bead mill treatment, ball mill treatment or cutter mill treatment, disc mill treatment, stamp mill treatment, hammer mill treatment. Any one or a plurality of milling operations capable of causing a mechanochemical reaction such as jet mill treatment may be mentioned. Among these, the planetary ball mill treatment is particularly preferable because the mechanochemical treatment is sufficiently performed.
上記メカノケミカル処理を遊星ボールミル処理により行う場合、湿式、乾式のいずれで行ってもよいが、乾式で行うことが好ましい。
また、遊星ボールミル処理に用いる粉砕メディアは、質量の大きいものを用いることが好ましく、具体的には、０．００００１ｇ以上のものが好ましい。より好ましくは、０．００１ｇ以上のものであり、更に好ましくは、０．１ｇ以上のものである。また、粉砕メディアは、通常、５００００ｇ以下のものを用いる。
粉砕メディアとしては、０．０１〜５００ｍｍφの、ジルコニアボール、メノウボール、アルミナボール、タングステンカーバイドボール、鉄球、ステンレス球等を用いることができる。
遊星ボールミル処理に用いる粉砕メディアは、遊星ボールミル処理に用いる容器の体積と遊星ボールミルに供される化合物の量を考慮し、メカノケミカル処理が充分に行われるよう、適宜最適な数を選択して用いればよい。
When the mechanochemical treatment is performed by a planetary ball mill treatment, it may be performed either by a wet method or a dry method, but is preferably performed by a dry method.
The grinding media used for the planetary ball mill treatment are preferably those having a large mass, specifically 0.00001 g or more. More preferably, it is 0.001 g or more, and still more preferably 0.1 g or more. In addition, as the grinding media, those having 50000 g or less are usually used.
As the grinding media, zirconia balls, agate balls, alumina balls, tungsten carbide balls, iron balls, stainless balls, etc. having a diameter of 0.01 to 500 mmφ can be used.
The grinding media used for the planetary ball mill treatment should be selected by appropriately selecting the optimum number so that the mechanochemical treatment is sufficiently performed in consideration of the volume of the container used for the planetary ball mill treatment and the amount of the compound used for the planetary ball mill. That's fine.
更に、遊星ボールミル処理の回転数は、高いほうが好ましく、具体的には、１０ｒｐｍ以上の回転数が好ましい。より好ましくは、５０ｒｐｍ以上の回転数であり、更に好ましくは、１００ｒｐｍ以上の回転数である。また、遊星ボールミル処理の回転数は、通常、１０００００ｒｐｍ以下で行われる。
このように、質量の大きい粉砕メディアを用い、高回転数で遊星ボールミル処理を行うことにより、メカノケミカル処理を充分に進めることができ、遷移金属固溶アルカリ金属酸化物をより高い収率で得ることができる。
Furthermore, the rotation speed of the planetary ball mill treatment is preferably higher, and specifically, the rotation speed of 10 rpm or more is preferable. More preferably, the number of rotations is 50 rpm or more, and still more preferably the number of rotations is 100 rpm or more. Further, the rotational speed of the planetary ball mill treatment is usually 100000 rpm or less.
Thus, by using the grinding media having a large mass and performing the planetary ball mill treatment at a high rotational speed, the mechanochemical treatment can be sufficiently advanced, and a transition metal solid solution alkali metal oxide can be obtained in a higher yield. be able to.
上記ミリング操作を行う雰囲気は特に制限されず、空気下、不活性ガス下等、いずれの雰囲気下で行ってもよいが、不活性ガス雰囲気下で行うことが不純物生成抑制の点から好ましい。不活性ガスとしては、ヘリウム、窒素、アルゴン等を用いることができる。
上記ミリング操作を行う時間は、０．１〜１００００００００時間が好ましい。より好ましくは、０．２〜１０００００００時間であり、更に好ましくは、０．３〜１０００００時間である。
The atmosphere in which the milling operation is performed is not particularly limited, and may be performed in any atmosphere such as air or inert gas, but is preferably performed in an inert gas atmosphere from the viewpoint of suppression of impurity generation. As the inert gas, helium, nitrogen, argon or the like can be used.
The time for performing the milling operation is preferably 0.1 to 100000000 hours. More preferably, it is 0.2-10000000 hours, More preferably, it is 0.3-100000 hours.
上記メカノケミカル処理工程に供されるアルカリ金属成分、遷移金属成分は、それぞれ金属の単体であってもよく、酸化物等の化合物であってもよいが、アルカリ金属成分、遷移金属成分ともに酸化物が好ましい。すなわち、上記メカノケミカル処理工程は、アルカリ金属酸化物と遷移金属酸化物とをメカノケミカル処理する工程であることが好ましい。アルカリ金属酸化物と遷移金属酸化物とを用いることで、アルカリ金属酸化物の結晶構造内に遷移金属原子が固溶した構造の化合物をより高い収率で製造することができる。 The alkali metal component and the transition metal component used in the mechanochemical treatment step may be a single metal or a compound such as an oxide, but both the alkali metal component and the transition metal component are oxides. Is preferred. That is, the mechanochemical treatment step is preferably a step of mechanochemical treatment of alkali metal oxide and transition metal oxide. By using an alkali metal oxide and a transition metal oxide, a compound having a structure in which transition metal atoms are dissolved in the crystal structure of the alkali metal oxide can be produced in a higher yield.
上記メカノケミカル処理工程に供するアルカリ金属成分と遷移金属成分との割合は、アルカリ金属成分に含まれるアルカリ金属原子数と遷移金属成分に含まれる遷移金属原子の数との比（遷移金属原子数／アルカリ金属原子数）が、０．００００１〜０．６となるような割合であることが好ましい。このような割合とすることで、アルカリ金属酸化物の結晶構造内に遷移金属原子が好ましい割合で固溶した構造の金属酸化物を得ることができる。より好ましくは、上記比が０．０００１〜０．４なるような割合であることであり、更に好ましくは、０．００１〜０．３なるような割合であることである。 The ratio of the alkali metal component and the transition metal component used for the mechanochemical treatment step is the ratio of the number of alkali metal atoms contained in the alkali metal component to the number of transition metal atoms contained in the transition metal component (number of transition metal atoms / The ratio of the number of alkali metal atoms) is preferably 0.00001 to 0.6. By setting such a ratio, it is possible to obtain a metal oxide having a structure in which transition metal atoms are dissolved in a preferable ratio in the crystal structure of the alkali metal oxide. More preferably, the ratio is such that the ratio is 0.0001 to 0.4, and still more preferably the ratio is 0.001 to 0.3.
