JP2014035868A - マグネシウム二次電池 - Google Patents
マグネシウム二次電池 Download PDFInfo
- Publication number
- JP2014035868A JP2014035868A JP2012176140A JP2012176140A JP2014035868A JP 2014035868 A JP2014035868 A JP 2014035868A JP 2012176140 A JP2012176140 A JP 2012176140A JP 2012176140 A JP2012176140 A JP 2012176140A JP 2014035868 A JP2014035868 A JP 2014035868A
- Authority
- JP
- Japan
- Prior art keywords
- magnesium
- mgo
- oxide
- secondary battery
- positive electrode
- 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
- 239000011777 magnesium Substances 0.000 title claims abstract description 58
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 49
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 169
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 169
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 169
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 50
- 239000001301 oxygen Substances 0.000 claims abstract description 47
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 47
- 239000010416 ion conductor Substances 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000003054 catalyst Substances 0.000 claims description 35
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 56
- 238000003487 electrochemical reaction Methods 0.000 description 18
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 13
- 239000011149 active material Substances 0.000 description 13
- 229910001882 dioxygen Inorganic materials 0.000 description 13
- -1 oxygen ions Chemical class 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000011255 nonaqueous electrolyte Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000007773 negative electrode material Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000012887 quadratic function Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-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
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 1
- 241001028048 Nicola Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000012300 argon atmosphere 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
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- NPLSMKXEGNZDGK-UHFFFAOYSA-N diethyl-methoxy-methylazanium Chemical compound CC[N+](C)(CC)OC NPLSMKXEGNZDGK-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- BJTUQCSQXJWURC-UHFFFAOYSA-L magnesium;1-fluorobutane-1-sulfonate Chemical compound [Mg+2].CCCC(F)S([O-])(=O)=O.CCCC(F)S([O-])(=O)=O BJTUQCSQXJWURC-UHFFFAOYSA-L 0.000 description 1
- DMFBPGIDUUNBRU-UHFFFAOYSA-N magnesium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Mg+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F DMFBPGIDUUNBRU-UHFFFAOYSA-N 0.000 description 1
- BZQRBEVTLZHKEA-UHFFFAOYSA-L magnesium;trifluoromethanesulfonate Chemical compound [Mg+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F BZQRBEVTLZHKEA-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/466—Magnesium based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/664—Ceramic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/666—Composites in the form of mixed materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/74—Meshes or woven material; Expanded metal
