WO2012033050A1 - イオン伝導性材料及びその製造方法 - Google Patents
イオン伝導性材料及びその製造方法 Download PDFInfo
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- WO2012033050A1 WO2012033050A1 PCT/JP2011/070165 JP2011070165W WO2012033050A1 WO 2012033050 A1 WO2012033050 A1 WO 2012033050A1 JP 2011070165 W JP2011070165 W JP 2011070165W WO 2012033050 A1 WO2012033050 A1 WO 2012033050A1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/18—Compositions for glass with special properties for ion-sensitive glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/14—Compositions for glass with special properties for electro-conductive glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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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
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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
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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
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 an ion conductive material (ion conductor) and a method for producing the same, and more particularly to an ion conductive material having a good proton conductivity and a method for producing the same.
- Fuel cells have a high theoretical value for power generation efficiency and can also use waste heat, so they can significantly reduce carbon dioxide and provide sufficient electricity and heat compared to state-of-the-art thermal power generation. Is possible. Further, solid polymer fuel cells represented by perfluoroalkyl sulfonic acid polymers (registered trademark Nafion) and the like have attracted attention as small-scale power generation applications such as home use and in-vehicle use. However, at present, the solid polymer fuel cell has a problem that its power generation efficiency (about 33%) is low because its operating temperature is as low as about 80 ° C.
- the phosphoric acid fuel cell has been put into practical use, there are problems that the operating temperature is about 200 ° C. and the manufacturing cost is high. Furthermore, since the solid oxide fuel cell has an extremely high operating temperature of around 1000 ° C., there is a problem that inexpensive stainless steel or the like cannot be used as a constituent member of the fuel cell. Under such circumstances, a fuel cell that can operate satisfactorily in a temperature range corresponding to the GAP portion shown in FIG. 1, that is, an intermediate temperature range of 200 to 500 ° C. is demanded. If the operating temperature of the fuel cell can be increased to about 500 ° C., it is said that overall efficiency exceeding 50% can be achieved.
- Non-Patent Document 1 In order to increase the operating temperature to about 500 ° C., it is essential to develop an electrolyte that exhibits high proton conductivity or oxygen ion conductivity in the temperature range. However, the actual situation is that no ion-conductive material having practical electric conductivity has been reported yet in an intermediate temperature range of 200 to 500 ° C. (see Non-Patent Document 1).
- Patent Document 1 phosphate glass is currently being studied as a candidate for ion conductive materials that operate in the middle temperature range, particularly proton conductive materials (see Patent Document 1 and Non-Patent Document 2).
- Patent Document 1 and Non-Patent Document 2 are produced by a sol-gel method, humidification is required during use, heat resistance is low, and moldability (particularly, , Film formability) and chemical durability.
- the present invention has developed an ion conductive material, particularly a proton conductive material, which has good ion conductivity in the middle temperature range of 200 to 500 ° C. without humidification, and has excellent moldability and long-term stability. Doing this is a technical issue.
- the present inventors have solved the above technical problem by regulating the contents of P 2 O 5 , SiO 2 , and alkali metal oxides within a predetermined range and using them in ion conductive materials.
- the present invention is found and proposed as the present invention. That is, the ion conductive material of the present invention has a composition expressed in mol%, P 2 O 5 15 to 80%, SiO 2 0 to 70%, R 2 O (Li 2 O, Na 2 O, K 2 O , Rb 2 O, Cs 2 O, and Ag 2 O) in an amount of 5 to 35%.
- the ion conductive material of the present invention contains 15 to 80% of P 2 O 5 , 0 to 70% of SiO 2 , and 5 to 35% of R 2 O. In this way, even if it is not humidified, it exhibits good ionic conductivity in the middle temperature range of 200 to 500 ° C., and long-term stability is also improved. In addition, since the meltability is improved in this way, it becomes easy to produce an ion conductive material by the melting method, and as a result, the moldability, homogeneity, and denseness can be improved.
- the ion conductive material of the present invention may contain at least two or more of Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 2 O, and Ag 2 O, which are R 2 O components. preferable. By doing so, the ion conduction of alkali ions is suppressed by the mixed alkali effect, so that the proportion of proton conduction increases, and as a result, it becomes easy to apply to the electrolyte of the fuel cell.