本発明の遷移金属固溶アルカリ金属酸化物は、遷移金属を固溶していないアルカリ金属酸化物に比べて、非常に低い電圧で酸化電流が流れることから、この化合物を用いて電極を形成した場合、低い電圧で充電することが可能となる。このため、本発明の遷移金属固溶アルカリ金属酸化物は、電極材料として好適な化合物である。また、この化合物は、酸素原子の含有割合が高いことから、酸素発生材料（酸素貯蔵物質）としての応用も期待される有用な化合物である。
このような、本発明の遷移金属固溶アルカリ金属酸化物を含む電極材料もまた、本発明の１つである。また、本発明の電極材料を用いて形成される電極、及び、該電極を用いて構成される電池もまた、本発明の１つである。
更に、このような、本発明の遷移金属固溶アルカリ金属酸化物を含む酸素発生材料もまた、本発明の１つである。
In the transition metal solid-solution alkali metal oxide of the present invention, an oxidation current flows at a very low voltage as compared with an alkali metal oxide not containing a transition metal. Therefore, an electrode was formed using this compound. In this case, it is possible to charge at a low voltage. For this reason, the transition metal solid solution alkali metal oxide of the present invention is a compound suitable as an electrode material. In addition, since this compound has a high oxygen atom content, it is a useful compound that is expected to be used as an oxygen generating material (oxygen storage material).
Such an electrode material containing the transition metal solid solution alkali metal oxide of the present invention is also one aspect of the present invention. Moreover, the electrode formed using the electrode material of this invention and the battery comprised using this electrode are also one of this invention.
Furthermore, such an oxygen generating material containing the transition metal solid solution alkali metal oxide of the present invention is also one aspect of the present invention.
本発明の電極材料（電極合剤）は、本発明の遷移金属固溶アルカリ金属酸化物を必須成分とし、導電助剤、有機化合物を含んで構成されることが好ましく、その他の成分を必要に応じて含んでいてもよい。 The electrode material (electrode mixture) of the present invention preferably comprises the transition metal solid solution alkali metal oxide of the present invention as an essential component, and includes a conductive additive and an organic compound, and requires other components. It may be included accordingly.
上記導電助剤としては、電子材料となり得る導電性を有する物質であることが好ましく、具体的には、金属、導電性セラミックス、炭素材料からなることが好ましい。金属としては、ニッケル粉、アルミニウム粉、亜鉛粉、金粉、メソポーラス金等が挙げられる。炭素材料（導電性カーボン）としては、黒鉛、アモルファス炭素、カーボンナノフォーム、活性炭、グラフェン、ナノグラフェン、グラフェンナノリボン、フラーレン、カーボンブラック、ファイバー状カーボン、カーボンナノチューブ、カーボンナノホーン、ケッチェンブラック、アセチレンブラック、炭素繊維、気相成長炭素繊維等が挙げられる。炭素材料としては、これらの中でも、グラフェン、ファイバー状カーボン、カーボンナノチューブ、アセチレンブラック、炭素繊維、気相成長炭素繊維が好ましい。上記導電助剤は、より好ましくは、グラフェン、ファイバー状カーボン、カーボンナノチューブ、アセチレンブラック、金属である。
上記導電助剤は、電極における導電性を向上させる作用を有するものであり、１種又は２種以上を用いることが出来る。
The conductive aid is preferably a conductive substance that can be used as an electronic material. Specifically, the conductive assistant is preferably made of a metal, conductive ceramic, or carbon material. Examples of the metal include nickel powder, aluminum powder, zinc powder, gold powder, and mesoporous gold. Carbon materials (conductive carbon) include graphite, amorphous carbon, carbon nanofoam, activated carbon, graphene, nanographene, graphene nanoribbon, fullerene, carbon black, fibrous carbon, carbon nanotube, carbon nanohorn, ketjen black, acetylene black, Examples thereof include carbon fiber and vapor grown carbon fiber. Among these, graphene, fibrous carbon, carbon nanotube, acetylene black, carbon fiber, and vapor grown carbon fiber are preferable as the carbon material. More preferably, the conductive assistant is graphene, fibrous carbon, carbon nanotube, acetylene black, or metal.
The said conductive support agent has the effect | action which improves the electroconductivity in an electrode, and can use 1 type (s) or 2 or more types.
上記導電助剤の配合量としては、電極材料（電極合剤）中の遷移金属固溶アルカリ金属酸化物１００質量％に対して、０．００１〜９０質量％であることが好ましい。導電助剤の配合量がこのような範囲であると、本発明の電極材料から形成される電極がより良好な電池性能を発揮することとなる。より好ましくは、０．０１〜７０質量％であり、更に好ましくは、０．０５〜５０質量％である。 As a compounding quantity of the said conductive support agent, it is preferable that it is 0.001-90 mass% with respect to 100 mass% of transition metal solid solution alkali metal oxides in an electrode material (electrode mixture). When the blending amount of the conductive auxiliary is within such a range, an electrode formed from the electrode material of the present invention will exhibit better battery performance. More preferably, it is 0.01-70 mass%, More preferably, it is 0.05-50 mass%.