-
- 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
Abstract
【解決手段】マグネシウムイオンを吸蔵、放出可能な負極(2)と、放電時にマグネシウム酸化物を生成する正極(1)と、前記負極と前記正極との間に介在する非水系のマグネシウムイオン伝導体(3)と、を有するマグネシウム二次電池であって、前記マグネシウム酸化物として、酸化マグネシウム(MgO)よりもマグネシウムイオンと酸素とに分解され易い酸化物の生成を促す促進剤(11)を有している。
【選択図】図3
Description
充電の際に正極で進行すべき電気化学反応を(i)式に示す。
MgO2→Mg2++O2+2e− (i)
同様に、放電時に生成される酸化物がMgOの場合の反応を(ii)式に示す。
2MgO→2Mg2++O2+4e− (ii)
ここで、放電時に生成されるマグネシウム酸化物は、正極活物質として酸素を使用して生成させるのが好ましい。この場合に、放電時の正極で進行すべき電気化学反応は、(i)式、(ii)式の逆向きの反応式で表される。
E=7.1294Q2−7.6742Q−1848 (iii)
同様にMgOに関する図2の曲線は、(iv)式の2次関数で表され、Q=0のときの傾きは−9.6296となる。
E=11.952Q2−9.6296Q−1413.7 (iv)
従って、MgO2の曲線の傾きの方がなだらかであるため、MgO2の方が、MgOよりも分解され易いことが分かる。
本実施形態に係る促進剤は、放電時の正極の電気化学反応によって、MgOよりも、マグネシウムイオンと酸素とに分解され易い酸化物の生成を促すものである。
本実施形態に係るマグネシウム二次電池において、正極には、上述したMgO2の生成を促す促進剤の具体例である酸化触媒が配されることが好ましい。例えば、正極の集電体に、酸化触媒を含有する触媒層を配することができる。
本実施形態に係る負極は、マグネシウムイオンを吸蔵、放出可能な負極活物質層を配した負極を備えることが好ましい。
本実施形態に係るマグネシウム二次電池の非水系のマグネシウムイオン伝導体は、正極と負極の間に介在して、正負極間のマグネシウムイオンの伝導を担う非水系の電解液であることが好ましい。
本発明のマグネシウム二次電池は、その製造方法が限定されるものではなく、従来公知の非水電解液二次電池の製造方法と同様に製造することができる。例えば、上述の正極及び負極を形成後、セパレータを介して積層して形成した電極体を電池容器内に収納した後、非水系のマグネシウムイオン伝導体を注入するといった通常の方法を挙げることができる。
(触媒層を配した正極の集電体)
MgOよりも、マグネシウムイオンと酸素とに分解されやすいマグネシウム酸化物の生成を促すための酸化触媒(促進剤)として、二酸化マンガン微粒子(東ソー社製、FMH)を20質量部と、導電材として、ケッチェンブラック(ケッチェンインターナショナル社製、KB−ECP600JD)を70質量部と、結着剤として、PTFEパウダー(ダイキン工業社製、D−2C)を10質量部と、を乾式で乳鉢を用いて練り合わせてシート状の触媒シートを作製した。その触媒シート4mgをニッケルメッシュ(ニコラ製)に圧着して、触媒層を配した正極の集電体とした。
直径14mm、厚さ0.1mmの金属マグネシウム(Goodfellow社製、純度3N)を負極とした。
非プロトン性の有機溶媒の全体積を100%とした場合に、テトラヒドロフランを15体積%と、ジエチレングリコールジメチルエーテルを85体積%と、になるように混合して、非プロトン性の有機溶媒を調製した。この非プロトン性の有機溶媒に、Mgカチオン濃度が0.3モル/リットルとなるように塩化マグネシウムを添加し、さらに、ホウ素系アニオン錯体であるエトキシ・クロロ・フェニル錯体を添加した非水系の電解液を調整した。
上記の正極、負極、非水系電解液等を用いて、図3に示すF型電気化学セルCを以下の手順で組み立てた。
触媒シート11が圧着されていない正極の集電体12を用いた以外は、実施例と同様にF型電気化学セルC´を製作した。
(充電容量)
上記のF型電気化学セルCを、北斗電工社製の充放電装置(HJ1001SM8A型)に接続し、正極1と負極2との間で5μAの電流(正極材料の単位重量あたり1.8mA/g)を流し、正極材料の単位重量あたり400mAh/gまで定電流放電した。その後、両電極の極性を切り替えて、5μAの電流を流して3.2Vになるまで定電流充電した。なお、正極材料の重量は、触媒シートの重量である。
実施例のF型電気化学セルCを用いて、正極材料あたり400mAh/gまで定電流放電した後に、これを分解して正極を取り出した。正極に析出したマグネシウム酸化物をXPSにて測定し、測定結果を図5に示した。図5中のスペクトルは、XPS測定により得られた酸素の結合エネルギー(Binding Energy)を表す。
上記と同様に、実施例のF型電気化学セルCを用いて、正極材料あたり400mAh/gまで定電流放電した後に、これを分解して正極を取り出した。正極に析出したマグネシウム酸化物の組成をEPMAによって分析した。放電時の電気化学反応によって生成したマグネシウム酸化物のマグネシウム(Mg)と酸素(O)の組成比が、Mg:O=1:1.43であることが判明した。つまり、1<x≦2の範囲のマグネシウム酸化物(MgO1.43)の存在が明らかとなった。
1:正極
11:触媒シート
2:負極
3:非水系の電解液
Claims (5)
- マグネシウムイオンを吸蔵、放出可能な負極(2)と、
放電時にマグネシウム酸化物を生成する正極(1)と、
前記負極と前記正極との間に介在する非水系のマグネシウムイオン伝導体(3)と、
を有するマグネシウム二次電池であって、
前記マグネシウム酸化物として、酸化マグネシウム(MgO)よりもマグネシウムイオンと酸素とに分解され易い酸化物の生成を促す促進剤(11)を有することを特徴とするマグネシウム二次電池。 - 前記マグネシウム酸化物は、MgOx(1<x≦2)で示される酸化物である請求項1に記載のマグネシウム二次電池。
- 前記マグネシウム酸化物は、二酸化マグネシウム(MgO2)と、0以上の物質量の酸化マグネシウム(MgO)と、が混在した状態の酸化物である請求項1又は2に記載のマグネシウム二次電池。
- 前記マグネシウム酸化物は、二酸化マグネシウム(MgO2)である請求項1ないし3のいずれかに記載のマグネシウム二次電池。
- 前記促進剤は、酸化触媒(11)である請求項1ないし4のいずれかに記載のマグネシウム二次電池。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012176140A JP5660086B2 (ja) | 2012-08-08 | 2012-08-08 | マグネシウム二次電池 |
