JP2018046017A - Solid alkali type fuel battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid alkali type fuel battery which is superior in heat resistance and durability and which enables the suppression of reduction in an electromotive force owing to fuel permeation.SOLUTION: A solid alkali type fuel battery comprises: an air electrode which is supplied with oxygen; a fuel electrode which is supplied with a liquid fuel and/or a gaseous fuel; and an inorganic solid electrolytic body interposed between the fuel electrode and the air electrode and having hydroxide ion conductivity. The inorganic solid electrolytic body is preferably composed of a layered composite hydroxide having a basic composition represented by MM(OH)AmHO (where Mis a divalent cation, Mis a trivalent cation, Ais an n-valent anion, n is an integer of 1 or more, and x is 0.1-0.4). The inorganic solid electrolytic body is densified by a hydrothermal treatment.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a solid alkaline fuel cell.

An alkaline fuel cell (AFC) is known as a fuel cell that operates at a relatively low temperature (for example, 200 ° C. or less). AFC can use a wide variety of fuels. For example, when methanol is used as a fuel, the reaction is as follows.
・ Fuel electrode (anode): CH ₃ OH + 6OH ⁻ → 6e ⁻ + CO ₂ + 5H ₂ O
・ Air electrode (cathode): 3 / 2O ₂ + 3H ₂ O + 6e ⁻ → 6OH ⁻
Overall: CH ₃ OH + 3 / 2O ₂ → CO ₂ + 2H ₂ O

Thus, AFC requires a hydroxide ion conductor as an electrolyte, and recently, AFC using an anion exchange membrane (AEM) or a layered double hydroxide (LDH) compact has been proposed. For example, in Patent Document 1 (Japanese Patent Laid-Open No. 2013-48066), in a fuel cell including an electrolyte layer made of an anion exchange membrane (AEM), a compound containing at least hydrogen and nitrogen such as hydrazine is used as a fuel. Is disclosed. Patent Document 2 (International Publication No. 2010/109670) discloses a general formula (M ²⁺ ₁₋ M ³⁺ _x (OH) ₂ A ⁿ⁻ _{x / n} · mH ₂ O (where M ²⁺ is 2)). the valence of the cation, M ³⁺ is a trivalent cation, a ^n-layered double hydroxide (LDH) alkaline electrolyte membrane directly alcohol fuel consisting represented by a is) n-valent anion It is disclosed for use in batteries. This alkaline electrolyte membrane is an LDH green compact made into a pellet form by cold pressing fine particles of layered double hydroxide.

JP 2013-48066 A International Publication No. 2010/109670

  Thus, in AFC, in addition to hydrogen, liquid fuel (for example, alcohol, hydrazine, etc.) that can be stored more easily than hydrogen can be used as fuel. However, since the AEM electrolyte layer disclosed in the cited document 1 is composed of an organic material, there is a problem in heat resistance and durability, and the electromotive force is reduced due to the permeation of fuel to the air electrode side. There is also a problem. On the other hand, the LDH green compact as disclosed in the cited document 2 has a problem that the electromotive force is lowered due to the permeation of the fuel to the air electrode side due to insufficient denseness.

  Inventors of the present invention have excellent heat resistance and durability and reduced electromotive force due to fuel permeation by using an inorganic solid electrolyte body made of a layered double hydroxide densified by hydrothermal treatment as an electrolyte. The present inventors have obtained knowledge that a solid alkaline fuel cell capable of suppressing the above problem can be provided.

  Accordingly, an object of the present invention is to provide a solid alkaline fuel cell that is excellent in heat resistance and durability and that can suppress a decrease in electromotive force due to fuel permeation.

According to one aspect of the present invention, an air electrode supplied with oxygen;
An anode supplied with liquid fuel and / or gaseous fuel;
An inorganic solid electrolyte body interposed between the fuel electrode and the air electrode and having hydroxide ion conductivity;
A solid alkaline fuel cell comprising:
The inorganic solid electrolyte body, preferably ^{_{M 2+ 1-x M 3+ x}} (OH) 2 A n- x / n · mH 2 O ( ^{wherein, M 2+} is a divalent ^{cation, M 3+} is 3 the valence of the cation, a ^n-is the n-valent anion, n is an integer of 1 or more, the layered double hydroxide having a basic composition of x is 0.1-0.4) And a solid alkaline fuel cell in which the inorganic solid electrolyte body is densified by hydrothermal treatment.