上記有機化合物としては、有機化合物の他、有機化合物塩を例示することができ、１種又は２種以上を用いることができる。例えば、ポリ（メタ）アクリル酸含有ポリマー、ポリ（メタ）アクリル酸塩含有ポリマー、ポリアクリロニトリル含有ポリマー、ポリアクリルアミド含有ポリマー、ポリ塩化ビニル含有ポリマー、ポリビニルアルコール含有ポリマー、ポリエチレンオキシド含有ポリマー、ポリプロピレンオキシド含有ポリマー、ポリブテンオキシド含有ポリマー、ポリエチレン含有ポリマー、ポリプロピレン含有ポリマー、ポリブテン含有ポリマー、ポリヘキセン含有ポリマー、ポリオクテン含有ポリマー、ポリブタジエン含有ポリマー、ポリイソプレン含有ポリマー、アナルゲン、ベンゼン、トリヒドロキシベンゼン、トルエン、ピペロンアルデヒド、カーボワックス、カルバゾール、セルロース、酢酸セルロース、ヒドロキシアルキルセルロース、カルボキシメチルセルロース、デキストリン、ポリアセチレン含有ポリマー、ポリエチレンイミン含有ポリマー、ポリアミド含有ポリマー、ポリスチレン含有ポリマー、ポリテトラフルオロエチレン含有ポリマー、ポリフッ化ビニリデン含有ポリマー、ポリペンタフルオロエチレン含有ポリマー、ポリ（無水）マレイン酸含有ポリマー、ポリマレイン酸塩含有ポリマー、ポリ（無水）イタコン酸含有ポリマー、ポリイタコン酸塩含有ポリマー、陽イオン・陰イオン交換膜等に使用されるイオン交換性重合体、環化重合体、スルホン酸塩、スルホン酸塩含有ポリマー、第四級アンモニウム塩、第四級アンモニウム塩含有ポリマー、第四級ホスホニウム塩、第四級ホスホニウム塩アンモニウムポリマー等が挙げられる。 As said organic compound, organic compound salt can be illustrated other than an organic compound, 1 type (s) or 2 or more types can be used. For example, poly (meth) acrylic acid-containing polymer, poly (meth) acrylate-containing polymer, polyacrylonitrile-containing polymer, polyacrylamide-containing polymer, polyvinyl chloride-containing polymer, polyvinyl alcohol-containing polymer, polyethylene oxide-containing polymer, polypropylene oxide-containing Polymer, polybutene oxide-containing polymer, polyethylene-containing polymer, polypropylene-containing polymer, polybutene-containing polymer, polyhexene-containing polymer, polyoctene-containing polymer, polybutadiene-containing polymer, polyisoprene-containing polymer, analgen, benzene, trihydroxybenzene, toluene, piperonaldehyde, Carbowax, carbazole, cellulose, cellulose acetate, hydroxyalkyl cellulose, cal Xymethylcellulose, dextrin, polyacetylene-containing polymer, polyethyleneimine-containing polymer, polyamide-containing polymer, polystyrene-containing polymer, polytetrafluoroethylene-containing polymer, polyvinylidene fluoride-containing polymer, polypentafluoroethylene-containing polymer, poly (anhydride) maleic acid-containing polymer , Polymaleate-containing polymers, poly (anhydride) itaconic acid-containing polymers, polyitaconate-containing polymers, ion-exchangeable polymers used for cation / anion exchange membranes, cyclized polymers, sulfonates, sulfones Examples thereof include acid salt-containing polymers, quaternary ammonium salts, quaternary ammonium salt-containing polymers, quaternary phosphonium salts, and quaternary phosphonium salt ammonium polymers.
上記有機化合物、有機化合物塩の配合量としては、電極材料中の遷移金属固溶アルカリ金属酸化物１００質量％に対して、０．０１〜５０質量％であることが好ましい。これら有機化合物、有機化合物塩の配合量がこのような範囲であると、本発明の電極材料から形成される電極が、より良好な電池性能を発揮することとなる。より好ましくは、０．０１〜４５質量％であり、更に好ましくは、０．１〜４０質量％である。 The blending amount of the organic compound and the organic compound salt is preferably 0.01 to 50% by mass with respect to 100% by mass of the transition metal solid solution alkali metal oxide in the electrode material. When the compounding amount of these organic compounds and organic compound salts is within such a range, the electrode formed from the electrode material of the present invention will exhibit better battery performance. More preferably, it is 0.01-45 mass%, More preferably, it is 0.1-40 mass%.
本発明の電極材料は、遷移金属固溶アルカリ金属酸化物、導電助剤、有機化合物以外の成分を含む場合、その配合量は、電極材料中の遷移金属固溶アルカリ金属酸化物１００質量％に対して、０．０１〜１０質量％であることが好ましい。より好ましくは、０．０５〜７質量％であり、更に好ましくは、０．１〜５質量％である。 When the electrode material of the present invention contains components other than the transition metal solid solution alkali metal oxide, the conductive additive, and the organic compound, the blending amount thereof is 100% by mass of the transition metal solid solution alkali metal oxide in the electrode material. On the other hand, it is preferable that it is 0.01-10 mass%. More preferably, it is 0.05-7 mass%, More preferably, it is 0.1-5 mass%.
本発明の電極は、遷移金属固溶アルカリ金属酸化物を必要により水及び／又は有機溶媒と、導電助剤や有機化合物と共に混練し、ペースト状としたものをアルミ箔等の金属箔やニッケルメッシュ等の金属メッシュ上に、できる限り膜厚が一定になるように塗工して乾燥する方法や、遷移金属固溶アルカリ金属酸化物、導電助剤、有機化合物を混練して粘土状にし、これを金属箔や金属メッシュに圧着する方法を用いることができる。
本発明の電極は、正極、負極のいずれに用いてもよいが、正極として用いることが好ましい。したがって、本発明の電極材料は、正極材料として用いられることが好ましい。
The electrode of the present invention is a metal foil such as an aluminum foil or a nickel mesh obtained by kneading a transition metal solid solution alkali metal oxide together with water and / or an organic solvent and a conductive additive or an organic compound as necessary. On a metal mesh such as a method of coating and drying so that the film thickness is as constant as possible, or by kneading a transition metal solid solution alkali metal oxide, a conductive additive and an organic compound into a clay, It is possible to use a method of pressure bonding to a metal foil or a metal mesh.
The electrode of the present invention may be used as either a positive electrode or a negative electrode, but is preferably used as a positive electrode. Therefore, the electrode material of the present invention is preferably used as a positive electrode material.
本発明の電極を正極として用いた場合、負極としては、リチウム、ナトリウム、マグネシウム、カルシウム等のアルカリ金属、アルカリ土類金属、又はアルカリ金属やアルカリ土類金属を含有する化合物、あるいはアルミニウムやアルミニウム含有化合物、錫、チタン、ホウ素、窒素、ケイ素、及び、炭素を用いることができる。上記炭素としては、例えば、黒鉛、アモルファス炭素、カーボンナノフォーム、活性炭、グラフェン、ナノグラフェン、グラフェンナノリボン、フラーレン、カーボンブラック、ファイバー状カーボン、カーボンナノチューブ、カーボンナノホーン、ケッチェンブラック、アセチレンブラック、炭素繊維、気相成長炭素繊維等が挙げられる。これらの中でも、黒鉛、グラフェン、ファイバー状カーボン、カーボンナノチューブ、アセチレンブラック、が好ましい。より好ましくは、黒鉛、グラフェン、ファイバー状カーボン、カーボンナノチューブ、アセチレンブラック、炭素繊維、気相成長炭素繊維である。 When the electrode of the present invention is used as a positive electrode, the negative electrode includes an alkali metal such as lithium, sodium, magnesium, calcium, an alkaline earth metal, or a compound containing an alkali metal or an alkaline earth metal, or aluminum or aluminum Compounds, tin, titanium, boron, nitrogen, silicon, and carbon can be used. Examples of the carbon include graphite, amorphous carbon, carbon nanofoam, activated carbon, graphene, nanographene, graphene nanoribbon, fullerene, carbon black, fibrous carbon, carbon nanotube, carbon nanohorn, ketjen black, acetylene black, carbon fiber, Examples include vapor grown carbon fiber. Among these, graphite, graphene, fibrous carbon, carbon nanotube, and acetylene black are preferable. More preferred are graphite, graphene, fibrous carbon, carbon nanotube, acetylene black, carbon fiber, and vapor grown carbon fiber.
