WO2010058562A1 - Corps à structure conductrice de protons et procédé de fabrication de celui-ci. - Google Patents

Corps à structure conductrice de protons et procédé de fabrication de celui-ci. Download PDF

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Publication number
WO2010058562A1
WO2010058562A1 PCT/JP2009/006180 JP2009006180W WO2010058562A1 WO 2010058562 A1 WO2010058562 A1 WO 2010058562A1 JP 2009006180 W JP2009006180 W JP 2009006180W WO 2010058562 A1 WO2010058562 A1 WO 2010058562A1
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Prior art keywords
proton
pyrophosphate
heat treatment
conducting structure
temperature
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PCT/JP2009/006180
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English (en)
Japanese (ja)
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銭谷勇磁
大塚隆
鈴木友子
小森知行
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パナソニック株式会社
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Priority to JP2010511844A priority Critical patent/JP4642155B2/ja
Priority to CN2009801203797A priority patent/CN102047351B/zh
Publication of WO2010058562A1 publication Critical patent/WO2010058562A1/fr
Priority to US12/871,266 priority patent/US8029941B2/en
Priority to US13/218,246 priority patent/US8298718B2/en
Priority to US13/617,793 priority patent/US8518595B2/en

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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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04701—Temperature
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4073—Composition or fabrication of the solid electrolyte
    • G01N27/4074—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen
    • 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
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • 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
    • 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
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • 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 conducting structure containing a pyrophosphoric acid metal salt and having excellent proton conductivity, and a method for producing the same.
  • Proton conductors conduct only protons and their electrical properties are insulators, and thus are used as electrolytes in fuel cells and the like.
  • solid electrolytes composed of solid polymer (for example, Nafion under the trade name) and solid oxides of the perovskite type are known, and are used in stationary fuel cells, small portable fuel cells, etc. ing.
  • the performance of the proton conductor is evaluated in proton conductivity (Siemens per centimeter: S / cm).
  • the proton conductivity indicates the unit volume and the number of protons conducted per unit time, and the proton conductivity in the operating temperature range is a standard for determining the performance of the proton conductor.
  • a proton conductor composed of a solid polymer currently put to practical use conducts protons by oxonium ion (H 3 O + ) in the solid polymer. Therefore, since proton conductivity is exhibited when a large amount of water is contained in the solid polymer, this solid polymer is used as a solid electrolyte at a temperature of 100 ° C. or less at which water does not evaporate.
  • a proton conductor composed of a perovskite-type solid oxide exhibits proton conductivity at a high temperature of 600 ° C. or more because the protons are conducted by hopping on the oxygen constituting the solid oxide. Therefore, this solid oxide is used as a solid electrolyte at a temperature of 600 ° C. or higher.
  • the proton conductivity of this solid oxide is raised by setting the temperature at the time of use to a higher temperature, but when it is used at a low temperature, the proton conductivity drops sharply. Since fuel cells increase the reaction efficiency of the catalyst when the operating temperature is raised and raise the power generation efficiency, a proton conductor that can be used at higher temperatures is desired. However, as described above, a solid polymer electrolyte can not be used at temperatures of 100 ° C. or higher. On the other hand, in order to operate a fuel cell at a high temperature of 600 ° C. or more, there are many restrictions such as the reliability and durability of the fuel cell system. Therefore, realization of a proton conductor that can be used in a temperature range of about 100 ° C. to 400 ° C. is desired.
  • tin pyrophosphate SnP 2 O 7 is produced by adding phosphoric acid H 3 PO 4 to tin oxide SnO 2 and heating, and the obtained tin pyrophosphate exhibits high proton conductivity Is disclosed.
  • this invention aims at providing the proton-conductive structure which shows a favorable proton conductivity in a temperature range 100 degreeC or more, and its manufacturing method.
  • the present inventors obtained the following findings as a result of intensive studies on a proton conductor which exhibits good proton conductivity in a temperature range of 100 ° C. or higher.
  • a metal salt of pyrophosphate such as tin pyrophosphate and phosphoric acid
  • two-stage heat treatment is performed under specific conditions to obtain a structure exhibiting extremely good proton conductivity in a medium temperature range it can.
  • the structure produced using tin pyrophosphate has a core of tin pyrophosphate inside, at least a part of the surface of the core contains Sn and P, and the arrangement of O relative to Sn It is coated with layers of order more than six.
  • the present invention has been made based on the above findings. That is, according to the present invention, a predetermined range of 80 ° C. or more and 150 ° C. or less is applied to a mixture containing pyrophosphate containing at least one metal element selected from the group consisting of Sn, Zr, Ti and Si and phosphoric acid.
  • the present invention relates to a method of manufacturing a proton conducting structure.