- the content of the two or more R 2 O components contained in the ion conductive material of the present invention is preferably 0.1 mol% or more.
- the content of P 2 O 5 is preferably 15 to 60%, and the content of SiO 2 is preferably 10 to 70%.
- the ion conductive material of the present invention preferably has a molar ratio (Na 2 O + K 2 O) / R 2 O of 0.2 to 1.0. In this way, it becomes easy to improve proton conductivity.
- “Na 2 O + K 2 O” is the total amount of Na 2 O and K 2 O.
- the ion conductive material of the present invention preferably has a molar ratio Na 2 O / R 2 O of 0.2 to 0.8. In this way, it becomes easy to improve proton conductivity.
- the ion conductive material of the present invention preferably has a molar ratio K 2 O / R 2 O of 0.2 to 0.8. In this way, it becomes easy to improve proton conductivity.
- the ion conductive material of the present invention preferably further contains 0.1 mol% or more of Al 2 O 3 as a composition. In this way, since the deliquescence is lowered, long-term stability is easily improved.
- the ion conductive material of the present invention preferably has an ion conductivity log 10 ⁇ (S / cm) at ⁇ 500 ° C. of ⁇ 5.5 or more and a proton transport number at 500 ° C. of 0.7 or more.
- ion conductivity at 500 ° C.” is obtained by, for example, alternating current after forming an Ag electrode with Ag paste on the surface of a sample (dimensions: 1.5 cm ⁇ 1.0 cm ⁇ thickness 1.0 mm, optically polished). It can be measured by the impedance method.
- “Proton transport number at 500 ° C.” is obtained, for example, by sputtering Pt on the surface of a sample (size: 1.5 cm ⁇ 1.0 cm ⁇ thickness 1.0 mm, optically polished) to form a Pt electrode. Then, measure the electromotive force when changing the hydrogen partial pressure on the other surface of the sample with one side of the sample as the reference side in an atmosphere of 1% by volume of hydrogen, and then calculating from the slope based on the Nernst equation. Can do.
- the ion conductive thin film material of the present invention preferably has an area resistance value ( ⁇ ⁇ cm 2 ) at 500 ° C. of 30 or less.
- the “area resistance value at 500 ° C.” can be measured by, for example, an AC impedance method.
- an Ag electrode formed on the surface of a sample (dimension: 1.5 cm ⁇ 1 cm, optically polished) with an Ag paste can be used.
- the ion conductive material of the present invention is preferably amorphous with a crystallinity of 50% or less.
- crystallinity for example, an X-ray diffractometer (manufactured by Rigaku) is used, and a scattering intensity area measured in a diffraction angle 2 ⁇ of 10 to 60 ° and a crystal peak area are measured using a multiple peak separation method. And calculated as the ratio (%) of the crystal peak area to the scattering intensity area.
- the ion conductive material of the present invention preferably has a thin plate shape (including a thin film shape) and a thickness of 1 to 500 ⁇ m.
- the sheet resistance value becomes small in the middle temperature range of 200 to 500 ° C., so that the ionic conductivity is increased in the middle temperature range of 200 to 500 ° C., and the performance of the electrochemical device is improved.
- the resistance of the electrolyte is reduced, so that the resistance loss is reduced, and as a result, the power generation efficiency of the fuel cell is improved.
- it is a thin plate shape, and homogeneity and denseness are favorable, it becomes easy to suppress a crossover in a direct methanol fuel cell.
- the ion conductive material of the present invention is preferably used for an electrochemical device.
- the ion conductive material of the present invention is preferably used for a fuel cell.
- the method for producing an ion conductive material according to the present invention is a method for producing the above ion conductive material, characterized by having a step of forming the molten glass obtained after melting the raw material. If it does in this way, a moldability can be improved.
- a molding method it is preferable to employ an overflow downdraw method, a slot downdraw method, or a redraw method. These molding methods have the advantage of being easily molded into a thin plate shape.
- composition of the ion conductive material of the present invention is limited as described above.
- “%” indicates mol%.
- P 2 O 5 is a component that increases ionic conductivity.
- the content of P 2 O 5 is 15 to 80%, preferably 20 to 70%, more preferably 25 to 65%, still more preferably 25 to 60%, particularly preferably 25 to 50%, and most preferably 25 to 45%. %.