本発明の電池を構成する電解液としては、特に制限されないが、例えば、有機溶剤系電解液としては、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、γ−ブチロラクトン、１，２−ジメトキシエタン、１，２−ジエトキシエタン、ジメトキシメタン、ジエトキシメタン、アセトニトリル、ジメチルスルホキシド、スルホラン、フッ素基含有カーボネート、フッ素基含有エーテル、イオン性液体、ゲル化合物含有電解液、ポリマー含有電解液等が好ましく、水系電解液としては、水酸化カリウム水溶液、水酸化ナトリウム水溶液、水酸化リチウム水溶液等が挙げられる。電解液は、上記１種又は２種以上使用してもよい。無機固体電解質を使用してもよい。
本発明の電池を構成する電解質としては、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＮ（ＳＯ２Ｆ）２、ＬｉＮ（ＳＯ２ＣＦ３）２、ＬｉＮ（ＳＯ２Ｃ２Ｆ５）２、Ｌｉ（ＢＣ４Ｏ８）、ＬｉＦ、ＬｉＢ（ＣＮ）４等が挙げられる。
Although it does not restrict | limit especially as electrolyte solution which comprises the battery of this invention, For example, as organic-solvent type electrolyte solution, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, (gamma) -butyrolactone, 1, 2 -Dimethoxyethane, 1,2-diethoxyethane, dimethoxymethane, diethoxymethane, acetonitrile, dimethyl sulfoxide, sulfolane, fluorine group-containing carbonate, fluorine group-containing ether, ionic liquid, gel compound-containing electrolyte, polymer-containing electrolyte The aqueous electrolyte includes potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, lithium hydroxide aqueous solution and the like. You may use 1 type, or 2 or more types of said electrolyte solution. An inorganic solid electrolyte may be used.
Examples of the electrolyte constituting the battery of the present invention include LiPF 6 , LiBF 4 , LiClO 4 , LiN (SO 2 F) 2 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , Li ( BC 4 O 8 ), LiF, LiB (CN) 4 and the like.
本発明の電池がセパレータを使用する場合、ポリエチレン、ポリプロピレン、ポリテトラフルオロエチレン、ポリフッ化ビニリデン、セルロース、酢酸セルロース、ヒドロキシアルキルセルロース、カルボキシメチルセルロース、ポリビニルアルコール、セロファン、ポリスチレン、ポリアクリロニトリル、ポリアクリルアミド、ポリ塩化ビニル、ポリアミド、ビニロン、ポリ(メタ)アクリル酸等のマイクロポアを有する高分子量体やそれら共重合体、ゲル化合物、イオン交換膜性重合体やそれら共重合体、環化重合体やそれら共重合体、ポリ（メタ）アクリル酸塩含有ポリマーやそれら共重合体、スルホン酸塩含有ポリマーやそれら共重合体、第四級アンモニウム塩含有ポリマーやそれら共重合体、第四級ホスホニウム塩含有ポリマーやそれら共重合体等を用いることができる。 When the battery of the present invention uses a separator, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, cellulose, cellulose acetate, hydroxyalkyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, cellophane, polystyrene, polyacrylonitrile, polyacrylamide, poly High molecular weight polymers having micropores such as vinyl chloride, polyamide, vinylon, poly (meth) acrylic acid, copolymers thereof, gel compounds, ion exchange membrane polymers, copolymers thereof, cyclized polymers and copolymers thereof. Polymers, poly (meth) acrylate-containing polymers and their copolymers, sulfonate-containing polymers and their copolymers, quaternary ammonium salt-containing polymers and their copolymers, quaternary phosphonium salt-containing polymers, So It can be used et copolymer.
本発明の遷移金属固溶アルカリ金属酸化物は、上述の構成よりなり、アルカリ金属酸化物と比較して非常に低い電圧で酸化電流が流れることから、電極材料として好適であり、また、酸素原子の含有割合が高いことから、酸素発生材料（酸素貯蔵物質）としての応用も期待される有用な化合物である。
また、本発明の遷移金属固溶アルカリ金属酸化物の製造方法は、このような遷移金属固溶アルカリ金属酸化物を簡便に製造することができる有用な方法である。
The transition metal solid solution alkali metal oxide of the present invention has the above-described configuration, and an oxidation current flows at a very low voltage compared to the alkali metal oxide. Is a useful compound that is expected to be used as an oxygen generating material (oxygen storage material).
In addition, the method for producing a transition metal solid solution alkali metal oxide of the present invention is a useful method for easily producing such a transition metal solid solution alkali metal oxide.
以下に実施例を掲げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「部」は「重量部」を、「％」は「質量％」を意味するものとする。 The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.
（ＸＲＤ測定）
ＸＲＤ測定は、全自動水平型Ｘ線回折装置（リガク社製、ＳＭＡＲＴ ＬＡＢ）を用いて、以下の条件により行った。
ＣｕＫα１線：０．１５４０６ｎｍ
走査範囲：１０°−９０°
Ｘ線出力設定：４５ｋＶ−２００ｍＡ
ステップサイズ：０．０２０°
スキャン速度：０．５°ｍｉｎ−１−４°ｍｉｎ−１
なお、ＸＲＤ測定は、試料をグローブボックス中にて気密試料台に装填することにより、不活性雰囲気を保った状態で行った。
(XRD measurement)
XRD measurement was performed under the following conditions using a fully automatic horizontal X-ray diffractometer (manufactured by Rigaku Corporation, SMART LAB).
CuKα1 line: 0.15406 nm
Scanning range: 10 ° -90 °
X-ray output setting: 45kV-200mA
Step size: 0.020 °
Scan speed: 0.5 ° min −1 -4 ° min −1
The XRD measurement was performed in a state where an inert atmosphere was maintained by loading the sample on an airtight sample stage in a glove box.
