WO2023017602A1 - プロトン伝導体及びその製造方法 - Google Patents
プロトン伝導体及びその製造方法 Download PDFInfo
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- WO2023017602A1 WO2023017602A1 PCT/JP2021/029746 JP2021029746W WO2023017602A1 WO 2023017602 A1 WO2023017602 A1 WO 2023017602A1 JP 2021029746 W JP2021029746 W JP 2021029746W WO 2023017602 A1 WO2023017602 A1 WO 2023017602A1
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- Prior art keywords
- geo
- proton conductor
- lithium ions
- protons
- hydrogen
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- 239000004020 conductor Substances 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 17
- 239000003125 aqueous solvent Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 239000005711 Benzoic acid Substances 0.000 claims description 6
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002152 aqueous-organic solution Substances 0.000 abstract description 6
- 229910005833 GeO4 Inorganic materials 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract 1
- 239000000446 fuel Substances 0.000 description 75
- 239000011701 zinc Substances 0.000 description 61
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 40
- 229910052739 hydrogen Inorganic materials 0.000 description 40
- 239000001257 hydrogen Substances 0.000 description 40
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 38
- 238000005342 ion exchange Methods 0.000 description 31
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 19
- 239000000126 substance Substances 0.000 description 19
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- 238000006356 dehydrogenation reaction Methods 0.000 description 13
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- 238000006243 chemical reaction Methods 0.000 description 12
- 239000007784 solid electrolyte Substances 0.000 description 11
- 229910005317 Li14Zn(GeO4)4 Inorganic materials 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- QPTUMKXXAAHOOE-UHFFFAOYSA-M cesium;hydron;phosphate Chemical compound [Cs+].OP(O)([O-])=O QPTUMKXXAAHOOE-UHFFFAOYSA-M 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
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- 238000011161 development Methods 0.000 description 6
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
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- 230000009467 reduction Effects 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000002227 LISICON Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
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- 238000005984 hydrogenation reaction Methods 0.000 description 3
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- 238000003756 stirring Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
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- 235000019253 formic acid Nutrition 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910006111 GeCl2 Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
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- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
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- QHGIKMVOLGCZIP-UHFFFAOYSA-N germanium dichloride Chemical compound Cl[Ge]Cl QHGIKMVOLGCZIP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a proton conductor, and more preferably to a proton conductor having sufficient proton conductivity in a medium temperature range of 200°C or higher, more preferably 300 to 600°C.
- PEFC Polymer electrolyte fuel cells
- PAFC phosphoric acid fuel cells
- MCFC molten carbonate fuel cells
- SOFC solid oxide fuels Batteries
- the operating temperature is room temperature to 100°C for polymer electrolyte fuel cells, 180 to 200°C for phosphoric acid fuel cells, 600 to 700°C for molten carbonate fuel cells, and 600 to 900°C for solid oxide fuel cells. is. However, there is no fuel cell that operates in the medium temperature range of 200-600°C.
- Fuel cells that operate in the medium temperature range of 200 to 600°C are not only hydrogen-oxygen fuel cells, but also generate hydrogen from various fuels in the fuel electrode chamber of the fuel cell, and use the generated hydrogen by the fuel cell reaction. Suitable for direct fuel cells that generate electricity.
- a fuel cell that operates in a medium temperature range of 200 to 600° C. can promote the fuel cell reaction compared to a fuel cell that operates in a low temperature range of 200° C. or less, so efficiency can be improved.
- Patent Document 1 discloses a direct fuel cell.
- organic hydrides such as methylcyclohexane and decalin are supplied as fuels to the fuel cells, and brought into contact with a noble metal catalyst fixed to the electrode of the fuel electrode for dehydrogenation.
- Hydrogen generated at the fuel electrode transfers electrons to the fuel electrode and becomes protons.
- Protons move in the electrolyte membrane and receive electrons from the electrode together with oxygen atoms activated at the air electrode of the counter electrode to advance the fuel cell reaction.