- the content of P 2 O 5 decreases, the ionic conductivity tends to decrease.
- the content of P 2 O 5 increases, it becomes easy to deliquesce, so that long-term stability tends to be lowered.
- SiO 2 is a network former and a component that enhances chemical durability.
- the content of SiO 2 is 0 to 70%, preferably 0.1 to 60%, more preferably 1 to 50%, still more preferably 5 to 49%, and particularly preferably 10 to 40%.
- chemical durability tends to decrease.
- the content of SiO 2 increases, the ionic conductivity tends to decrease, and it tends to devitrify during melting and molding, and the viscosity increases unreasonably, making melting and molding difficult. Furthermore, a temperature range in which the viscosity changes abruptly tends to occur, and the moldability tends to decrease.
- the content of R 2 O (the total amount of Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 2 O, and Ag 2 O) is 5 to 35%, preferably 8 to 30%, more preferably 10-25%.
- the content of R 2 O decreases, the ionic conductivity tends to decrease, and the viscosity increases unreasonably, making melting and molding difficult.
- the content of R 2 O increases chemical durability tends to decrease. Moreover, it becomes easy to generate
- Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 2 O, and Ag 2 O which are R 2 O components, and particularly preferably 3 or more types. If only one R 2 O component is used, the mixed alkali effect cannot be enjoyed, so that it may be difficult to suppress ionic conduction of alkali ions, resulting in a decrease in proton conduction ratio (proton transport number). It becomes easy.
- Li 2 O is a component that increases the ionic conductivity and is a component that decreases the viscosity and increases the meltability.
- the content of Li 2 O is preferably 0 to 20%, 0 to 15%, particularly preferably 0 to 10%. When the content of Li 2 O increases, chemical durability tends to decrease.
- Na 2 O is a component that increases the ionic conductivity and is a component that decreases the viscosity and increases the meltability.
- the content of Na 2 O is preferably 0 to 25%, 1 to 20%, particularly 3 to 15%.
- chemical durability tends to decrease.
- the viscosity is unduly increased, melting, molding becomes difficult.
- K 2 O is a component that increases the ionic conductivity and is a component that decreases the viscosity and increases the meltability.
- the content of K 2 O is preferably 0 to 25%, 1 to 20%, particularly 3 to 15%.
- chemical durability tends to decrease.
- the ionic conductivity tends to decrease, and the viscosity increases unreasonably, making melting and molding difficult.
- Ag 2 O is a component that increases the ionic conductivity, and also decreases the viscosity and increases the meltability.
- the content of Ag 2 O is preferably 0 to 20%, 0 to 15%, 0 to 10%, particularly not substantially contained, that is, 0.1% or less. When the content of Ag 2 O is increased, the raw material cost is likely to increase.
- the molar ratio (Na 2 O + K 2 O) / R 2 O is preferably 0.2 to 1.0, 0.25 to 1.0, and particularly preferably 0.3 to 1.0. If it does in this way, while it becomes easy to improve proton conductivity, it can enjoy a mixed alkali effect using an inexpensive raw material. “Na 2 O + K 2 O” indicates the total amount of Na 2 O and K 2 O.
- the molar ratio Na 2 O / R 2 O is preferably 0.2 to 0.8, 0.25 to 0.7, particularly 0.3 to 0.65.
- the molar ratio K 2 O / R 2 O is preferably 0.2 to 0.8, 0.25 to 0.7, and particularly preferably 0.3 to 0.65.
- the molar ratio Li 2 O / R 2 O is preferably 0.8 or less, 0.6 or less, particularly 0.5 or less for the same reason.
- Al 2 O 3 is a component that suppresses deliquescence and improves long-term stability.
- the content of Al 2 O 3 is preferably 0 to 20%, 0.1 to 16%, 1 to 12%, particularly 2 to 10%.
- the content of Al 2 O 3 is increased, the ionic conductivity is likely to be lowered, the glass is easily devitrified during melting and molding, and the viscosity is unduly increased to make melting and molding difficult. Furthermore, a temperature range in which the viscosity changes abruptly tends to occur, and the moldability tends to decrease.
- MgO, CaO, SrO, BaO, ZrO 2 , TiO 2 , La 2 O 3 , ZnO, Sb 2 O 3 are used for the purpose of adjusting viscosity, improving chemical durability, and improving the clarification effect.
- the content of MgO + CaO + SrO + BaO causes a decrease in ionic conductivity. desirable.
- the contents of Bi 2 O 3 , CoO, Cr 2 O 3 , MnO 2 , and NiO are each preferably 1% or less because they cause an increase in raw material cost, and are not substantially contained, that is, 0.1% or less. desirable. Since B 2 O 3 also causes an increase in raw material cost, it is preferably 2% or less, and is preferably not contained, that is, 0.1% or less.
- the ion conductivity log 10 ⁇ (S / cm) at 500 ° C. is preferably ⁇ 5.5 or more, ⁇ 5.0 or more, particularly preferably ⁇ 4.8 or more. This makes it suitable as a fuel cell in an intermediate temperature range of 200 to 500 ° C.
- the proton transport number at 500 ° C. is preferably 0.7 or more, 0.8 or more, and particularly preferably 0.9 or more. In this way, since the rate of proton conduction increases, it can be easily applied to a fuel cell.
- the area resistance value ( ⁇ ⁇ cm 2 ) at 500 ° C. is preferably 30 or less, 15 or less, particularly preferably 10 or less.
- the ionic conductivity is increased in the middle temperature range of 200 to 500 ° C., and the performance of the electrochemical device is improved.
- the resistance of the electrolyte is reduced, so that the resistance loss is reduced, and as a result, the power generation efficiency of the fuel cell is improved.
- the thickness is preferably 1 to 500 ⁇ m, 2 to 200 ⁇ m, 3 to 100 ⁇ m, particularly preferably 5 to 50 ⁇ m or less.
- the thickness is smaller than 1 ⁇ m, the handling property is lowered and the production efficiency of the electrochemical device is lowered.
- the thickness is larger than 500 ⁇ m, the sheet resistance value increases, the performance of the electrochemical device decreases, and particularly the power generation efficiency of the fuel cell decreases.
- the ion conductive material of the present invention is preferably amorphous with a crystallinity of 50% or less. If it does in this way, it will become easy to improve homogeneity and denseness. Furthermore, the ion conductive material of the present invention is preferably phase-separated and more preferably spinodal phase-separated in view of ion conductivity. This makes it easy to use a high polarity phase obtained by phase separation as an ion conduction path, so that the concentration of the conductive carrier can be locally increased, and ion conductivity can be easily increased.
- a method for producing the ion conductive material of the present invention will be described. First, raw materials are prepared so as to be in the above composition range. Next, the raw materials prepared in the continuous melting furnace are charged and then melted by heating. Subsequently, the molten glass obtained is supplied to a molding apparatus, molded into a flat plate shape or a thin plate shape, and then slowly cooled. In this way, an ion conductive material can be produced.
- the ion conductive material of the present invention does not completely exclude the embodiment produced by the sol-gel method, but as described above, such an embodiment is disadvantageous from various viewpoints.
- the melting temperature is preferably 800 ° C. or higher, 1000 ° C. or higher, 1200 ° C. or higher, particularly 1400 ° C. or higher. If it does in this way, it will become easy to shorten melting time, and it will become easy to homogenize an ion conductive material.
- phase separation and crystallization can also be performed by reheating after slow cooling.
- glass that is not substantially phase-separated is preferable, and it is preferable not to have a phase separation step by heat treatment.
- a molding method of molten glass a molding method such as a roll-out method, an overflow down-draw method, a slot-down draw method, a float method, a redraw method or the like can be employed.
- the overflow down draw method, the slot down draw method, and the redraw method are preferable because they can be easily formed into a thin plate shape and have excellent surface accuracy.
- Tables 1 to 4 show examples of the present invention (sample Nos. 1 to 34).
- Each sample in the table was prepared as follows. First, raw materials were prepared so as to have the composition shown in the table, and then charged into an alumina crucible and melted at 1400 to 1600 ° C. for 2 hours. Next, the obtained molten glass was poured out on a carbon plate, formed, and then gradually cooled in an electric furnace maintained at 600 ° C. Subsequently, after processing into a flat plate shape of 1.5 cm ⁇ 1 cm ⁇ thickness 1.5 mm, each sample is obtained by polishing the surface of the sample in the order of # 100, # 400, # 2000 using polishing paper. It was. Each sample was evaluated for ionic conductivity, proton transport number, deliquescence, water resistance, vitrification, and moldability.
- Each sample was confirmed to be amorphous (glass) having a crystallinity of 50% or less by an X-ray diffractometer. Further, a molten glass was prepared in the same manner as described above using a Pt crucible, and formed into a balloon shape using a blower, and then 1.5 cm ⁇ 1 cm was cut with a glass cutter to obtain a measurement sample. The sheet resistance value was measured for this measurement sample. These results are shown in the table.
- the ionic conductivity log 10 ⁇ (S / cm) is a value measured by the AC impedance method at each temperature in the table after forming an Ag electrode on the surface of the sample with Ag paste.
- the proton transport number at 500 ° C. was evaluated as follows. First, Pt was sputtered on the surface of the sample to form a Pt electrode. Next, the electromotive force when the hydrogen partial pressure on the other surface was changed after measuring one side of the sample as the reference side and making the atmosphere 1% hydrogen by volume was measured. Subsequently, the proton transport number was calculated from the slope based on the Nernst equation.
- a sample was immersed in pure water, allowed to stand at room temperature for 24 hours, washed and dried, and then the change in mass of the sample was measured to obtain an indicator of deliquescence.
- the ratio (%) of the mass decrease with respect to the mass of the sample before immersion is described.
- the sample was immersed in pure water in a sealed container, allowed to stand at 60 ° C. for 24 hours, washed and dried, and then the change in mass of the sample was measured to obtain a water resistance index.
- the value (mg / cm 2 ) obtained by dividing the mass reduction amount with respect to the mass of the sample before immersion by the surface area of the sample is described.
- a molten glass produced in the same manner as described above was poured out using a Pt crucible, and the presence or absence of vitrification was confirmed. The case where vitrification was confirmed was evaluated as “ ⁇ ”, and the case where vitrification was not confirmed was evaluated as “x”.
- the area resistance value ( ⁇ ⁇ cm 2 ) was obtained by forming an Ag electrode on the surface of the sample using an Ag paste, measuring the resistance value by the AC impedance method at each temperature in the table, and then obtaining the resistance value. It is a value calculated from the resistance value and the area of the electrode.
- sample no. Nos. 1 to 3 and 15 have a very high proton transport number, high ion conductivity as a proton conductive material (proton conductor), and good evaluation of deliquescence.
- Sample No. Nos. 4 to 14 and 16 to 34 are expected to have high proton transport numbers, high ion conductivity as proton conductive materials (proton conductors), and good deliquescence evaluation.
- Sample No. 1 to 31, 34 were vitrified. Sample No. Nos. 4 to 31 and 34 had good moldability.
- sample No. 1, no. 7, no. No. 15 was subjected to a power generation test under the conditions of electrode: sputtered Pt, anode side: pure hydrogen, cathode side: pure oxygen, measurement temperature: 500 ° C., a voltage of 1.1 V, 0.2, 0.03, An output value of 0.3 mW / cm 2 was obtained. Therefore, sample no. 1, no. 7, no. 15 is considered to be applicable as an electrolyte for fuel cells. It is estimated that other samples can also be applied as fuel cell electrolytes.
- the ion conductive material of the present invention can be applied to electrochemical devices, and is suitable, for example, as an electrolyte for a fuel cell, an electrolyte for a capacitor, a sensing member for a gas sensor, and a humidity detecting member for a humidity control device.
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Abstract
Description
Claims (16)
- 組成として、モル%表示で、P2O5 15~80%、SiO2 0~70%、R2O(Li2O、Na2O、K2O、Rb2O、Cs2O、及びAg2Oの合量) 5~35%を含有することを特徴とするイオン伝導性材料。
- R2O成分であるLi2O、Na2O、K2O、Rb2O、Cs2O、及びAg2Oの内、少なくとも2種以上を含むことを特徴とする請求項1に記載のイオン伝導性材料。
- P2O5の含有量が15~60%であり、SiO2の含有量が10~60%であることを特徴とする請求項1又は2に記載のイオン伝導性材料。
- モル比(Na2O+K2O)/R2Oが0.2~1.0であることを特徴とする請求項1~3のいずれかに記載のイオン伝導性材料。
- モル比Na2O/R2Oが0.2~0.8であることを特徴とする請求項1~4のいずれかに記載のイオン伝導性材料。
- モル比K2O/R2Oが0.2~0.8であることを特徴とする請求項1~5のいずれかに記載のイオン伝導性材料。
- 更に、組成として、Al2O3を0.1モル%以上含むことを特徴とする請求項1~6のいずれかに記載のイオン伝導性材料。
- 500℃におけるイオン伝導率log10σ(S/cm)が-5.5以上であり、且つ500℃におけるプロトンの輸率が0.7以上であることを特徴とする請求項1~7のいずれかに記載のイオン伝導性材料。
- 500℃における面積抵抗値(Ω・cm2)が30以下であることを特徴とする請求項1~8のいずれかに記載のイオン伝導性薄膜材料。
- 結晶化度が50%以下の非晶質であることを特徴とする請求項1~9のいずれかに記載のイオン伝導性材料。
- 薄板形状を有し、その厚みが1~500μmであることを特徴とする請求項1~10の何れかに記載のイオン伝導性材料。
- 電気化学デバイスに用いることを特徴とする請求項1~11のいずれかに記載のイオン伝導性材料。
- 燃料電池に用いることを特徴とする請求項1~11のいずれかに記載のイオン伝導性材料。
- 請求項1~11のいずれかに記載のイオン伝導性材料を含むことを特徴とする電気化学デバイス。
- 請求項1~11のいずれかに記載のイオン伝導性材料の製造方法であって、
原料を溶融した後、得られた溶融ガラスを成形する工程を有することを特徴とするイオン伝導性材料の製造方法。 - 成形方法が、オーバーフローダウンドロー法、スロットダウンドロー法、リドロー法のいずれかであることを特徴とする請求項15に記載のイオン伝導性材料の製造方法。
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EP11823525.8A EP2615070A1 (en) | 2010-09-06 | 2011-09-05 | Ionically conductive material and process for producing same |
CN2011800414251A CN103068760A (zh) | 2010-09-06 | 2011-09-05 | 离子传导性材料及其制造方法 |
US13/820,579 US20130157172A1 (en) | 2010-09-06 | 2011-09-05 | Ionically conductive material and process for producing same |
KR1020137000260A KR20140020222A (ko) | 2010-09-06 | 2011-09-05 | 이온 전도성 재료 및 그 제조 방법 |
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EP (1) | EP2615070A1 (ja) |
KR (1) | KR20140020222A (ja) |
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CN110981186A (zh) * | 2020-01-02 | 2020-04-10 | 中国建筑材料科学研究总院有限公司 | 一种低电阻率的电子导电型玻璃及其制备方法和应用 |
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JP6992966B2 (ja) * | 2017-08-24 | 2022-01-13 | 株式会社住田光学ガラス | リチウムリン系複合酸化物の前駆体ガラス及びその製造方法、リチウムリン系複合酸化物の前駆体結晶化ガラスの製造方法、並びに、リチウムリン系複合酸化物粉末及びその製造方法 |
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- 2011-09-05 WO PCT/JP2011/070165 patent/WO2012033050A1/ja active Application Filing
- 2011-09-05 CN CN2011800414251A patent/CN103068760A/zh active Pending
- 2011-09-05 EP EP11823525.8A patent/EP2615070A1/en not_active Withdrawn
- 2011-09-05 US US13/820,579 patent/US20130157172A1/en not_active Abandoned
- 2011-09-05 KR KR1020137000260A patent/KR20140020222A/ko not_active Application Discontinuation
- 2011-09-06 TW TW100132125A patent/TW201228973A/zh unknown
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CN110981186A (zh) * | 2020-01-02 | 2020-04-10 | 中国建筑材料科学研究总院有限公司 | 一种低电阻率的电子导电型玻璃及其制备方法和应用 |
CN110981186B (zh) * | 2020-01-02 | 2022-10-14 | 中国建筑材料科学研究总院有限公司 | 一种低电阻率的电子导电型玻璃及其制备方法和应用 |
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CN103068760A (zh) | 2013-04-24 |
TW201228973A (en) | 2012-07-16 |
KR20140020222A (ko) | 2014-02-18 |
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