比較例１（Ｌｉ２Ｏ微粉末の調製工程）
酸化リチウム（株式会社高純度化学研究所製）２．２４ｇを遊星ボールミル用のポットに入れ、遊星ボールミル混合（混合条件；１０ｍｍφのジルコニアボール２５個を用いて回転数６００ｒｐｍにて６０時間処理）を行った。作業は全てアルゴン置換された水分濃度１ｐｐｍ以下のグローブボックス中で行った。得られた固体粉末のＸＲＤ測定結果を図１に示す。併せて遊星ボールミル混合前の酸化リチウムの測定結果も示す。得られた固体粉末は遊星ボールミル前と比較して酸化リチウムに帰属されるピークが平坦化しており微粉化された酸化リチウムであった。
Comparative Example 1 (Li 2 O fine powder preparation process)
2.24 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) is put in a pot for a planetary ball mill, and mixed with a planetary ball mill (mixing conditions; treated with 25 10 mmφ zirconia balls for 60 hours at a rotation speed of 600 rpm). went. All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon. The XRD measurement result of the obtained solid powder is shown in FIG. In addition, the measurement results of lithium oxide before mixing with the planetary ball mill are also shown. The obtained solid powder was a finely divided lithium oxide in which the peak attributed to lithium oxide was flattened as compared with that before the planetary ball mill.
実施例１（Ｆｅ固溶Ｌｉ２Ｏ微粉末の調製工程）
酸化リチウム（株式会社高純度化学研究所製）２．７６ｇと、α−酸化鉄（和光純薬工業社製）０．５８ｇとを遊星ボールミル用のポットに入れ、遊星ボールミル混合（混合条件；１０ｍｍφのジルコニアボール２５個を用いて回転数６００ｒｐｍにて６０時間処理）を行った。作業は全てアルゴン置換された水分濃度１ｐｐｍ以下のグローブボックス中で行った。得られた固体粉末のＸＲＤ測定結果を図２に示す。併せて遊星ボールミル混合前のα−酸化鉄の測定結果も示す。得られた固体粉末は遊星ボールミル前と比較してα−酸化鉄に帰属されるピークが消失しており、鉄原子が酸化リチウムの結晶構造内に固溶した微粉化された酸化リチウムであった。
Example 1 (Preparation process of Fe solid solution Li 2 O fine powder)
2.76 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) and 0.58 g of α-iron oxide (manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a pot for a planetary ball mill and mixed with a planetary ball mill (mixing conditions; 10 mmφ) For 60 hours at a rotational speed of 600 rpm). All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon. The XRD measurement result of the obtained solid powder is shown in FIG. In addition, the measurement results of α-iron oxide before mixing with the planetary ball mill are also shown. The obtained solid powder was a finely divided lithium oxide in which the peak attributed to α-iron oxide disappeared compared to before the planetary ball mill, and the iron atoms were dissolved in the crystal structure of lithium oxide. .
実施例２（Ｆｅ固溶Ｌｉ２Ｏ微粉末の調製工程）
酸化リチウム（株式会社高純度化学研究所製）１．９９ｇと、α−酸化鉄（和光純薬工業社製）２．０８ｇとを遊星ボールミル用のポットに入れ、遊星ボールミル混合（混合条件；１０ｍｍφのジルコニアボール２５個を用いて回転数６００ｒｐｍにて６０時間処理）を行った。作業は全てアルゴン置換された水分濃度１ｐｐｍ以下のグローブボックス中で行った。得られた固体粉末のＸＲＤ測定結果を図３に示す。得られた固体粉末は遊星ボールミル前と比較してα−酸化鉄に帰属されるピークが消失しており、鉄原子が酸化リチウムの結晶構造内に固溶した微粉化された酸化リチウムとＬｉＦｅＯ２との混合物であった。
Example 2 (Preparation process of Fe solid solution Li 2 O fine powder)
1.99 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) and 2.08 g of α-iron oxide (manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a pot for a planetary ball mill, and mixed with a planetary ball mill (mixing conditions: 10 mmφ) For 60 hours at a rotational speed of 600 rpm). All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon. The XRD measurement result of the obtained solid powder is shown in FIG. In the obtained solid powder, the peak attributed to α-iron oxide disappeared compared with that before the planetary ball mill, and finely divided lithium oxide in which iron atoms were dissolved in the crystal structure of lithium oxide and LiFeO 2. And a mixture.
実施例３（Ｆｅ、Ｃｏ固溶Ｌｉ２Ｏ微粉末の調製工程）
酸化リチウム（株式会社高純度化学研究所製）２．４７ｇと、α−酸化鉄（和光純薬工業社製）０．３２ｇ及び酸化コバルト（Ｃｏ３Ｏ４、和光純薬工業社製）０．３３ｇとを遊星ボールミル用のポットに入れ、遊星ボールミル混合（混合条件；１０ｍｍφのジルコニアボール２５個を用いて回転数６００ｒｐｍにて１００時間処理）を行った。作業は全てアルゴン置換された水分濃度１ｐｐｍ以下のグローブボックス中で行った。得られた固体粉末のＸＲＤ測定結果を図４に示す。併せて遊星ボールミル混合前の酸化コバルトの測定結果も示す。得られた固体粉末は遊星ボールミル前と比較してα−酸化鉄と酸化コバルトに帰属されるピークがそれぞれ消失しており、鉄原子とコバルト原子とが酸化リチウムの結晶構造内に固溶した微粉化された酸化リチウムであった。
Example 3 (Preparation process of Fe, Co solid solution Li 2 O fine powder)
2.47 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.), 0.32 g of α-iron oxide (manufactured by Wako Pure Chemical Industries, Ltd.) and cobalt oxide (Co 3 O 4 , manufactured by Wako Pure Chemical Industries, Ltd.) 0. 33 g was put into a pot for a planetary ball mill, and planetary ball mill mixing (mixing conditions; treatment using 100 10 mmφ zirconia balls at 100 rpm for 100 hours) was performed. All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon. The XRD measurement result of the obtained solid powder is shown in FIG. In addition, the measurement results of cobalt oxide before planetary ball mill mixing are also shown. The obtained solid powder is a fine powder in which peaks attributed to α-iron oxide and cobalt oxide have disappeared compared to before the planetary ball mill, and iron atoms and cobalt atoms are dissolved in the crystal structure of lithium oxide. Lithium oxide.
実施例４（Ｆｅ、Ｃｏ固溶Ｌｉ２Ｏ微粉末の調製工程）
酸化リチウム（株式会社高純度化学研究所製）２．４６ｇと、α−酸化鉄（和光純薬工業社製）０．６５ｇ及び酸化コバルト（Ｃｏ３Ｏ４、和光純薬工業社製）０．６８ｇとを遊星ボールミル用のポットに入れ、遊星ボールミル混合（混合条件；１０ｍｍφのジルコニアボール２５個を用いて回転数６００ｒｐｍにて１００時間処理）を行った。作業は全てアルゴン置換された水分濃度１ｐｐｍ以下のグローブボックス中で行った。得られた固体粉末のＸＲＤ測定結果を図５に示す。得られた固体粉末は遊星ボールミル前と比較してα−酸化鉄と酸化コバルトに帰属されるピークがそれぞれ消失しており、鉄原子とコバルト原子とが酸化リチウムの結晶構造に固溶した微粉化された酸化リチウムであった。
Example 4 (Preparation process of Fe, Co solid solution Li 2 O fine powder)
2.46 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.), 0.65 g of α-iron oxide (manufactured by Wako Pure Chemical Industries) and cobalt oxide (Co 3 O 4 , manufactured by Wako Pure Chemical Industries) 0. 68 g was put in a pot for a planetary ball mill, and planetary ball mill mixing (mixing conditions; treatment using 100 zirconia balls of 25 mm of 10 mmφ for 100 hours at a rotation speed of 600 rpm) was performed. All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon. The XRD measurement result of the obtained solid powder is shown in FIG. The resulting solid powder has lost the peaks attributed to α-iron oxide and cobalt oxide, respectively, compared to before the planetary ball mill, and pulverized with iron and cobalt atoms dissolved in the crystal structure of lithium oxide. Was lithium oxide.
実施例５（Ｆｅ、Ｃｏ固溶Ｌｉ２Ｏ微粉末の調製工程）
酸化リチウム（株式会社高純度化学研究所製）２．６２ｇと、α−酸化鉄（和光純薬工業社製）１．３８ｇ及び酸化コバルト（Ｃｏ３Ｏ４、和光純薬工業社製）１．３６ｇとを遊星ボールミル用のポットに入れ、遊星ボールミル混合（混合条件；１０ｍｍφのジルコニアボール２５個を用いて回転数６００ｒｐｍにて６０時間処理）を行った。作業は全てアルゴン置換された水分濃度１ｐｐｍ以下のグローブボックス中で行った。得られた固体粉末のＸＲＤ測定結果を図６に示す。得られた固体粉末は遊星ボールミル前と比較してα−酸化鉄と酸化コバルトに帰属されるピークがそれぞれ消失しており、鉄原子とコバルト原子とが酸化リチウムの結晶構造内に固溶した微粉化された酸化リチウムとＬｉＦｅＯ２の混合物であった。
Example 5 (Process for preparing Fe, Co solid solution Li 2 O fine powder)
Lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) 2.62 g, α-iron oxide (manufactured by Wako Pure Chemical Industries, Ltd.) 1.38 g and cobalt oxide (Co 3 O 4 , manufactured by Wako Pure Chemical Industries, Ltd.) 1. 36 g was put into a pot for a planetary ball mill, and planetary ball mill mixing (mixing conditions; treatment using 60 10 mmφ zirconia balls for 60 hours at a rotation speed of 600 rpm) was performed. All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon. The XRD measurement result of the obtained solid powder is shown in FIG. The obtained solid powder is a fine powder in which peaks attributed to α-iron oxide and cobalt oxide have disappeared compared to before the planetary ball mill, and iron atoms and cobalt atoms are dissolved in the crystal structure of lithium oxide. It was a mixture of oxidized lithium oxide and LiFeO 2 .
比較例２（Ｌｉ２Ｏ正極合剤及び正極の調製）
比較例１で得られたＬｉ２Ｏ微粉末９３ｍｇ、導電助剤としてのアセチレンブラック１０６ｍｇ、結着剤としてのポリテトラフルオロエチレン粉末１４ｍｇをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を６０ｍｇのアルミニウムメッシュに圧着して正極とした。
Comparative Example 2 (Preparation of Li 2 O positive electrode mixture and positive electrode)
93 mg of Li 2 O fine powder obtained in Comparative Example 1, 106 mg of acetylene black as a conductive additive, and 14 mg of polytetrafluoroethylene powder as a binder were mixed in an agate mortar, processed into a clay shape, and mixed with a positive electrode Got. The obtained positive electrode mixture was pressure-bonded to a 60 mg aluminum mesh to obtain a positive electrode.
実施例６（Ｆｅ固溶Ｌｉ２Ｏ正極合剤及び正極の調製）
Ｌｉ２Ｏ微粉末の代わりに実施例１で得られたＦｅ固溶Ｌｉ２Ｏ微粉末を使用した以外は比較例２と同様の手法でＦｅ固溶Ｌｉ２Ｏ正極を調製した。
Example 6 (Preparation of Fe solid solution Li 2 O positive electrode mixture and positive electrode)
Except for using Fe
実施例７（Ｆｅ固溶Ｌｉ２Ｏ正極合剤及び正極の調製）
Ｌｉ２Ｏ微粉末の代わりに実施例２で得られたＦｅ固溶Ｌｉ２Ｏ微粉末を使用した以外は比較例２と同様の手法でＦｅ固溶Ｌｉ２Ｏ正極を調製した。
Example 7 (Preparation of Fe solid solution Li 2 O positive electrode mixture and positive electrode)
Except for using Fe
実施例８（Ｆｅ、Ｃｏ固溶Ｌｉ２Ｏ正極合剤及び正極の調製）
Ｌｉ２Ｏ微粉末の代わりに実施例３で得られたＦｅ、Ｃｏ固溶Ｌｉ２Ｏ微粉末を使用した以外は比較例２と同様の手法でＦｅ、Ｃｏ固溶Ｌｉ２Ｏ正極を調製した。
Example 8 (Preparation of Fe, Co solute Li 2 O positive electrode mixture and positive electrode)
Li 2 O Fe obtained in Example 3 in place of the fine powder, Co solid solution Li 2 O powder Fe in the same manner as in Comparative Example 2 except for using to prepare a Co solid solution Li 2 O positive .