  • the present invention also includes a core comprising tin pyrophosphate, and a coating layer formed on at least a part of the surface of the core, containing Sn and O, and having a coordination number of O to Sn of more than 6
  • the invention also relates to a proton conducting structure. Furthermore, the present invention has a core comprising tin pyrophosphate, and a coating layer formed on at least a part of the surface of the core, containing Sn and O, and having a coordination number of O to Sn of more than 6
  • the present invention also relates to a power generation method including the step of generating electricity by conducting protons in a fuel cell including an electrolyte and an electrode provided on the surface of the covering layer.
  • the present invention it is possible to obtain a proton conducting structure exhibiting proton conductivity which greatly exceeds the performance of single phase tin pyrophosphate in a medium temperature range of 100 ° C. or more. As a result, it is possible to realize a practical proton conducting structure that exhibits good proton conductivity in an intermediate temperature range of 100 ° C. or higher where a conventional proton conductor can not be used.
  • FIG. 1 is a conceptual view of the configuration of a proton conducting structure according to an embodiment of the present invention.
  • a coating layer 12 containing Sn and O is coated on the surface of a core 11 made of tin pyrophosphate.
  • the covering layer 12 may cover the entire surface of the core 11. Also, as shown in FIG. 1, only a part of the surface of the core 11 may be coated. That is, the surface of the core may have a region not covered by the covering layer.
  • the shape and size of the core 11 made of tin pyrophosphate are not particularly limited. However, in order to increase the contact area with protons to achieve good proton conductivity, powder is preferred.
  • the covering layer 12 in the present invention contains Sn and O as constituent elements. Furthermore, in the covering layer 12, the coordination number of O to Sn (the number of O atoms per one Sn atom) exhibits a value larger than 6.
  • the coordination number of O with respect to Sn can be conveniently determined by measuring the structure by X-ray absorption spectroscopy, in particular, the conversion particle yield method. According to this method, it is possible to observe the coordination number to a depth of about 100 nm from the sample surface.
  • the covering layer 12 made of Sn and O containing material other than tin pyrophosphate is formed on the surface of the core 11 made of tin pyrophosphate.
  • the covering layer 12 does not contain phosphoric acid as a main component. However, a trace amount of phosphoric acid may be contained. As described later, since the constituent material of the covering layer is not observed by X-ray diffraction, the covering layer does not have a crystalline structure and is considered to be amorphous.
  • the coordination number of O to Sn indicated by the covering layer 12 is less than 12.
  • the coordination number of O to Sn represented by the covering layer 12 is preferably in the range of 7 to 8.5.
  • the thickness of the covering layer 12 is not particularly limited, and may vary depending on the place as shown in FIG. 1, but is usually about 0 to several hundred nm.
  • the proton conducting structure of the present invention is a solid electrolyte.
  • the core 11 is powdery, it is preferable that the proton conducting structure of the present invention is formed into a predetermined shape such as, for example, a pellet or a sheet in order to facilitate handling.
  • FIG. 2 is a flow chart showing a method of manufacturing a proton conducting structure according to the embodiment of the present invention.
  • a proton conducting structure can be prepared, for example, by the method as shown in FIG.
  • a pyrophosphate containing at least one metal element selected from the group consisting of Sn, Zr, Ti and Si that is, tin pyrophosphate, zirconium pyrophosphate, titanium pyrophosphate and silicon pyrophosphate
  • tin pyrophosphate At least one selected from the group consisting of
  • the above-mentioned proton conducting structure of the present invention can be obtained.
  • the resulting proton conducting structure has the same structure as the proton conducting structure of the present invention. That is, a core made of any of zirconium pyrophosphate, titanium pyrophosphate and silicon pyrophosphate, and a covering layer formed on at least a part of the surface of the core and containing any of Zr, Ti, Si and O It is believed that a proton conducting structure is formed.
  • a film layer is formed according to the substance of the above-mentioned core, for example, if a core is a zirconium pyrophosphate, the film layer contains Zr and O.
  • the core described above may contain not only any one of zirconium pyrophosphate, titanium pyrophosphate and silicon pyrophosphate but also any two or three of the three substances.
  • the above-mentioned coating layer contains not only one of Zr, Ti and Si but also any two or three of the three substances, depending on the kind of the material of the above-mentioned core. It may be
  • the above-mentioned metal pyrophosphate, preferably its powder, and phosphoric acid (H 3 PO 4 ) are mixed.
  • Phosphoric acid may be pure or aqueous solution may be used.
  • the conditions at the time of mixing are not particularly limited, it is preferable to sufficiently stir both components after combining the two components so that the surface of the metal pyrophosphate and the phosphoric acid contact uniformly.
  • the use ratio of the metal pyrophosphate and the phosphoric acid is not particularly limited. It can be suitably adjusted according to the surface area of the metal pyrophosphate.
  • the amount of phosphoric acid used is too small, the amount of formation of the coating layer is small, and sufficient proton conductivity can not be ensured, so the phosphorus in phosphoric acid to metal (Sn, Zr, Ti, Si) in metal pyrophosphate
  • the ratio is preferably such that the molar ratio of about 0.1 to about 0.7.
  • the particle size of the particles may be, for example, on the order of 0.1 to 10 microns or so.
  • the mixture obtained in the processing step 20 may be formed into a predetermined shape such as a sheet or a pellet using a general forming processor. Forming at this stage is preferable because it can be easily carried out.
  • the formed mixture is treated in the next heat treatment step 21.
  • the mixture obtained in the treatment step 20 is subjected to a heat treatment held at a temperature of 80 ° C. or more and 150 ° C. or less.
  • the heating temperature may be in the range of 80 ° C. to 150 ° C., and the temperature may be kept constant within this range. Also, the temperature may be changed continuously or stepwise within this range.
  • the time for performing the heat treatment can be appropriately adjusted, but for example, a treatment of about 10 minutes or more may be performed. Preferably, it is about 1 hour.
  • the mixture heat-treated in heat treatment step 21 is then treated in heat treatment step 22.
  • the mixture is heat-treated under temperature conditions of 200 ° C. or more and 400 ° C. or less.
  • the heating temperature in this step may be in the range of 200 ° C. to 400 ° C., and the temperature may be maintained constant in this range, or the temperature is changed continuously or stepwise in this range. It is also good.
  • the time for performing the heat treatment can be appropriately adjusted, but for example, a treatment of about 10 minutes or more may be performed. Preferably, it is about 1 hour.
  • the above two-step heat treatment provides a structure exhibiting good proton conductivity.
  • the reaction process is sequentially performed in the temperature range of 80 ° C. to 150 ° C. and the temperature range of 200 ° C. or more as described later, the surface of the metal salt of pyrophosphate reacts with phosphoric acid in any way Thus, it is presumed that a coating layer containing metals (Sn, Zr, Ti, Si) and O is formed on the surface, and this coating layer promotes proton conduction.
  • the proton conducting structure of the present invention can be used as an electrolyte in a fuel cell.
  • a fuel cell is comprised by including the said electrolyte and the electrode arrange
  • the fuel cell generates electricity by conducting protons through the electrolyte.
  • Example 1 The proton conducting structure of the present invention was produced by the following method. Powdered (about 1 ⁇ m) tin pyrophosphate (manufactured by Nippon Chemical Industrial Co., Ltd.) 0.9807 g and H 3 PO 4 (manufactured by Wako Pure Chemical Industries, 85%) such that the molar ratio of Sn: P is 1: 0.5 Concentration (concentrated phosphoric acid aqueous solution) 0.1931 g was weighed. Then, both components were put into an agate mortar and mixed by stirring for 30 minutes. The obtained mixture was filled in a mold and formed into pellets at a pressure of 100 kg / cm 2 using a uniaxial pressure molding machine.
  • the formed mixture was heated and held at a temperature of 120 ° C. for one hour in an electric furnace (heat treatment step 21), and then held at a temperature of 400 ° C. for one hour (heat treatment step 22).
  • heat treatment step 21 The formed mixture was heated and held at a temperature of 120 ° C. for one hour in an electric furnace (heat treatment step 21), and then held at a temperature of 400 ° C. for one hour (heat treatment step 22).
  • the coordination number of O to Sn in the vicinity of the surface of the proton conducting structure obtained in Example 1 was confirmed by the following method.
  • the coordination number of O to Sn in the vicinity of the surface of the proton conducting structure was measured using the conversion electron yield method in which the coordination number of O to Sn can be observed from the sample surface to a depth of about 100 nm.
  • the conversion electron yield method which is one technique of X-ray absorption spectroscopy, is used to measure the X-ray absorption spectrum at 4290 eV to 5400 eV including 4467 eV which is the energy of the SnL1 shell absorption edge. The order was observed.
  • the coordination number of O to Sn was 8.5. From this, it was confirmed that the coordination number of O to Sn was more than 6 in the vicinity of the surface of the proton conducting structure.
  • tin pyrophosphate made by Nippon Chemical Industrial Co., Ltd.
  • the coordination number of O to Sn was 5.2.
  • tin pyrophosphate usually has an octahedral structure of SnO 6 , and the coordination number of O to Sn is 6 theoretically. It is considered that the above-mentioned measured value is lower than the theoretical value due to oxygen deficiency and the like near the surface.
  • the proton conducting structure of the present invention has, as the core 11, tin pyrophosphate in which the crystal structure is maintained, It was found that a cover layer 12 of an amorphous structure was formed on at least a part of the surface of the core 11 and the coordination number of O to Sn was more than 6 and was different from tin pyrophosphate.
  • the proton conductivity of the proton conducting structure obtained in Example 1 was evaluated by impedance measurement using a four-terminal conductivity measuring device. Electrodes were formed directly on the surface of the structure by depositing platinum and palladium on the front and back surfaces of the pellet-like proton conducting structure. After adhering a gold wire to the formed electrode using a silver paste, the measurement was performed at a temperature range of room temperature to 250 ° C. under experimental conditions of a measurement frequency of 0.1 Hz to 10 MHz and a voltage amplitude of 2V.
  • FIG. 4 The result of temperature dependency of the obtained proton conductivity is shown in FIG.
  • C shows the measurement result of the proton conducting structure of Example 1
  • D shows the measurement result of the tin pyrophosphate formed into a pellet shape under the same conditions.
  • the horizontal axis in FIG. 4 represents a value obtained by converting the measured temperature into Kelvin units and multiplying the reciprocal thereof by 1000. From these results, it was confirmed that the proton conducting structure of the present invention exhibits much higher proton conductivity in the temperature range from room temperature to 250 ° C. as compared with tin pyrophosphate.
  • the proton conducting structure of the present invention has excellent proton conductivity and high reproducibility in a temperature range of 100 ° C. or more.
  • FIG. 5 shows the results of DTA measurement using a mixture of tin pyrophosphate and H 3 PO 4 .
  • 0.9807 g of tin pyrophosphate and 0.1931 g of H 3 PO 4 were weighed.
  • FIG. 6 shows the result of first derivative of the DTA measurement result of FIG.
  • the synthesis reaction proceeds in the range of 80 ° C. to 150 ° C., and another synthesis reaction starts again at 200 ° C.
  • FIG. 7 the DTA measurement result about a comparative example is shown.
  • A is a mixture of tin oxide SnO 2 and H 3 PO 4 (Wako Pure Chemical Industries, Ltd., 85% concentrated phosphoric acid aqueous solution) in a ratio that the molar ratio of Sn: P is 1: 3.
  • the DTA measurement result about the obtained mixture is shown.
  • B is a powder (about 1 ⁇ m) tin pyrophosphate (manufactured by Nippon Chemical Industrial Co., Ltd.) and H 3 PO 4 (manufactured by Wako Pure Chemical Industries, Ltd., 85% concentrated phosphoric acid aqueous solution) in a molar ratio of Sn: P 1 : DTA measurement result of a mixture obtained by mixing at a ratio of 0.5 and then performing a heat treatment step at 400 ° C. for 1 hour.
  • Example 2 In order to examine the upper limit of the temperature conditions applied to the heat treatment step 22 in the process of producing the proton conductive structure of the present invention, the set temperature in the heat treatment step 22 in Example 1 is 200 ° C., 300 ° C., or 500 ° C., 600 ° C.
  • Example 1 A structure was produced in the same manner as in Example 1 except that the temperature was changed to ° C.
  • the proton conductivity of the produced sample was measured by the above-mentioned method.
  • the proton conductivity at a measurement temperature of 100 ° C. or 200 ° C. in each sample is shown in Table 1 together with the results of Example 1.
  • the heat treatment step 22 when the heat treatment step 22 is performed at 200 ° C. or more and 400 ° C. or less, the obtained structure exhibits good proton conductivity, and when the set temperature of the heat treatment step 22 reaches 500 ° C. or more, the proton conductivity is remarkable. It was confirmed to decrease. Furthermore, for the structure obtained by changing the temperature in the heat treatment step 22 to 300 ° C. or 600 ° C., the coordination number of O to Sn was measured by the above-described conversion electron yield method.
  • the coordination number of the sample obtained by setting the temperature in the heat treatment step 22 to 300 ° C. was 7.0. From this, as in Example 1, formation of the covering layer 12 in which the coordination number of O to Sn was more than 6 was confirmed.
  • the sample obtained by setting the temperature in the heat treatment step 22 to 600 ° C. had a coordination number of 5.5, which was almost the same as the value (5.2) of tin pyrophosphate. From this, it was confirmed that when the temperature in the heat treatment step 22 is increased to 600 ° C., the covering layer 12 in the present invention is not formed.
  • FIG. 8 shows the above results of the coordination number of O to Sn together with the results of Example 1.
  • heat treatment step 21 in which tin pyrophosphate and phosphoric acid are mixed with the raw materials and heated at a temperature of 80 ° C. or more and 150 ° C. or less and heat treatment step 22 subsequently heated at a temperature of 200 ° C. or more and 400 ° C. or less
  • a proton conducting structure showing good proton conductivity was produced by performing.
  • the proton conducting structure has a structure in which tin pyrophosphate is contained as the core 11 and the covering layer 12 in which the coordination number of O to Sn is more than 6 is formed at least partially on the surface. confirmed.
  • Example 3 A structure is prepared in the same manner as in Example 1, except that titanium pyrophosphate, silicon pyrophosphate, or zirconium pyrophosphate (all of which are manufactured by Nippon Chemical Industrial Co., Ltd.) is used in place of tin pyrophosphate in Example 1. Was produced. However, the weight used of each metal pyrophosphate was changed so that the molar ratio of metal: P in the metal pyrophosphate becomes 1: 0.5. The proton conductivity of each of the obtained structures was measured in the temperature range from room temperature to 250 ° C. according to the conditions described above.
  • FIG. 9 The result of temperature dependence of the obtained proton conductivity is shown in FIG.
  • the proton conducting structure of the present invention and the proton conducting structure obtained by the production method of the present invention are most suitable as a solid electrolyte used in a fuel cell in a medium temperature range of 100 ° C. or more. That is, if the solid electrolyte layer of the present invention is used in a fuel cell, the conductivity will be improved, and therefore the improvement of the power generation rate of the fuel cell is expected.
  • the proton conducting structure according to the present invention and the proton conducting structure obtained by the production method of the present invention have excellent proton conductivity, and can be used as a solid electrolyte used for fuel cells, hydrogen sensors, and the like.