It is a schematic cross section for demonstrating one aspect | mode of the solid alkaline fuel cell by this invention. It is a schematic cross section for demonstrating other one aspect | mode of the solid alkaline fuel cell by this invention. It is a schematic cross section for demonstrating other one aspect | mode of the solid alkaline fuel cell by this invention. It is a schematic cross section which shows one aspect | mode of the inorganic solid electrolyte body with a porous base material. It is a schematic cross section which shows the other one aspect | mode of the inorganic solid electrolyte body with a porous base material. It is a schematic diagram which shows a layered double hydroxide (LDH) plate-like particle. FIG. 3 is an exploded perspective view of a denseness determination measurement system used in the denseness determination test I of Examples 1 and 2. 3 is a schematic cross-sectional view of a denseness determination measurement system used in the denseness determination test I of Examples 1 and 2. FIG. It is a disassembled perspective view of the airtight container for measurement used in the denseness determination test II of Examples 1 and 2. It is a schematic cross section of the measurement system used in the denseness determination test II of Examples 1 and 2. 4 is a SEM image of the surface of an alumina porous substrate produced in Example 2. 3 is an XRD profile obtained for the crystal phase of the sample in Example 2. 6 is a SEM image showing the surface microstructure of the film sample observed in Example 2. 4 is a SEM image of a polished cross-sectional microstructure of a composite material sample observed in Example 2. FIG. 6 is an exploded perspective view of a solid alkaline fuel cell according to the present invention produced in Example 3. FIG. It is a figure which shows each structural member for hold | maintaining the inorganic solid electrolyte body in Example 3. FIG.

FIG. 1 schematically shows an example of the solid alkaline fuel cell of the present invention. A solid alkaline fuel cell 10 shown in FIG. 1 includes an air electrode 12, a fuel electrode 14, and an inorganic solid electrolyte body 16. The air electrode 12 can function as a cathode when oxygen is supplied via the air supply means 13. The fuel electrode 14 is supplied with liquid fuel and / or gaseous fuel via the fuel supply means 15 and can function as an anode. The inorganic solid electrolyte body 16 is a ceramic that is interposed between the fuel electrode 14 and the air electrode 12 and has hydroxide ion conductivity. Inorganic solid electrolyte body 16 is preferably ^{_{M 2+ 1-x M 3+ x}} (OH) 2 A n- x / n · mH 2 O ( ^{wherein, M 2+} is a divalent ^{cation, M 3+} is 3 the valence of the cation, a ^n-is the n-valent anion, n is an integer of 1 or more, the layered double hydroxide having a basic composition of x is 0.1-0.4) Consists of. The inorganic solid electrolyte body 16 is densified by hydrothermal treatment. As described above, in the solid alkaline fuel cell 10 of the present invention, by using the inorganic solid electrolyte body 16 made of a densified layered double hydroxide as an electrolyte, it has excellent heat resistance and durability, and fuel. It is possible to provide a solid alkaline fuel cell capable of suppressing a decrease in electromotive force due to permeation.

  That is, as described above, in the alkaline fuel cell (AFC), in addition to hydrogen, liquid fuel (for example, alcohol, hydrazine, etc.) that can be stored more easily than hydrogen can be used. Since such an AEM electrolyte layer is composed of an organic material, there is a problem in heat resistance and durability, and there is also a problem of a decrease in electromotive force due to the permeation of fuel to the air electrode side. Further, in the layered double hydroxide (LDH) green compact as disclosed in the cited document 2, there is a problem of a decrease in electromotive force due to permeation of fuel to the air electrode side due to insufficient denseness. is there. In this regard, since the inorganic solid electrolyte body 16 used in the solid alkaline fuel cell 10 of the present invention is made of a ceramic material, it has higher heat resistance and higher organic resistance than the organic material such as the AEM electrolyte layer described in the cited document 1. Excellent durability. In addition, since the inorganic solid electrolyte body 16 is densified by hydrothermal treatment, it does not have liquid permeability or air permeability, and therefore prevents permeation of fuel to the air electrode 12 side and lowers electromotive force. Can be suppressed. As a result, according to the present invention, it is possible to provide a solid alkaline fuel cell that is excellent in heat resistance and durability and that can suppress a decrease in electromotive force due to fuel permeation.