実施例９（Ｆｅ、Ｃｏ固溶Ｌｉ２Ｏ正極合剤及び正極の調製）
Ｌｉ２Ｏ微粉末の代わりに実施例４で得られたＦｅ、Ｃｏ固溶Ｌｉ２Ｏ微粉末を使用した以外は比較例２と同様の手法でＦｅ、Ｃｏ固溶Ｌｉ２Ｏ正極を調製した。
Example 9 (Preparation of Fe, Co solute Li 2 O positive electrode mixture and positive electrode)
Li 2 O Fe obtained in Example 4 in place of the fine powder, Co solid solution Li 2 O powder Fe in the same manner as in Comparative Example 2 except for using to prepare a Co solid solution Li 2 O positive .
実施例１０（Ｆｅ、Ｃｏ固溶Ｌｉ２Ｏ正極合剤及び正極の調製）
Ｌｉ２Ｏ微粉末の代わりに実施例５で得られたＦｅ、Ｃｏ固溶Ｌｉ２Ｏ微粉末を使用した以外は比較例２と同様の手法でＦｅ、Ｃｏ固溶Ｌｉ２Ｏ正極を調製した。
Example 10 (Preparation of Fe, Co solute Li 2 O positive electrode mixture and positive electrode)
Li 2 O Fe obtained in Example 5 instead of the fine powder, Co solid solution Li 2 O powder Fe in the same manner as in Comparative Example 2 except for using to prepare a Co solid solution Li 2 O positive .
比較例３（電気化学的酸化試験）
電気化学的酸化試験は従来の三極式セルを用いて行った。ワーキング電極に比較例２において作成したＬｉ２Ｏ正極合剤電極（正極）、カウンター電極、及び、リファレンス電極にはリチウム金属を使用し、電解液には１Ｍ 過塩素酸リチウム（ＬｉＣｌＯ４）／ＥＣ−ＤＭＥ電解液（ＥＣ：エチレンカーボネート、ＤＭＥ：１，２−ジメトキシエタン）を使用した。正極活物質に対して４．５ｍＡ／ｇの電流密度で電気化学的酸化を行った。結果を図７に示す。図７の結果から遷移金属が固溶されていないＬｉ２Ｏ微粉末を用いると酸化容量は生じないことがわかった。
Comparative Example 3 (electrochemical oxidation test)
The electrochemical oxidation test was performed using a conventional triode cell. Li 2 O positive electrode mixture electrode (positive electrode) prepared in Comparative Example 2 was used as a working electrode, lithium metal was used as a counter electrode, and a reference electrode, and 1 M lithium perchlorate (LiClO 4 ) / EC was used as an electrolyte. -DME electrolyte (EC: ethylene carbonate, DME: 1,2-dimethoxyethane) was used. Electrochemical oxidation was performed on the positive electrode active material at a current density of 4.5 mA / g. The results are shown in FIG. From the results of FIG. 7, it was found that the oxidation capacity does not occur when Li 2 O fine powder in which the transition metal is not dissolved is used.
実施例１１（電気化学的酸化試験）
ワーキング電極に実施例６において作成したＦｅ固溶Ｌｉ２Ｏ微粉末正極合剤電極（正極）を使用した以外は比較例３と同様の手法で電気化学的酸化試験を行った。結果を図８に示す。図８の結果からＦｅ固溶Ｌｉ２Ｏ微粉末を用いると３．３Ｖ付近から電位平坦部が見られ酸化容量が発現することがわかった。
Example 11 (electrochemical oxidation test)
An electrochemical oxidation test was performed in the same manner as in Comparative Example 3 except that the working electrode used was the Fe solid solution Li 2 O fine powder positive electrode mixture electrode (positive electrode) prepared in Example 6. The results are shown in FIG. From the results of FIG. 8, it was found that when the Fe solid solution Li 2 O fine powder was used, a potential flat portion was seen from around 3.3 V and the oxidation capacity was expressed.
実施例１２（電気化学的酸化試験）
ワーキング電極に実施例７において作成したＦｅ固溶Ｌｉ２Ｏ微粉末正極合剤電極（正極）を使用した以外は比較例３と同様の手法で電気化学的酸化試験を行った。結果を図９に示す。図９の結果からＦｅ固溶Ｌｉ２Ｏ微粉末を用いると３．２Ｖ付近から電位平坦部が見られ酸化容量が発現することがわかった。
Example 12 (electrochemical oxidation test)
An electrochemical oxidation test was conducted in the same manner as in Comparative Example 3 except that the working electrode used was the Fe solid solution Li 2 O fine powder positive electrode mixture electrode (positive electrode) prepared in Example 7. The results are shown in FIG. From the results shown in FIG. 9, it was found that when Fe solid solution Li 2 O fine powder was used, a potential flat portion was observed from around 3.2 V and oxidation capacity was developed.
比較例４（電気化学的酸化試験）
電気化学的酸化試験は市販の２極式セル（ＨＳセル、宝泉社製）を用いて行った。ワーキング電極に比較例２において作成したＬｉ２Ｏ微粉末正極合剤電極、カウンター電極にはリチウム金属を使用し、電解液には４．２Ｍ ＬｉＴＦＳＩ アセトニトリル電解液（ＬｉＴＦＳＩ：リチウムビストリフルオロメタンスルホニルイミド〔ＬｉＮ（ＳＯ２ＣＦ３）２〕、ＤＭＥ：１，２−ジメトキシエタン）を使用した。正極活物質に対して４．５ｍＡ／ｇの電流密度で電気化学的酸化を行った。結果を図１０に示す。図１０の結果から本電気化学的酸化条件においても遷移金属が固溶されていないＬｉ２Ｏ微粉末を用いると酸化容量は生じないことがわかった。
Comparative Example 4 (electrochemical oxidation test)
The electrochemical oxidation test was performed using a commercially available bipolar cell (HS cell, manufactured by Hosen Co., Ltd.). Li 2 O fine powder positive electrode mixture electrode prepared in Comparative Example 2 was used for the working electrode, lithium metal was used for the counter electrode, and 4.2 M LiTFSI acetonitrile electrolyte (LiTFSI: lithium bistrifluoromethanesulfonylimide [ LiN (SO 2 CF 3 ) 2 ], DME: 1,2-dimethoxyethane) was used. Electrochemical oxidation was performed on the positive electrode active material at a current density of 4.5 mA / g. The results are shown in FIG. From the results shown in FIG. 10, it was found that the oxidation capacity does not occur when using Li 2 O fine powder in which the transition metal is not dissolved in this electrochemical oxidation condition.