US13/960,065 US8986887B2 (en) | 2012-08-08 | 2013-08-06 | Magnesium secondary battery |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012176140A JP5660086B2 (ja) | 2012-08-08 | 2012-08-08 | マグネシウム二次電池 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2014035868A true JP2014035868A (ja) | 2014-02-24 |
JP5660086B2 JP5660086B2 (ja) | 2015-01-28 |
Family
ID=50066424
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2012176140A Active JP5660086B2 (ja) | 2012-08-08 | 2012-08-08 | マグネシウム二次電池 |
Country Status (2)
Country | Link |
---|---|
US (1) | US8986887B2 (ja) |
JP (1) | JP5660086B2 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016105356A (ja) * | 2014-12-01 | 2016-06-09 | 俊彦 川畑 | 金属空気電池 |
WO2016143675A1 (ja) * | 2015-03-06 | 2016-09-15 | 学校法人東京理科大学 | マグネシウム二次電池及び充放電方法 |
JP2016181506A (ja) * | 2015-03-23 | 2016-10-13 | 株式会社デンソー | 再充電可能マグネシウム電池 |
JP2017103215A (ja) * | 2015-12-01 | 2017-06-08 | 株式会社デンソー | 非水型マグネシウム酸素電池 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10263305B2 (en) | 2015-12-01 | 2019-04-16 | Denso Corporation | Magnesium oxygen battery |
US9997815B2 (en) * | 2016-08-05 | 2018-06-12 | Toyota Motor Engineering & Manufacturing North America, Inc. | Non-aqueous magnesium-air battery |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005228589A (ja) * | 2004-02-13 | 2005-08-25 | Sony Corp | 電気化学デバイス及び電極 |
JP2006505109A (ja) * | 2002-10-29 | 2006-02-09 | ソニー株式会社 | 電気化学電池 |
JP2009064731A (ja) * | 2007-09-07 | 2009-03-26 | Sony Corp | 正極活物質及びその製造方法、並びに電気化学デバイス |
JP2010182570A (ja) * | 2009-02-06 | 2010-08-19 | Toyota Central R&D Labs Inc | 非水系空気二次電池 |
JP2011054389A (ja) * | 2009-09-01 | 2011-03-17 | Toyota Central R&D Labs Inc | 二次電池及び正極の製造方法 |
JP2011142049A (ja) * | 2010-01-08 | 2011-07-21 | Sumitomo Electric Ind Ltd | 電極、マグネシウムイオン2次電池、および電力システム |
JP2011171072A (ja) * | 2010-02-17 | 2011-09-01 | Toyota Central R&D Labs Inc | 非水電解液空気電池 |
JP2011249155A (ja) * | 2010-05-27 | 2011-12-08 | Toyota Central R&D Labs Inc | 非水電解液空気電池 |
JP2013037993A (ja) * | 2011-08-10 | 2013-02-21 | Toyota Central R&D Labs Inc | 非水系マグネシウム電池 |
JP2013218786A (ja) * | 2012-04-04 | 2013-10-24 | Toyota Central R&D Labs Inc | 非水系空気電池 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4015826B2 (ja) | 2001-06-19 | 2007-11-28 | 株式会社東芝 | 非水電解質空気電池 |
KR20130103333A (ko) * | 2010-04-23 | 2013-09-23 | 리옥스 파워, 인코퍼레이티드 | 재충전가능한 금속-공기 배터리용의 가용성 산소 발생 촉매 |
-
2012
- 2012-08-08 JP JP2012176140A patent/JP5660086B2/ja active Active
-
2013
- 2013-08-06 US US13/960,065 patent/US8986887B2/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006505109A (ja) * | 2002-10-29 | 2006-02-09 | ソニー株式会社 | 電気化学電池 |
JP2005228589A (ja) * | 2004-02-13 | 2005-08-25 | Sony Corp | 電気化学デバイス及び電極 |
JP2009064731A (ja) * | 2007-09-07 | 2009-03-26 | Sony Corp | 正極活物質及びその製造方法、並びに電気化学デバイス |
JP2010182570A (ja) * | 2009-02-06 | 2010-08-19 | Toyota Central R&D Labs Inc | 非水系空気二次電池 |
JP2011054389A (ja) * | 2009-09-01 | 2011-03-17 | Toyota Central R&D Labs Inc | 二次電池及び正極の製造方法 |