The air electrode 12 is an electrode that functions as a cathode when supplied with oxygen. The oxygen is preferably supplied as air and the air is preferably humidified air. The air electrode 12 is not particularly limited as long as it includes various known air electrode catalysts used in alkaline fuel cells. Examples of the air electrode catalyst include platinum group elements (Ru, Rh, Pd, Os, Ir, Pt), group 8-10 elements (periodic table in IUPAC format) such as iron group elements (Fe, Co, Ni), etc. Element belonging to Group 8 to 10), Group 11 elements such as Cu, Ag, Au (elements belonging to Group 11 in the periodic table in IUPAC format), rhodium phthalocyanine, tetraphenylporphyrin, Co salen, Ni salen (Salen = N, N′-bis (salicylidene) ethylenediamine), silver nitrate, and any combination thereof. The amount of the catalyst supported on the air electrode 12 is not particularly limited, but is preferably 0.1 to 10 mg / cm ² , more preferably 0.1 to 5 mg / cm ² . The air electrode catalyst is preferably supported on carbon. Preferred examples of the air electrode 12 or the catalyst constituting it include platinum-supported carbon (Pt / C), palladium-supported carbon (Pd / C), rhodium-supported carbon (Rh / C), nickel-supported carbon (Ni / C). , Copper-supported carbon (Cu / C), and silver-supported carbon (Ag / C). The method for producing the air electrode 12 is not particularly limited. For example, the air electrode catalyst and, if desired, a carrier are mixed with a binder to form a paste, and this paste mixture is applied to one surface of the inorganic solid electrolyte body 16. What is necessary is just to form.

  The fuel electrode 14 is an electrode that functions as an anode when supplied with liquid fuel and / or gaseous fuel. The fuel electrode 14 is not particularly limited as long as it includes various known fuel electrode catalysts used in alkaline fuel cells. Examples of the fuel electrode catalyst include metal catalysts such as Pt, Ni, Co, Fe, Ru, Sn, and Pd. The metal catalyst is preferably supported on a carrier such as carbon. Moreover, it is good also as a form of the organometallic complex which makes the metal atom of a metal catalyst a central metal, and also you may carry | support such an organometallic complex on a support | carrier. A diffusion layer made of a porous material or the like may be disposed on the surface of the catalyst. Preferred examples of the fuel electrode 14 or the catalyst constituting it include nickel, cobalt, silver, platinum-supported carbon (Pt / C), palladium-supported carbon (Pd / C), rhodium-supported carbon (Rh / C), nickel support Examples include carbon (Ni / C), copper-supported carbon (Cu / C), and silver-supported carbon (Ag / C). The method for producing the fuel electrode 14 is not particularly limited. For example, the fuel electrode catalyst and optionally a carrier are mixed with a binder to form a paste, and this paste-like mixture is the surface of the inorganic solid electrolyte body 16 opposite to the air electrode 12. What is necessary is just to form by apply | coating to.

The fuel supplied to the fuel electrode 14 may be either liquid fuel or gaseous fuel. The liquid fuel may be a liquid fuel compound itself, or may be obtained by dissolving a solid fuel compound in a liquid such as water or alcohol. Examples of fuel compounds that can be used for fuel include (i) hydrazine (NH ₂ NH ₂ ), hydrazine hydrate (NH ₂ NH ₂ .H ₂ O), hydrazine carbonate ((NH ₂ NH ₂ ) ₂ CO ₂ ). , Hydrazine sulfate (NH ₂ NH ₂ .H ₂ SO ₄ ), monomethyl hydrazine (CH ₃ NHNH ₂ ), dimethyl hydrazine ((CH ₃ ) ₂ NNH ₂ , CH ₃ NHNHCH ₃ ), carboxylic hydrazide ((NHNH ₂ ) ₂ CO ) Hydrazines such as (ii) urea (NH ₂ CONH ₂ ), (iii) ammonia (NH ₃ ), (iv) imidazole, 1,3,5-triazine, 3-amino-1,2,4-triazole heterocycles compounds such, (v) hydroxylamine _(NH 2 OH), such as hydroxylamine sulfate _{(NH 2 OH · H 2 SO} 4) Hydroxylamines, and (vi) any combination thereof. Among the above fuel compounds, compounds that do not contain carbon (that is, hydrazine, hydrazine hydrate, hydrazine sulfate, ammonia, hydroxylamine, hydroxylamine sulfate, etc.) have no problem of catalyst poisoning due to carbon monoxide, thus improving durability. In addition, carbon dioxide emissions can be eliminated. The fuel compound may be used as a fuel as it is, but may be used as a solution in which the fuel compound is dissolved in water and / or alcohol (for example, lower alcohol such as methanol, ethanol, propanol, isopropanol, etc.). For example, among the fuel compounds listed above, hydrazine, hydrated hydrazine, monomethyl hydrazine, and dimethyl hydrazine are liquid and can be used as liquid fuel. In addition, hydrazine carbonate, hydrazine sulfate, carboxylic hydrazide, urea, imidazole, 3-amino-1,2,4-triazole, and hydroxylamine sulfate are solid but soluble in water. Triazine and hydroxylamine are solid but soluble in alcohol. Ammonia is a gas but is soluble in water. Therefore, these solid fuel compounds can be dissolved in water or alcohol and used as a liquid fuel. When the fuel compound is used after being dissolved in water and / or alcohol, the concentration of the fuel compound in the solution is, for example, 1 to 90% by weight, and preferably 1 to 30% by weight. Alternatively, a hydrocarbon liquid fuel containing alcohols such as methanol and ethanol, a hydrocarbon gas such as methane, and pure hydrogen may be used as fuel.

  More preferably, liquid fuel is supplied to the fuel electrode 14. Since the inorganic solid electrolyte body 16 is excellent in liquid impermeability, the permeation of liquid fuel to the air electrode side can be reliably prevented to suppress a decrease in electromotive force. As described above, the liquid fuel is preferably a liquid containing water and / or alcohol. The liquid fuel preferably contains at least one selected from the group consisting of ethanol, methanol, ethylene glycol, hydrated hydrazine, and ammonia.

The inorganic solid electrolyte body 16 is a ceramic having hydroxide ion conductivity. Inorganic solid electrolyte body 16 is preferably ^{_{M 2+ 1-x M 3+ x}} (OH) 2 A n- x / n · mH 2 O ( ^{wherein, M 2+} is a divalent ^{cation, M 3+} is 3 the valence of the cation, a ^n-is the n-valent anion, n is an integer of 1 or more, the layered double hydroxide having a basic composition of x is 0.1-0.4) (LDH). In the above general formula, M ²⁺ may be any divalent cation, and preferred examples include Mg ²⁺ , Ca ²⁺ and Zn ²⁺ , and more preferably Mg ²⁺ . M ³⁺ may be any trivalent cation, but preferred examples include Al ³⁺ or Cr ³⁺ , and more preferred is Al ³⁺ . A ^n- may be any anion, preferred examples OH ^- and _CO ^{3 2-} and the like. Therefore, in the general ^{formula, M 2+} comprises ^{Mg 2+, M 3+} comprises ^{Al 3+, A n-is} OH ^- and / or _CO preferably contains ^{3 2-.} n is an integer of 1 or more, preferably 1 or 2. x is 0.1 to 0.4, preferably 0.2 to 0.35. m is an arbitrary real number. It is also possible to replace the part or all of the M ³⁺ in the general formula tetravalent or higher valency cation, in which case, the anion A ^n- coefficients x / n of the above general formula It may be changed as appropriate.

  The inorganic solid electrolyte body 16 is densified by hydrothermal treatment. Hydrothermal treatment is extremely effective for the densification of layered double hydroxides, especially Mg—Al type layered double hydroxides. The inorganic solid electrolyte body 16 thus densified by hydrothermal treatment typically does not have liquid permeability and air permeability. Therefore, the inorganic solid electrolyte body 16 not only has excellent heat resistance and durability, but also can suppress a decrease in electromotive force due to fuel permeation. Thus, it is desirable that the inorganic solid electrolyte body 16 is so dense that it does not have liquid permeability and air permeability. For example, it is preferable that the inorganic solid electrolyte body 16 has a relative density of 90% or more, more preferably 92% or more, and still more preferably 95% or more, calculated by the Archimedes method or a similar method. Such an inorganic solid electrolyte body 16 that should be referred to as an LDH dense body can be manufactured through hydrothermal treatment, and a simple LDH green compact that has not undergone hydrothermal treatment is not preferable because the denseness is insufficient. A preferred method for producing the inorganic solid electrolyte body 16 using hydrothermal treatment will be described later.