- the electrolyte membrane is a membrane made of a mixture of microcrystals of cesium dihydrogen phosphate (CsH 2 PO 4 ) and polytetrafluoroethylene.
- the direct fuel cell of Patent Document 1 has an output of 40 mW/cm 2 at an operating temperature of 170-220°C.
- the operating temperature is generally 100°C or less, and the heat resistance of the organic film is not sufficient at 200°C or more.
- Cesium dihydrogen phosphate is known as a solid electrolyte that can be used at 200° C. or higher.
- the use limit temperature of cesium dihydrogen phosphate is 270° C., there is a demand for a novel proton conductor that can be used at even higher temperatures.
- Non-Patent Document 1 discloses Li 13.9 Sr 0.1 Zn ( Li 13.9 Sr 0.1 Zn ( GeO 4 ) 4 are disclosed. Li 13.9 Sr 0.1 Zn(GeO 4 ) 4 exhibits a conductivity of 0.039 S/cm at 600° C., which is higher than that of conventional zirconia-based or ceria-based solid electrolytes. A fuel cell using Li13.9Sr0.1Zn ( GeO4 ) 4 has an output of about 0.4 W/ cm2 at an operating temperature of 600C.
- Li 13.9 Sr 0.1 Zn(GeO 4 ) 4 improves the conductivity to 0.048 S/cm at an operating temperature of 600°C.
- Lithium ions and protons are exchanged in water or dilute acetic acid.
- ion exchange has been performed by stirring Li 13.9 Sr 0.1 Zn(GeO 4 ) 4 in 5 mM aqueous acetic acid for 24 hours.
- Non-Patent Document 2 discloses a proton conductor in which Li 14-2x Zn 1+x (GeO 4 ) 4 is ion-exchanged in a 5 mM acetic acid aqueous solution to exchange lithium ions for protons.
- ion exchange is performed on Li 14 Zn(GeO 4 ) 4 , Li 12 Zn 2 (GeO 4 ) 4 and Li 10 Zn 3 (GeO 4 ) 4 with varying Li + /Zn 2+ ratios.
- identifying each sample and measuring the weight change during heating it was confirmed that the amount of ion-exchanged to protons is greater in samples with a higher lithium content.
- Non-Patent Document 2 finds the possibility of obtaining the same conductivity as the proton conductor disclosed in Non-Patent Document 1 from the results of electromotive force measurement of a hydrogen concentration cell using a proton conductor. .
- an object of the present invention is to provide a proton conductor suitable for use in the temperature range of 200-600°C.
- Another object of the present invention is to provide a method for producing a proton conductor suitable for use in a temperature range of 200 to 600.degree.
- one aspect of the present invention provides Li 14-2x Zn 1+x (GeO 4 ) 4 in which some of the lithium ions are replaced with protons, and has a conductivity of 0.01 S/cm or more at 300 ° C.
- x is a number of 0 or more. x may contain decimals.
- the structure in which some of the lithium ions of Li 14-2x Zn 1+x (GeO 4 ) 4 are substituted with protons is (Li, H) 14-2x Zn 1+x (GeO 4 ) 4 or (Li, H) 2+2y It can be written as Zn 1-y GeO 4 .
- the x may be 0.
- Mobile lithium ions refer to lithium ions that can move in Li 14-2x Zn 1+x (GeO 4 ) 4 among all lithium ions contained in Li 14-2x Zn 1+x (GeO 4 ) 4 .
- the ratio of mobile lithium ions to all lithium ions in Li 14-2x Zn 1+x (GeO 4 ) 4 is (3 ⁇ x)/(14 ⁇ 2x).
- Another aspect of the present invention is a method for producing a proton conductor, in which Li 14-2x Zn 1+x (GeO 4 ) 4 is immersed in a non-aqueous organic solution containing an acid to convert some of the lithium ions to A step of substituting protons is included.
- x is a number of 0 or more.
- x may contain decimals. In this aspect, the x may be 0.
- a proton conductor that can be used in the temperature range of 200 to 600° C.
- the ion exchange rate of mobile lithium ions contained in Li 14-2x Zn 1+x (GeO 4 ) 4 to protons can be 40% or more and 70% or less.
- the proton conductor has improved structural stability and relatively high electrical conductivity.
- the acid may contain at least one selected from the group including benzoic acid, m-nitrophenol, acetic acid, p-toluenesulfonic acid, oxalic acid, and methanesulfonic acid.
- the non-aqueous solvent may contain at least one selected from the group including toluene, dimethylsulfoxide, tetrahydrofuran, and N,N-dimethylformamide.
- the proton conductor has a structure in which part of Li in Li 14-2x Zn 1+x (GeO 4 ) 4 is replaced with protons.
- x is a number greater than or equal to 0 and may include decimals.
- Li 14-2x Zn 1+x (GeO 4 ) 4 is (Li, H) 14-2x Zn 1+x (GeO 4 ) 4 or (Li, H) 2+2y It can be written as Zn 1-y GeO 4 .
- Li 14-2x Zn 1+x (GeO 4 ) 4 is a kind of LISICON (lithium superion conductor) which is a solid electrolyte. x may be 0, 1, 2, for example.
- LISICON Lithium super ionic conductor
- Li 14 Zn(GeO 4 ) 4 is a solid solution of Zn in the matrix structure of Li 4 GeO 4 and has high conductivity.
- a proton conductor has a conductivity of 0.01 S/cm or more at 300°C.
- 40% or more and 70% or less of mobile lithium ions contained in Li 14-2x Zn 1+x (GeO 4 ) 4 are replaced with protons.
- 50% or more and 60% or less of the movable lithium ions contained in Li 14-2x Zn 1+x (GeO 4 ) 4 are preferably replaced with protons.
- Li 14-2x Zn 1+x (GeO 4 ) 4 before ion exchange is described.
- a method for preparing Li 14-2x Zn 1+x (GeO 4 ) 4 is also disclosed in Non-Patent Document 2 above.
- Li 14-2x Zn 1+x (GeO 4 ) 4 can be prepared by solid phase methods. Li source, Zn source, and Ge source reagent powders are mixed overnight in an organic solvent, and after pulverization, the organic solvent is evaporated to obtain a mixture.
- the Li source may include at least one selected from the group including LiOH, Li2O , and LiNO3 .
- the Zn source may include at least one selected from the group including Zn(OH) 2 , ZnCO 3 and Zn(NO 3 ) 2 .
- the Ge source may comprise at least one selected from the group comprising GeO and GeCl2 .
- a combination of Li source, Zn source, and Ge source may be, for example, Li 2 CO 3 , ZnO, GeO 2 .
- the organic solvent may be at least one selected from the group including ethanol, methanol, 1-propanol, 2-propanol, and 1-butanol. Thereafter, the mixture is molded into pellets using a molding machine, the molded product is sintered in air, and then pulverized into powder to obtain Li 14-2x Zn 1+x (GeO 4 ) 4 .
- the air firing temperature of the molding is preferably 1000 to 1200°C, more preferably 1100 to 1150°C. If the firing temperature is lower than 1000°C, the solid phase reaction does not progress, and if the firing temperature is higher than 1200°C, the molding melts.
- the firing time of the molding is preferably 3 to 7 hours, more preferably 4 to 6 hours.
- the molding may be sintered, for example, at 1150° C. in air for 5 hours.
- Li 14-2x Zn 1+x (GeO 4 ) 4 may be, for example, Li 14 Zn(GeO 4 ) 4 , Li 12 Zn 2 (GeO 4 ) 4 , Li 10 Zn 3 (GeO 4 ) 4 .
- the ratio of Li to Zn in Li 14-2x Zn 1+x (GeO 4 ) 4 can be changed by changing the ratio of Li source, Zn source and Ge source to be mixed.
- Non-aqueous solvents are preferably aprotic solvents.
- the non-aqueous solvent may include one selected from the group including toluene, dimethylsulfoxide, tetrahydrofuran, N,N-dimethylformamide.
- the acid preferably contains at least one selected from the group including benzoic acid, m-nitrophenol, acetic acid, p-toluenesulfonic acid, oxalic acid, and methanesulfonic acid.
- benzoic acid Li 14-2x Zn 1+x (GeO 4 ) in 100 mL of a non-aqueous organic solution in which toluene from which water has been removed with a dehydrating agent is used as a non-aqueous solvent, and benzoic acid is dissolved to a concentration of 5 mM as a proton source. 4 is preferably stirred for 24 hours for ion exchange.
- the ion exchange rate of mobile lithium ions contained in Li 14-2x Zn 1+x (GeO 4 ) 4 to protons was adjusted by changing the concentration of Li 14-2x Zn 1+x (GeO 4 ) 4 with respect to the solvent and the acid species. can do. It has been confirmed that when the solvent is aqueous and the acid species is acetic acid, the ion exchange rate of mobile lithium ions contained in Li 14-2x Zn 1+x (GeO 4 ) 4 to protons is 100%.
- the proton conductor powder after ion exchange is obtained by removing the solvent.
- the drying temperature at this time is preferably at least the boiling point of the solvent used and at most 300°C. If the temperature is lower than the boiling point, the problem of residual solvent occurs, and if the temperature is higher than 300° C., the problem of desorption of protons in the sample occurs. A powdery proton conductor is thus obtained.
- the powdered proton conductor prepared as described above can be formed into a thin film, and can be used as an electrolyte membrane for fuel cells, electrolytic cells, solid batteries, and the like.
- a direct fuel cell which is a type of fuel cell, supplies a substance different from hydrogen as a fuel to the fuel electrode of the fuel cell. Activate the oxygen fuel cell.
- the chemical energy of the generated hydrogen gas is higher than that of the fuel used, so the hydrogen generation reaction from the fuel is an endothermic reaction.
- the combustion reaction of hydrogen progresses and is converted into electrical energy and thermal energy.
- a fuel cell using hydrogen, methylcyclohexane, ammonia, methanol, dimethyl ether, formic acid, etc. as fuel which can operate in a temperature range of 200 ° C. or higher.
- the reaction temperature for generating hydrogen from these fuels is in the temperature range of 300 to 500° C., and a hydrogen generating catalyst suitable for each fuel should be used.
- the hydrogen generation catalyst may be a known catalyst, an ammonia decomposition catalyst, a reforming catalyst such as methanol, dimethyl ether, or formic acid.
- Cyclohexane which is used as a fuel in direct fuel cells, is one of the organic chemical hydride compounds expected as a hydrogen energy carrier.
- the organic chemical hydride method is a method of "storing" and “carrying” hydrogen as an organic chemical hydride compound (hydrogenated organic compound) in which hydrogen is incorporated into the molecular structure of a chemical product through a chemical reaction.
- hydrogen gas is reacted with toluene in a hydrogenation reactor to produce methylcyclohexane (MCH).
- MCH methylcyclohexane
- Toluene is a chemical that is liquid at normal temperature and normal pressure, and is a general-purpose chemical that is widely used in large quantities as a general-purpose solvent with low toxicity for paints and the like.
- MCH is in a liquid state under normal temperature and pressure.
- Existing chemical tankers are used for large-scale transportation of chemical products like toluene, and MCH is also used at home as a solvent for correction ink. It is an industrial agent that is used as office supplies and is a general-purpose chemical with low toxicity.
- This MCH can be transported by sea on a large scale using large vessels such as chemical tankers.
- Marine-transported MCH is used for power generation and chemical raw materials after being unloaded into large tanks in coastal areas. It can be transported to bases and remote islands in the same way as existing kerosene and gasoline.
- the MCH transported to the place where hydrogen is used generates hydrogen in the dehydrogenator, and the generated hydrogen is supplied as power generation and chemical raw materials. Since the MCH after generating hydrogen in this dehydrogenation reaction returns to toluene, the toluene is transported again to the hydrogen production site and reused again as a raw material for the hydrogenation reaction.
- the characteristics of the organic chemical hydride method and the process of completing the international hydrogen supply chain demonstration between Southeast Asia and Japan completed in 2020 and moving to the commercialization stage are described in the literature (Journal of the Gas Turbine Society, Vol.49, No. 2, p.1-6 (2021)).
- the organic chemical hydride method has been proposed since the 1980s, but the dehydrogenation catalyst that generates hydrogen from MCH that has taken in hydrogen has an extremely short life, making it difficult to implement industrially.
- the key to technological development was the development of a new dehydrogenation catalyst with sufficient performance such as catalyst life for industrial use.
- development of a platinum-supported alumina catalyst with high performance has been completed, and technical improvements that contribute to cost reductions in each process of the above scheme are being implemented.
- a hydrogen energy carrier system based on the organic chemical hydride method. is the only system whose technology has been established after all processes have been verified, and which can be put into practical use at an early stage.
- Japan has included a policy to promote the practical application and spread of hydrogen energy as a national policy in the 4th Strategic Energy Plan after the Great East Japan Earthquake. has been decided by the Cabinet.
- the organic chemical hydride method mentioned above is a hydrogen energy carrier that “stores” and “transports” hydrogen energy on a large scale, and its practical application is included in the basic hydrogen strategy. 30/Nm 3 , and ⁇ 20/Nm 3 for 2050. For this reason, there is a demand for cost reduction through continuous improvement technology development.
- the 2030 target of ⁇ 30/ Nm3 is planned to be achieved through technological improvements and the diversion of existing facilities, but the 2050 target of ⁇ 20/ Nm3 is unlikely to be achieved.
- the MCH manufacturing side is at the stage of planning various improvements and developments, such as increasing the size of tankers and using MCH after transportation. Since it can be used for fuel cells, we recognize that it is a technology that can be expected to have an extremely high cost reduction effect when used for power generation.
- the dehydrogenation reaction of MCH is an endothermic reaction as in the case of other hydrogen generating raw materials described above, and the dehydrogenation reaction requires heat corresponding to 30% of the energy possessed by the hydrogen transported as MCH. For this reason, when hydrogen is generated by the current dehydrogenation equipment and used as power generation fuel for turbines, SOFCs, etc., the heat generated by these high-temperature power generation equipment must be used for the dehydrogenation reaction, which poses the problem of reduced power generation efficiency. In addition, since CO 2 is generated when fossil fuel is used as a heat source, there is also a problem that LCA CO 2 increases when hydrogen is used.
- the heat generated at the counter electrode of the fuel electrode can be used for the dehydrogenation reaction of the fuel electrode .
- the problem to be solved is also solved.
- the hydrogen supply cost is ⁇ 30/ Nm3 in 2030
- the purchase cost of natural gas necessary for the dehydrogenation heat source will be ⁇ 5/Nm3 or more .
- the MCH direct fuel cell does not require a heat source, there is a cost reduction effect of ⁇ 5/Nm3 or more.
- This catalyst is a platinum-supported alumina catalyst in which fine particles of platinum, which is an active metal, are supported on a ⁇ -alumina carrier. Compared to conventional platinum-alumina catalysts, platinum particles that are extremely small in size are supported. .
- the proton conductor according to this embodiment can be used as a proton exchange membrane for electrolytic cells.
- This makes it possible to provide an electrolytic cell that operates in a medium temperature range of 200 to 600°C.
- a chloralkali electrolytic cell that operates at about 90° C. and a PEM electrolytic cell in which both electrodes are provided on both sides of a polymer electrolyte membrane for water electrolysis have been put to practical use.
- a solid electrolyte electrolyzer (SOEC) that utilizes SOFC fuel cell cells for high-temperature electrolysis is being researched and developed.
- SOEC solid electrolyte electrolyzer
- the proton conductor according to the present embodiment has a high electrical conductivity at 200 to 600° C.
- various electrolytic cells that operate in a temperature range of 200° C. or higher can be constructed by using the proton conductor as an ion exchange membrane. can do.
- BACKGROUND ART In recent years, technological development for manufacturing various substances by an electrolysis reaction has been actively carried out.
- the proton conductor according to this embodiment can increase the temperature of these electrolytic cells and improve efficiency.
- the proton conductor according to this embodiment has a wide range of applications and a very large ripple effect.
- FIG. 1 is a graph showing the conductivity of various solid electrolytes.
- the conductivity plotted with circles indicates the conductivity of the proton conductor ((Li, H) 14 Zn(GeO 4 ) 4 ) according to this embodiment.
- the electrical conductivity of the proton conductor according to this embodiment at 300°C is higher than that of cesium dihydrogen phosphate (CsH 2 PO 4 ) at 250°C.
- the electrical conductivity of the proton conductor according to the present embodiment at 600° C. is higher than that of various solid electrolytes used in SOFCs.
- Nafion ion-exchange membrane which is a type of organic polymer ion-exchange membrane used in automotive fuel cells
- the conductivity of the proton conductor according to this embodiment at 500 to 600°C is equivalent to the conductivity of the Nafion membrane at an operating temperature of about 90°C.
- a PEFC using a Nafion ion exchange membrane is a 100 kW class fuel cell and is small in size. SOFCs are much larger in size than PEFCs. When the proton conductor according to this embodiment is used as a solid electrolyte, the operating temperature of the current SOFC can be lowered and the size can be reduced.
- the proton conductor according to this embodiment has a higher electrical conductivity than that of cesium dihydrogen phosphate as a solid electrolyte that operates in the temperature range of 200°C to 250°C.
- the proton conductor according to this embodiment has high electrical conductivity even in the temperature range of 300 to 600.degree.
- the proton conductor according to this embodiment has a conductivity equivalent to that of Nafion ion exchange membranes used in fuel cells for automobiles in a temperature range of 500° C. or higher.
- the proton conductor according to the present embodiment can be used at a high temperature of 600° C. or higher, and the electrical conductivity at 600° C. is equivalent to that of the solid electrolytes used in existing SOFCs.
- the proton conductor according to this embodiment moves protons instead of oxide ions, its operating temperature can be lowered to about 600.degree. As a result, the proton conductor according to this embodiment can provide a fuel cell that is more efficient and easier to handle than existing SOFCs.
- Li 14-2x Zn 1+x (GeO 4 ) 4 is immersed in a non-aqueous organic solution containing acid and stirred to form Li 14-2x Zn 1+x (
- the ion exchange rate of mobile lithium ions contained in GeO 4 ) 4 to protons can be 40% or more and 70% or less.
- the proton conductor has improved structural stability and relatively high electrical conductivity.
- Lithium carbonate was used as the Li source, zinc oxide as the Zn source, and germanium oxide as the Ge source. Lithium carbonate, zinc oxide, and germanium oxide were added in a weight ratio of 25:4:21, and the slurry was finely mixed with ethanol and zirconia balls for 24 hours in a closed vessel. , and molded into pellets in a press. The pellets were calcined in air at 1150° C. for 5 hours in an alumina crucible, pulverized in a magnetic mortar for 2 hours, molded into pellets again, and calcined in air at 1150° C. for 5 hours in an alumina crucible. The fired pellets were again pulverized in a magnet mortar for 2 hours to obtain Li 14 Zn(GeO 4 ) 4 powder before ion exchange.
- Example 1 A 2.5 g sample of Li 14 Zn(GeO 4 ) 4 powder before ion exchange was mixed with toluene from which water was removed with a dehydrating agent as a non-aqueous solvent, and benzoic acid was added as a proton source to a concentration of 5 mM. Ion exchange was carried out in 100 ml of dissolved non-aqueous organic solution with stirring for 24 hours. After the ion exchange, the powder was collected by filtration, washed with toluene, and vacuum-dried at 130° C. overnight to obtain the ion-exchanged powder of Example 1. The ion exchange rate of mobile lithium ions to protons in the proton conductor of Example 1 was 52%.
- Example 1 Comparison between Example 1 and Comparative Example 1
- the conductivity of the ion exchangers of Example 1 and Comparative Example 1 was measured.
- the measurement was performed using an electrochemical evaluation device (ModuLab, manufactured by Solartron Analytical) in a 10% humidified nitrogen atmosphere by a direct current four-terminal method and an alternating current two-terminal method.
- the measurement results are shown in Table 1 below.
- Example 1 had a higher electrical conductivity than Comparative Example 1.
- Example 2 Using dimethyl sulfoxide as a non-aqueous solvent and using m-nitrophenol, acetic acid, benzoic acid, p-toluenesulfonic acid, oxalic acid, and methanesulfonic acid as proton sources, and varying the concentration in the range of 5 to 100 mM, An ion exchange operation was performed in the same manner as in 1. After that, the amount of ion exchange was confirmed by thermogravimetric analysis of the Li 14 Zn(GeO 4 ) 4 powder subjected to the ion exchange operation. As a result, the ion exchange rate was 45-65% for each proton source.
- the proton conductive material of the present invention can be suitably used as ion-exchange membranes for various fuel cells and various electrolytic cells that operate in a medium temperature range of 200 to 600°C, which has not existed before.
- various fuels that can generate hydrogen in the medium temperature range are directly supplied to the fuel cell as fuel for the fuel cell, and hydrogen is generated by the catalytic reaction in the cell to generate power from the fuel cell.
- the reaction heat required for the reaction to generate hydrogen from the fuel cell can be covered by the fuel cell reaction.
- it is possible to provide fuel cells with higher efficiency that can operate in the medium temperature range compared to low temperature types. can be realized.
- it can be applied to medium-temperature electrolysis tanks.
- the present invention is a basic technology relating to proton conductors used in cells such as fuel cells and electrolysis, and thus has extremely high industrial applicability.
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Abstract
Description
Li源として炭酸リチウム、Zn源として酸化亜鉛、Ge源として酸化ゲルマニウムを用いた。炭酸リチウム、酸化亜鉛、酸化ゲルマニウムを重量比で25:4:21の比率で加え、密閉容器内でエタノールとジルコニアボールと共に24時間微細化混合したスラリーを130℃で乾燥させて得られた粉末を、プレス機でペレットに成型した。このペレットをアルミナるつぼ内で空気中1150℃、5時間焼成した後に、マグネット乳鉢で2時間粉砕し、ふたたびペレットに成型してアルミナるつぼ内で空気中1150℃、5時間焼成した。焼成後のペレットを再びマグネット乳鉢で2時間粉砕してイオン交換前のLi14Zn(GeO4)4粉末を得た。
イオン交換前のLi14Zn(GeO4)4粉末の試料2.5gを、非水系溶媒として脱水剤で水分を除去したトルエンを用い、ここにプロトン源として安息香酸を5mMの濃度となるように溶解させた非水系有機溶液100ml中で、24時間攪拌してイオン交換を実施した。イオン交換後にろ過して粉末を回収して、トルエンで洗浄後に、130℃で一晩真空乾燥することによって、実施例1のイオン交換粉末を得た。実施例1のプロトン伝導体の可動リチウムイオンのプロトンへのイオン交換率は52%であった。
イオン交換前のLi14Zn(GeO4)4粉末を重量の40倍の5mM酢酸水溶液中、室温下で24時間攪拌してイオン交換を行い、ろ過洗浄後に130℃の真空乾燥機で乾燥を行って比較例1のイオン交換体を得た。比較例1のプロトン伝導体の可動リチウムイオンのプロトンへのイオン交換率は100%であった。
実施例1及び比較例1のイオン交換体の導電率を測定した。測定は、電気化学評価装置(Solartron analytical社製、ModuLab)を使用して、10%加湿窒素雰囲気下で、直流四端子法及び交流二端子法で行った。測定結果を以下の表1に示す。
非水系溶媒としてジメチルスルホキシドを用いプロトン源としてm-ニトロフェノール、酢酸、安息香酸、p-トルエンスルホン酸、シュウ酸,メタンスルホン酸を用いて、5~100mMの範囲で濃度を変えて、実施例1と同様の方法でイオン交換操作を行った。その後、イオン交換操作を行ったLi14Zn(GeO4)4粉末の熱重量分析によって、イオン交換量を確認した。結果、各プロトン源に対して、イオン交換率は45~65%であった。
非水溶媒のみで、イオン交換前のLi14Zn(GeO4)4粉末をイオン交換した際の効果を確認した。非水溶媒としてトルエン、テトラヒドロフラン、エタノール、N,N-ジメチルホルムアミド、ジメチルスルホキシド、炭酸プロピレンを脱水剤で処理して用い、プロトン源を用いずに比較例1と同様の方法でイオン交換操作を行った。その後、イオン交換操作を行ったLi14Zn(GeO4)4粉末の熱重量分析によって、イオン交換量を確認した。結果、イオン交換はほとんど進まないことが確認された。
Claims (9)
- Li14-2xZn1+x(GeO4)4のリチウムイオンの一部がプロトンに置換され、300℃において0.01S/cm以上の導電率を有するプロトン伝導体。
ここでxは、0以上の数である。 - 前記xは、0である請求項1に記載のプロトン伝導体。
- Li14-2xZn1+x(GeO4)4に含まれる可動リチウムイオンの40%以上70%以下がプロトンに置換されている請求項1又は2に記載のプロトン伝導体。
- Li14-2xZn1+x(GeO4)4に含まれる可動リチウムイオンの50%以上60%以下がプロトンに置換されている請求項1又は2に記載のプロトン伝導体。
- Li14-2xZn1+x(GeO4)4の全てのリチウムイオンに対する可動リチウムイオンの割合が(3-x)/(14-2x)である請求項3又は4に記載のプロトン伝導体。
- プロトン伝導体の製造方法であって、
Li14-2xZn1+x(GeO4)4を、酸を含む非水系溶媒に浸漬させることによって、リチウムイオンの一部をプロトンに置換する工程を含むプロトン伝導体の製造方法。
ここでxは、0以上の整数である。 - 前記xは、0である請求項6に記載のプロトン伝導体の製造方法。
- 前記酸は、安息香酸、m-ニトロフェノール、酢酸、p-トルエンスルホン酸、シュウ酸、及びメタンスルホン酸を含む群から選択される少なくとも1つを含む請求項6又は7に記載のプロトン伝導体の製造方法。
- 前記非水系溶媒は、トルエン、ジメチルスルホキシド、テトラヒドロフラン、N,N-ジメチルホルムアミドを含む群から選択される少なくとも1つを含む請求項6~8のいずれか1つの項に記載のプロトン伝導体の製造方法。
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JP2005166486A (ja) | 2003-12-03 | 2005-06-23 | Kri Inc | 直接型燃料電池システム |
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JP2005166486A (ja) | 2003-12-03 | 2005-06-23 | Kri Inc | 直接型燃料電池システム |
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