実施例１３（電気化学的酸化試験）
ワーキング電極に実施例８において作成したＦｅ、Ｃｏ固溶Ｌｉ２Ｏ微粉末正極合剤電極（正極）を使用した以外は比較例４と同様の手法で電気化学的酸化試験を行った。結果を図１１に示す。図１１の結果からＦｅ固溶Ｌｉ２Ｏ微粉末を用いると３．３Ｖ付近から電位平坦部が見られ酸化容量が発現することがわかった。
Example 13 (electrochemical oxidation test)
An electrochemical oxidation test was performed in the same manner as in Comparative Example 4 except that the working electrode was the Fe and Co solid solution Li 2 O fine powder positive electrode mixture electrode (positive electrode) prepared in Example 8. The results are shown in FIG. From the results shown in FIG. 11, it was found that when Fe solid solution Li 2 O fine powder was used, a potential flat portion was observed from around 3.3 V and an oxidation capacity was developed.
実施例１４（電気化学的酸化試験）
ワーキング電極に実施例９において作成したＦｅ、Ｃｏ固溶Ｌｉ２Ｏ微粉末正極合剤電極（正極）を使用した以外は比較例４と同様の手法で電気化学的酸化試験を行った。結果を図１２に示す。図１２の結果からＦｅ固溶Ｌｉ２Ｏ微粉末を用いると３．２Ｖ付近から電位平坦部が見られ酸化容量が発現することがわかった。
Example 14 (electrochemical oxidation test)
An electrochemical oxidation test was performed in the same manner as in Comparative Example 4 except that the working electrode was the Fe, Co solid solution Li 2 O fine powder positive electrode mixture electrode (positive electrode) prepared in Example 9. The results are shown in FIG. From the results of FIG. 12, it was found that when the Fe solid solution Li 2 O fine powder was used, a potential flat portion was seen from around 3.2 V and an oxidation capacity was developed.
実施例１５（電気化学的酸化試験）
ワーキング電極に実施例１０において作成したＦｅ、Ｃｏ固溶Ｌｉ２Ｏ微粉末正極合剤電極（正極）を使用した以外は比較例４と同様の手法で電気化学的酸化試験を行った。結果を図１３に示す。図１３の結果からＦｅ固溶Ｌｉ２Ｏ微粉末を用いると３．２Ｖ付近から電位平坦部が見られ酸化容量が発現することがわかった。
Example 15 (electrochemical oxidation test)
An electrochemical oxidation test was performed in the same manner as in Comparative Example 4 except that the working electrode was the Fe, Co solid solution Li 2 O fine powder positive electrode mixture electrode (positive electrode) prepared in Example 10. The results are shown in FIG. From the results shown in FIG. 13, it was found that when Fe solid solution Li 2 O fine powder was used, a potential flat portion was seen from around 3.2 V and oxidation capacity was developed.
実施例１６（電気化学的酸化後のワーキング電極のＸＲＤ分析）
実施例１５と同様の条件にて電気化学的酸化試験を行った。カットオフ電圧は３．３Ｖとし充電後の正極をアセトニトリル溶媒にて洗浄した後に乾燥した。得られた充電後の正極をアルゴン封入した気密試料台に入れＸＲＤ測定を行った。結果を図１４に示す。酸化容量に応じて３３．５°付近のＬｉ２Ｏのシグナルの減衰が見られた。これらのことから電気化学的に得られた酸化容量はＬｉ２Ｏの電気化学的酸化によるものであることが確認出来た。
Example 16 (XRD analysis of working electrode after electrochemical oxidation)
An electrochemical oxidation test was performed under the same conditions as in Example 15. The cutoff voltage was 3.3 V, and the positive electrode after charging was washed with an acetonitrile solvent and then dried. The obtained positive electrode after charging was placed in an airtight sample table filled with argon, and XRD measurement was performed. The results are shown in FIG. Attenuation of the Li 2 O signal around 33.5 ° was observed depending on the oxidation capacity. From these facts, it was confirmed that the electrochemically obtained oxidation capacity was due to the electrochemical oxidation of Li 2 O.
Claims (8)
該金属酸化物は、アルカリ金属酸化物の結晶構造内に遷移金属原子が固溶した構造を有することを特徴とする遷移金属固溶アルカリ金属酸化物。 A metal oxide containing an alkali metal atom and a transition metal atom,
The metal oxide has a structure in which transition metal atoms are in solid solution in the crystal structure of the alkali metal oxide.
［Ａ２−ｘＢｘ］Ｏ （１）
（式中、Ａは、アルカリ金属原子を表す。Ｂは、遷移金属原子を表す。ｘは、０＜ｘ＜２の数を表す。）で表されることを特徴とする請求項１に記載の遷移金属固溶アルカリ金属酸化物。 The transition metal solid solution alkali metal oxide has the following formula (1):
[A 2-x B x] O (1)
(Wherein, A represents an alkali metal atom, B represents a transition metal atom, and x represents a number of 0 <x <2). Transition metal solid solution alkali metal oxide.
該製造方法は、メカノケミカル処理によりアルカリ金属酸化物の結晶構造内に遷移金属原子を固溶させる工程を含むことを特徴とする遷移金属固溶アルカリ金属酸化物の製造方法。 A method for producing a transition metal solid solution alkali metal oxide having a structure in which a transition metal atom is dissolved in the crystal structure of an alkali metal oxide,
The manufacturing method includes a step of solid-dissolving transition metal atoms in the crystal structure of the alkali metal oxide by mechanochemical treatment.
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| CN107104232A (en) * | 2016-02-19 | 2017-08-29 | 松下知识产权经营株式会社 | Positive active material and battery |
| JP2018041677A (en) * | 2016-09-09 | 2018-03-15 | 株式会社Ｇｓユアサ | Positive electrode active material, positive electrode, and nonaqueous electrolyte power storage device |
| WO2019163475A1 (en) | 2018-02-20 | 2019-08-29 | 株式会社Ｇｓユアサ | Positive electrode active material, positive electrode, non-aqueous electrolyte power storage element, method for producing positive electrode active material, and method for producing non-aqueous electrolyte power storage element |
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| JP2015130316A (en) * | 2013-12-04 | 2015-07-16 | 国立大学法人 東京大学 | Active material for sealed battery |
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| 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 |
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| JP2017152370A (en) * | 2016-02-19 | 2017-08-31 | パナソニックＩｐマネジメント株式会社 | Positive electrode active material and battery |
| CN107104232B (en) * | 2016-02-19 | 2022-01-07 | 松下知识产权经营株式会社 | Positive electrode active material and battery |
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