JP2011142049A (ja) * | 2010-01-08 | 2011-07-21 | Sumitomo Electric Ind Ltd | 電極、マグネシウムイオン2次電池、および電力システム |
JP2011171072A (ja) * | 2010-02-17 | 2011-09-01 | Toyota Central R&D Labs Inc | 非水電解液空気電池 |
JP2011249155A (ja) * | 2010-05-27 | 2011-12-08 | Toyota Central R&D Labs Inc | 非水電解液空気電池 |
JP2013037993A (ja) * | 2011-08-10 | 2013-02-21 | Toyota Central R&D Labs Inc | 非水系マグネシウム電池 |
JP2013218786A (ja) * | 2012-04-04 | 2013-10-24 | Toyota Central R&D Labs Inc | 非水系空気電池 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016105356A (ja) * | 2014-12-01 | 2016-06-09 | 俊彦 川畑 | 金属空気電池 |
WO2016143675A1 (ja) * | 2015-03-06 | 2016-09-15 | 学校法人東京理科大学 | マグネシウム二次電池及び充放電方法 |
JP2016181506A (ja) * | 2015-03-23 | 2016-10-13 | 株式会社デンソー | 再充電可能マグネシウム電池 |
JP2017103215A (ja) * | 2015-12-01 | 2017-06-08 | 株式会社デンソー | 非水型マグネシウム酸素電池 |
Also Published As
Publication number | Publication date |
---|---|
JP5660086B2 (ja) | 2015-01-28 |
US8986887B2 (en) | 2015-03-24 |
US20140045071A1 (en) | 2014-02-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9941559B2 (en) | Water enhanced ionic liquid electrolytes for metal-air batteries | |
JP5660086B2 (ja) | マグネシウム二次電池 | |
JP5942549B2 (ja) | 空気電池、空気電池の使用方法および電子機器 | |
JP4788560B2 (ja) | 蓄電デバイス | |
JP2015130287A (ja) | 炭素複合体及び蓄電デバイス | |
JP2012084379A (ja) | 金属空気電池システム、及び金属空気電池の充電方法 | |
JP2016092010A (ja) | 金属空気電気化学セル、リチウム空気電池、および車両 | |
US9515317B2 (en) | Surface treating method of negative electrode for magnesium secondary battery, negative electrode for magnesium secondary battery, and magnesium secondary battery | |
JP2010140821A (ja) | 空気電池 | |
JP5256649B2 (ja) | 水系リチウム二次電池 | |
WO2014100560A1 (en) | Cathode material for lithium-oxygen battery | |
JP5880224B2 (ja) | 空気電池および電子機器 | |
JP2010086924A (ja) | マグネシウム空気二次電池 | |
JP2015138581A (ja) | 非水電解液空気二次電池 | |
JP2013118145A (ja) | 金属空気二次電池 | |
US10629970B2 (en) | Lithium air battery including negative electrode, positive electrode, nonaqueous lithium ion conductor, and copper ion | |
US11289745B2 (en) | Elimination of gaseous reactants in lithium ion batteries | |
JP2014044896A (ja) | 非水電解質空気電池及びその使用方法 | |
JP5669405B2 (ja) | リチウム空気電池 | |
US10147969B2 (en) | Electrolytic solution for electrochemical devices and electrochemical device in which the electrolytic solution is used | |
JP5928293B2 (ja) | 化合物、及びリチウムイオン電池 | |
JP5223461B2 (ja) | 空気電池 | |
JP2018133168A (ja) | リチウム空気電池及びその使用方法 | |
JP2009211912A (ja) | 空気電池 | |
US9960467B2 (en) | Magnesium oxygen battery |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20131202 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140619 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140703 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140806 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20141104 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20141117 |
|
R151 | Written notification of patent or utility model registration |
Ref document number: 5660086 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |