WO2023079910A1 - Électrolyte solide conducteur d'ions oxyde - Google Patents

Électrolyte solide conducteur d'ions oxyde Download PDF

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WO2023079910A1
WO2023079910A1 PCT/JP2022/037879 JP2022037879W WO2023079910A1 WO 2023079910 A1 WO2023079910 A1 WO 2023079910A1 JP 2022037879 W JP2022037879 W JP 2022037879W WO 2023079910 A1 WO2023079910 A1 WO 2023079910A1
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solid electrolyte
oxide
oxide ion
ion conductive
mol
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PCT/JP2022/037879
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English (en)
Japanese (ja)
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喜丈 戸田
洋史 加賀
暁 留野
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Ａｇｃ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
    • C04B35/057—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on calcium oxide
    • 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
    • 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

Definitions

  • the present invention relates to oxide ion conductive solid electrolytes.
  • Solid electrolytes with oxide ion conductivity can be used as various electrochemical devices such as solid oxide fuel cells (SOFC), solid oxide electrolysis cells (SOEC), oxygen sensors, and oxygen pumps.
  • SOFC solid oxide fuel cells
  • SOEC solid oxide electrolysis cells
  • oxygen sensors oxygen sensors
  • oxygen pumps oxygen pumps
  • Both SOFC and SOEC are electrochemical cells that operate at high temperatures.
  • the former can handle various fuels such as hydrogen, carbon monoxide, and methane, while the latter electrolyzes the water and carbon dioxide produced by SOFC operation. It can be converted back to hydrogen and carbon monoxide.
  • SOFC and SOEC have a solid electrolyte provided between two electrodes, and operate by conducting oxide ions in this solid electrolyte.
  • YSZ yttria-stabilized zirconia
  • ScSZ scandia-stabilized zirconia
  • Mayenite-type compounds exhibit oxide ion conductivity (Non-Patent Document 1). Mayenite-type compounds have a crystal structure that contains free oxide ions within cages. Therefore, it is possible that this free oxide ion can contribute to ion conduction.
  • the ionic conductivity of conventional mayenite-type compounds is not very high (for example, about 1/10 that of YSZ).
  • the present invention has been made in view of such a background, and an object of the present invention is to provide a solid electrolyte having a mayenite-type compound structure and having significantly high oxide ion conductivity.
  • an oxide ion conductive solid electrolyte Having a mayenite type compound having a representative composition represented by Ca 12 Al 14 O 33 , at least one alkali metal M selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs); Titanium (Ti); has The alkali metal M is contained in the range of 0.1 mol% to 10 mol% in terms of oxide with respect to the entire oxide ion conductive solid electrolyte, An oxide ion conductive solid electrolyte is provided in which the Ti is contained in a range of 8.1 mol % to 30 mol % in terms of oxide with respect to the entire oxide ion conductive solid electrolyte.
  • the present invention can provide a solid electrolyte having a mayenite-type compound structure and having significantly high oxide ion conductivity.
  • FIG. 4 is a diagram showing results of evaluation by simulation of major diffusion species in a mayenite-type compound having a C12A7 structure (Ca 12 Al 14 O 33 ) containing Na and Ti.
  • 1 is a diagram schematically showing an example of the configuration of an SOFC having an oxide ion-conducting solid electrolyte according to one embodiment of the present invention
  • FIG. 1 is a diagram schematically showing an example of the configuration of an SOEC having an oxide ion-conducting solid electrolyte according to one embodiment of the present invention
  • FIG. BRIEF DESCRIPTION OF THE DRAWINGS It is the figure which showed typically an example of the flow of the manufacturing method of the oxide ion conductive solid electrolyte by one Embodiment of this invention.
  • FIG. 4 is a diagram schematically showing an example flow of another method for producing an oxide ion conductive solid electrolyte according to one embodiment of the present invention.
  • FIG. 4 is a diagram showing results of evaluation by simulation of diffusion characteristics of oxide ions in a mayenite-type compound having a C12A7 structure (Ca 12 Al 14 O 33 ) according to each example.
  • FIG. 2 is a diagram summarizing Cole-Cole plots of each sample at 900° C.
  • FIG. FIG. 2 is a diagram summarizing Cole-Cole plots of each sample at 700° C.
  • an oxide ion-conducting solid electrolyte comprising: Having a mayenite type compound having a representative composition represented by Ca 12 Al 14 O 33 , at least one alkali metal M selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs); Titanium (Ti); has The alkali metal M is contained in the range of 0.1 mol% to 10 mol% in terms of oxide with respect to the entire oxide ion conductive solid electrolyte, An oxide ion conductive solid electrolyte is provided in which the Ti is contained in a range of 8.1 mol % to 30 mol % in terms of oxide with respect to the entire oxide ion conductive solid electrolyte.
  • first solid electrolyte contains a mayenite type compound having a C12A7 structure.
  • the mayenite type compound has a typical composition represented by 12CaO.7Al 2 O 3 and has a characteristic crystal structure with three-dimensionally connected voids (cages) with a diameter of about 0.4 nm.
  • the framework that makes up this cage is positively charged, forming 12 cages per unit cell.
  • One-sixth of this cage is occupied with oxide ions in order to satisfy the electroneutrality condition of the crystal.
  • the caged oxide ions have chemically different properties from the other oxygen ions that make up the framework, and for this reason the caged oxide ions are specifically called free oxide ions.
  • the mayenite type compound is also represented by the composition formula [Ca 24 Al 28 O 64 ] 4+ (O 2 ⁇ ) 2 (Non-Patent Document 2).
  • the mayenite-type compound contains free oxide ions in the cage, so it may function as an oxide ion conductor (Non-Patent Document 1).
  • the inventors of the present application have been earnestly conducting research and development on measures for increasing the oxide ion conductivity of mayenite-type compounds.
  • the inventors of the present application have found that the ionic conductivity of the mayenite type compound is significantly enhanced when the alkali metal M and titanium (Ti) are contained in the mayenite type compound, leading to the present invention.
  • the first solid electrolyte contains alkali metal M and titanium (Ti).
  • the alkali metal M is selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs), or combinations thereof.
  • the alkali metal M is contained in the first solid electrolyte in the range of 0.1 mol % to 10 mol % in terms of oxide.
  • the content of the alkali metal M By setting the content of the alkali metal M to 0.1 mol% or more, a solid electrolyte having high oxide ion conductivity can be obtained.
  • the amount of the alkali metal M added by setting the amount of the alkali metal M added to 10 mol % or less, it is possible to obtain an oxide ion conductive solid electrolyte in which the alkali metal M is included in the crystal structure of the mayenite type compound with less heterogeneous phases. .
  • the alkali metal M is preferably contained in the first solid electrolyte at 5.1 mol% or more in terms of oxide.
  • the alkali metal M tends to be arranged at Ca atom sites in the mayenite compound.
  • the molar ratio of alkali metal M to Ca atoms may be in the range of 0.002 ⁇ M/Ca ⁇ 0.30.
  • Ti is contained in the first solid electrolyte in a range of 8.1 mol % to 30 mol % in terms of TiO 2 oxide.
  • the Ti content is less than 8.1 mol%, no significant effect appears on the ionic conductivity of the mayenite type compound. Moreover, when Ti is added in an amount of more than 30 mol %, heterogeneous phases increase, making it difficult to obtain an oxide ion conductive solid electrolyte mainly composed of a mayenite type compound.
  • the content of Ti is preferably 9 mol% or more, more preferably 10 mol% or more, in terms of oxide.
  • Ti tends to be arranged at Al atom sites in the mayenite compound.
  • the molar ratio Ti/Al of Ti atoms to Al atoms may be 0.015 ⁇ Ti/Al ⁇ 0.50.
  • the molar ratio of alkali metals M and Ti may satisfy 0.84 ⁇ (M+Ca)/(Al+Ti) ⁇ 0.88.
  • the first solid electrolyte contains alkali metals M and Ti and has significantly high ionic conductivity.
  • Both Ca ions and Al ions constitute a cage structure in mayenite-type compounds.
  • the Ca ions which are divalent cations, have a relatively strong interaction with the free oxide ions in the cage, which are conducting carriers, while the Al ions, which are trivalent cations, are free It is believed that the interaction with oxide ions is relatively weak.
  • the mechanism for improving the ionic conductivity is based on current experimental considerations, and the first solid electrolyte may have improved ionic conductivity by another mechanism.
  • Such a first solid electrolyte has significantly higher ionic conductivity than conventional mayenite compounds. Therefore, the first solid electrolyte can be expected to be used as a solid electrolyte in electrochemical devices such as SOFC and SOEC.
  • the code used for the calculation is LAMMPS. Values reported by Pedone et al. (see Non-Patent Documents 3 and 4) were used for the two-body potential of the constituent elements of each material, which is an input parameter.
  • NPT NPT A 1 ns molecular dynamics simulation was performed on the ensemble. We also performed 1 ns molecular dynamics simulations with the NVE ensemble after the temperature, internal energy, and lattice constant were stabilized.
  • Figure 1 shows the results of the simulation.
  • the horizontal axis is the elapsed time
  • the vertical axis is the MSD of each element.
  • FIG. 1 shows that an element with a larger MSD slope is more likely to diffuse inside the mayenite compound.
  • oxide ions were the main ionic conductors in the compound system used.
  • the first solid electrolyte is stable even at high temperatures and has a significantly higher oxide ion conductivity. Therefore, the first solid electrolyte can be applied as, for example, a solid oxide fuel cell (SOFC) cell solid electrolyte and a solid electrolyte for SOEC.
  • SOFC solid oxide fuel cell
  • FIG. 2 schematically shows a configuration example of an SOFC cell.
  • the SOFC cell 100 has an oxygen electrode 110, a fuel electrode 120, and a solid electrolyte 130 between the electrodes.
  • the following reactions occur: O 2 +4e ⁇ ⁇ 2O 2 ⁇ (1)
  • Oxide ions generated at the oxygen electrode 110 pass through the solid electrolyte 130 and reach the fuel electrode 120 on the opposite side.
  • the following reactions occur: 2H 2 +2O 2 ⁇ ⁇ 2H 2 O+4e ⁇ Equation (2) Therefore, when the SOFC cell 100 is connected to the external load 140 , the reactions of equations (1) and (2) continue and the external load 140 can be powered.
  • the first solid electrolyte can be applied as the solid electrolyte 130, for example.
  • FIG. 3 schematically shows a configuration example of an SOEC cell.
  • the SOEC cell 200 has an oxygen electrode 210, a fuel electrode 220, and a solid electrolyte 230 between the electrodes.
  • the first solid electrolyte can be applied as the solid electrolyte 230, for example.
  • the solid electrolyte according to one embodiment of the present invention may be used in any form.
  • a solid electrolyte according to one embodiment of the invention may be provided as a powder.
  • the solid electrolyte according to an embodiment of the present invention may be provided in the form of slurry, paste or dispersion by mixing with a solvent and/or binder.
  • FIG. 4 schematically shows an example flow of a method for producing an oxide ion conductive solid electrolyte according to one embodiment of the present invention (hereinafter referred to as "first production method").
  • the first manufacturing method includes: (1) a step of mixing a Ca source, an Al source, an alkali metal M source, and a Ti source in a predetermined ratio to obtain a mixed powder (step S110); (2) a step of calcining the mixed powder to obtain a calcined powder (step S120); (3) a step of sintering the calcined powder to obtain a sintered body (step S130); have
  • Step S110 First, a mixed powder is prepared. Therefore, a Ca source, an Al source, an alkali metal M source, and a Ti source are mixed at a predetermined ratio.
  • the Ca source may be selected from, for example, metallic calcium, calcium carbonate, calcium oxide, calcium hydroxide, calcium nitrate, and calcium acetate.
  • the Al source may be selected from, for example, metallic aluminum, ⁇ -alumina, ⁇ -alumina, aluminum hydroxide, aluminum nitrate, and aluminum sulfate.
  • the alkali metal M source may be selected from, for example, alkali metal M, alkali metal M oxide, alkali metal M carbonate, alkali metal M hydroxide, and alkali metal M nitrate.
  • the Ti source may be selected from, for example, metallic titanium and titanium oxide.
  • Each raw material is weighed and mixed so as to obtain a mayenite-type compound having the desired composition.
  • the mixing method is not particularly limited as long as a uniform mixed powder can be obtained.
  • Step S120 Next, the mixed powder is calcined.
  • the calcination process is carried out to desorb compounds such as carbonic acid and nitric acid contained in the mixed powder, and to facilitate the formation of the desired mayenite type compound in the next sintering process.
  • the calcination conditions are not particularly limited, but the calcination temperature is preferably 1000°C or higher in order to obtain the desired mixed oxide. However, if the calcining temperature is too high, crystallization will proceed excessively in the mixed powder. Therefore, the calcination temperature is preferably 1300° C. or less.
  • the calcination time is, for example, about 5 hours to 24 hours. However, the calcining time varies depending on the calcining temperature, and the higher the calcining temperature, the shorter the calcining time.
  • the calcined powder may be pulverized as necessary.
  • the average particle size after pulverization may range, for example, from 0.1 ⁇ m to 100 ⁇ m.
  • Step S130 Next, the calcined powder is sintered.
  • the sintering process is carried out to obtain a dense sintered body with the desired crystal phase.
  • the calcined powder Before the sintering process, the calcined powder may be molded and the sintering process may be performed using the obtained molded body.
  • the molding conditions are not particularly limited, and a general molding method such as uniaxial molding or hydrostatic molding may be employed.
  • the sintering method is not particularly limited.
  • the calcined powder or compact may be sintered by a pressureless sintering method under normal pressure.
  • the calcined powder may be sintered using a pressure sintering method such as hot press sintering or discharge plasma sintering.
  • a pressure sintering method such as hot press sintering or discharge plasma sintering.
  • molding and sintering may be performed at once.
  • the sintering temperature is not particularly limited as long as a proper sintered body can be obtained, but is preferably in the range of 1200°C to 1400°C. If the sintering temperature is too low, a dense sintered body may not be obtained. Also, if the sintering temperature is too high, the object to be processed may melt.
  • the optimum sintering time varies depending on the sintering temperature, but in the case of pressureless sintering, it is, for example, about 5 to 48 hours, and in the case of pressure sintering by discharge plasma, it is, for example, 5 minutes. ⁇ 60 minutes.
  • carbon may adhere to the surface of the sintered body.
  • the adhered carbon can be removed by heat-treating in the air at 800° C. to 1000° C. for about 5 hours.
  • an oxide ion conductive solid electrolyte according to one embodiment of the present invention can be produced.
  • FIG. 5 schematically shows an example flow of another method for producing an oxide ion conductive solid electrolyte (hereinafter referred to as "second production method") according to one embodiment of the present invention.
  • the second manufacturing method includes: (1) a step of mixing a Ca source and an Al source in a predetermined ratio to obtain a first mixed powder (step S210); (2) a step of calcining the first mixed powder to obtain a first calcined powder (step S220); (3) mixing the first calcined powder, the alkali metal M source, and the Ti source in a predetermined ratio to obtain a second mixed powder (step S230); (4) a step of calcining the second mixed powder to obtain a second calcined powder (step S240); (5) Sintering the second calcined powder to obtain a sintered body (step S250); have
  • each step included in the second manufacturing method can be easily understood by a person skilled in the art from the description of each step S110 to S130 in the first manufacturing method. Therefore, detailed description of each step is omitted here.
  • the oxide ion conductive solid electrolyte is manufactured through two calcination steps (steps S220 and S240).
  • oxide ions having a more homogeneous composition Conductive solid electrolytes can be produced.
  • highly reactive Ca may react with alkali metal M to form a heterogeneous phase.
  • step S220 in the first calcination step (step S220), calcined powder in which Ca and Al are reacted and bonded can be prepared in advance. Therefore, in the second calcination step (step S240), the alkali metals M and Ti can be more reliably introduced into desired sites within the mayenite compound.
  • the method for producing an oxide ion conductive solid electrolyte according to one embodiment of the present invention has been described above using the first production method and the second production method as examples.
  • the above description is merely an example, and the oxide ion conductive solid electrolyte according to one embodiment of the present invention may be produced by other methods such as a hydrothermal method, a sol-gel method, and a liquid-phase combustion method. good.
  • Examples 1 to 3, Examples 11 to 16, and Example 51 are examples, and Examples 21 to 23, Examples 31 to 34, and Examples 61 to 62 are comparative examples. is.
  • Example 1 The diffusion characteristics of oxide ions at 1200 K were evaluated in the mayenite type compound having the C12A7 structure containing Na and Ti by the simulation based on the classical molecular dynamics calculation described above.
  • the mayenite type compound was a system containing 5.1 mol% Na and 15.4 mol% Ti in terms of oxide.
  • Na/Ca (molar ratio) is 0.2 and Ti/Al (molar ratio) is 0.3.
  • the slope ⁇ of the straight line was obtained from the relational diagram of time and oxide ion MSD shown in FIG. 1 above.
  • Example 2 to Example 3 By the same method as in Example 1, the diffusion properties of oxide ions in the mayenite type compound were evaluated. However, in Examples 2 and 3, the simulation was performed by changing the contents of Na and Ti from those in Example 1, respectively.
  • Example 21 By the same method as in Example 1, the diffusion properties of oxide ions in the mayenite type compound were evaluated. However, in Example 21, the simulation was performed for a mayenite type compound having a C12A7 structure containing neither Na nor Ti.
  • Example 22 to Example 23 By the same method as in Example 1, the diffusion properties of oxide ions in the mayenite type compound were evaluated. However, in Examples 22 and 23, the simulation was performed by changing the contents of Na and Ti from those in Example 1, respectively.
  • FIG. 6 collectively shows the simulation results obtained in Examples 1, 21, and 23. As shown in FIG.
  • Table 1 summarizes the composition of the mayenite type compound in each example and the results of the simulation (slope ⁇ ).
  • the mayenite type compound containing 2.6 mol % or more of Na and 10 mol % or more of Ti provides significantly high ionic conductivity.
  • Example 11 to 16 By the same method as in Example 1, the diffusion properties of oxide ions in the mayenite type compound were evaluated. However, in Examples 11 to 16, the simulation was performed by changing the type and content of the alkali metal and the content of Ti from those in Example 1, respectively.
  • Example 31 to 34 By the same method as in Example 1, the diffusion properties of oxide ions in the mayenite type compound were evaluated. However, in Examples 31 to 34, the simulation was performed by changing the type and content of the alkali metal and the content of Ti from those of Example 1, respectively.
  • Example 51 A sintered body was produced by the following method.
  • the amount of sodium carbonate was 1.3 times the stoichiometry.
  • sample 51 The obtained sintered body is called "Sample 51".
  • the composition of sample 51 was substantially the same as the composition of the mayenite type compound shown in Example 1 above.
  • Example 61 A sintered body was produced in the same manner as in Example 51. However, in Example 61, only calcium carbonate (4.12 g) and ⁇ -alumina (2.57 g) were mixed in the above-described [Preparation step] to prepare a mixed powder. That is, a mixed powder was prepared without adding an alkali metal M source and a Ti source. Other steps are the same as in Example 51.
  • the obtained sintered body is called "Sample 61".
  • Example 62 A sintered body was produced in the same manner as in Example 1. However, in Example 62, calcium carbonate (2.90 g), ⁇ -alumina (1.75 g), sodium carbonate (0.14 g), and rutile-type titanium oxide (0.21 g) were used in the above [preparation step]. ) to prepare a mixed powder.
  • sample 62 The obtained sintered body is called "Sample 62".
  • the composition of sample 62 was substantially the same as the composition of the mayenite type compound shown in Example 23 above.
  • each sample was polished with #80 to #1000 sandpaper to remove the surface layer and smooth it.
  • a platinum electrode with a diameter of 6 mm and a thickness of 10 ⁇ m was placed on the polished surface via platinum paste. This sample was heat treated at 1000° C. for 15 minutes in an air atmosphere to solidify the platinum paste.
  • the sample was placed in an electric furnace in an air atmosphere.
  • the sample was also connected to a potentiogalvanostat (Solartron Analytical 1260A) via a platinum wire coupled to the platinum electrode.
  • the measurement temperatures were 900°C and 700°C.
  • the impedance was measured and a Cole-Cole plot was created.
  • the measurement frequency was 10 MHz to 1 Hz.
  • the resistivity was obtained from the intersection with the horizontal axis (real number axis).
  • FIG. 7 summarizes the Cole-Cole plots at 900°C obtained for each sample.
  • FIG. 8 collectively shows the Cole-Cole plots at 700° C. obtained for each sample.
  • the present invention can have the following aspects.
  • (Aspect 1) An oxide ion conductive solid electrolyte, Having a mayenite type compound having a representative composition represented by Ca 12 Al 14 O 33 , at least one alkali metal M selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs); Titanium (Ti); has The alkali metal M is contained in the range of 0.1 mol% to 10 mol% in terms of oxide with respect to the entire oxide ion conductive solid electrolyte, The oxide ion conductive solid electrolyte, wherein the Ti is contained in a range of 8.1 mol % to 30 mol % in terms of oxide with respect to the entire oxide ion conductive solid electrolyte.
  • SOFC cell 110 oxygen electrode 120 fuel electrode 130 solid electrolyte 140 external load 200 SOEC cell 210 oxygen electrode 220 fuel electrode 230 solid electrolyte 240 external power supply

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Abstract

L'invention concerne un électrolyte solide conducteur d'ions oxyde, qui comprend un composé de mayénite ayant une formule de composition représentative représentée par Ca12AI14O33 ; et qui contient du titane (Ti) et au moins un type de métal alcalin M choisi parmi le lithium (Li), le sodium (Na), le potassium (K), le rubidium (Rb) et le césium (Cs). Le métal alcalin M est contenu en une quantité de 0,1 à 10 % en moles en termes d'oxyde par rapport à l'électrolyte solide conducteur d'ions oxyde global. Le Ti est contenu en une quantité de 8,1 à 30 % en moles par rapport à l'électrolyte solide conducteur d'ions oxyde global.
PCT/JP2022/037879 2021-11-08 2022-10-11 Électrolyte solide conducteur d'ions oxyde WO2023079910A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005077859A1 (fr) * 2004-02-13 2005-08-25 Asahi Glass Company, Limited Procédé de préparation d'un composé électroconducteur de type mayenite
JP2014055313A (ja) * 2012-09-11 2014-03-27 Tokyo Institute Of Technology マイエナイト複合材および電子放出用陰極
JP2015122286A (ja) * 2013-12-25 2015-07-02 株式会社ノリタケカンパニーリミテド 電極材料とその利用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005077859A1 (fr) * 2004-02-13 2005-08-25 Asahi Glass Company, Limited Procédé de préparation d'un composé électroconducteur de type mayenite
JP2014055313A (ja) * 2012-09-11 2014-03-27 Tokyo Institute Of Technology マイエナイト複合材および電子放出用陰極
JP2015122286A (ja) * 2013-12-25 2015-07-02 株式会社ノリタケカンパニーリミテド 電極材料とその利用

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