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Abstract

L'invention propose un corps à structure conductrice de protons qui possède une bonne conductivité de protons à une échelle de température égale ou supérieure à 100°C, ainsi que un procédé de fabrication de celui-ci. On fabrique le corps à structure conductrice de protons en mélangeant de l'acide pyrophosphorique contenant soit de l'étain (Sn), soit du zirconium (Zn), soit du titane(Ti), soit du silicium(Si), avec de l'acide phosphorique, puis en maintenant le mélange obtenu à une température égale ou supérieure à 80°C et égale ou inférieure à 150°C, puis ensuite, en le maintenant à une température égale ou supérieure à 200°C et égale ou inférieure à 400°C. Le corps à structure conductrice de protons qui fait l'objet de l'invention comporte un coeur formé de pyrophosphate stanneux et une couche de revêtement formée à la surface de ce coeur qui comprend de l'étain (Sn) et de l'oxygène (O), l'indice de coordination de l'oxygène (O) par rapport à l'étain (Sn) étant supérieur à 6.
PCT/JP2009/006180 2008-11-21 2009-11-18 Corps à structure conductrice de protons et procédé de fabrication de celui-ci. WO2010058562A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2010511844A JP4642155B2 (ja) 2008-11-21 2009-11-18 プロトン伝導構造体及びその製造方法
CN2009801203797A CN102047351B (zh) 2008-11-21 2009-11-18 质子传导结构体及其制造方法
US12/871,266 US8029941B2 (en) 2008-11-21 2010-08-30 Proton-conducting structure and method for manufacturing the same
US13/218,246 US8298718B2 (en) 2008-11-21 2011-08-25 Proton-conducting structure and method for manufacturing the same
US13/617,793 US8518595B2 (en) 2008-11-21 2012-09-14 Proton-conducting structure and method for manufacturing the same

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JP2008-297541 2008-11-21
JP2008297541 2008-11-21

Related Child Applications (1)

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US12/871,266 Continuation-In-Part US8029941B2 (en) 2008-11-21 2010-08-30 Proton-conducting structure and method for manufacturing the same

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JP7055535B2 (ja) 2018-09-20 2022-04-18 株式会社東芝 半導体装置

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