  The inorganic solid electrolyte body 16 may be a composite of a particle group including an inorganic solid electrolyte having hydroxide ion conductivity and an auxiliary component that assists densification and hardening of the particle group. Alternatively, a composite of an open-pore porous material as a base material and an inorganic solid electrolyte (for example, layered double hydroxide) deposited and grown in the pores so as to fill the pores of the porous material is also used. Is possible. Examples of the substance constituting the porous body include ceramics such as alumina and zirconia, and insulating substances such as a porous sheet made of a foamed resin or a fibrous substance.

The inorganic solid electrolyte body 16 may be in the form of a plate, a film, or a layer. When the inorganic solid electrolyte body 16 is in the form of a film or a layer, the inorganic solid electrolyte body in the form of a film or layer is on a porous substrate or It is preferable that it is formed in it. The preferred thickness of the plate-like inorganic solid electrolyte body is 0.01 to 0.5 mm, more preferably 0.02 to 0.2 mm, and still more preferably 0.05 to 0.1 mm. Moreover, the higher the hydroxide ion conductivity of the inorganic solid electrolyte body, the better, but it typically has a conductivity of 10 ⁻⁴ to 10 ⁻¹ S / m. On the other hand, in the case of a film-like or layered form, the thickness is preferably 100 μm or less, more preferably 75 μm or less, still more preferably 50 μm or less, particularly preferably 25 μm or less, and most preferably 5 μm or less. Such thinness can realize low resistance of the inorganic solid electrolyte body. The lower limit of the thickness is not particularly limited because it varies depending on the application, but it is preferably 1 μm or more, more preferably 2 μm, in order to ensure a certain degree of rigidity desired as the inorganic solid electrolyte membrane or layer. That's it.

  A porous substrate may be provided on one side or both sides (preferably one side) of the inorganic solid electrolyte body 16. Since the strength can be imparted by the porous substrate, the inorganic solid electrolyte body 16 can be made thin to reduce the resistance. Also, a dense film or a dense layer of an inorganic solid electrolyte (preferably LDH) can be formed on or in the porous substrate. In the case of providing a porous substrate on one side of the inorganic solid electrolyte body 16, a method of preparing a porous substrate and depositing an inorganic solid electrolyte on the porous substrate can be considered (this method will be described later). To do). On the other hand, when providing a porous base material on both surfaces of the inorganic solid electrolyte body 16, it can be considered that the inorganic solid electrolyte raw material powder is sandwiched between two porous base materials for densification. The porous substrate may be provided over the entire surface of one side of the inorganic solid electrolyte body 16, or may be provided only on a part of one side of the inorganic solid electrolyte body 16. For example, when the inorganic solid electrolyte body 16 is formed in the form of a film or a layer on or in the porous base material, the porous base material is provided over the entire surface of one side of the inorganic solid electrolyte body derived from the manufacturing method. It is typically a configuration. On the other hand, when the inorganic solid electrolyte body 16 is formed in a self-supporting plate shape (which does not require a base material), it is porous only on a part of one side of the inorganic solid electrolyte body 16 (for example, a region involved in the charge / discharge reaction). A porous substrate may be retrofitted, or a porous substrate may be retrofitted over the entire surface of one side.

  According to a preferred embodiment of the present invention, the porous substrate can be composed of a material having hydroxide ion conductivity. The porous base material having hydroxide ion conductivity may be provided on any surface of the inorganic solid electrolyte body 16 or on both sides. For example, the porous base material 18 may be provided on the air electrode 12 side as shown in FIG. 2, or the porous base material 18 may be provided on the fuel electrode 14 side as shown in FIG. This is because, in this embodiment, hydroxide ions can pass through the porous substrate itself, so that hydroxide ions can be exchanged between the air electrode 12 and / or the fuel electrode 14 and the inorganic solid electrolyte body 16. This is because sufficient conductivity can be secured. Therefore, in this aspect, both liquid fuel and gaseous fuel can be used. The porous substrate having hydroxide ion conductivity is preferably composed of a ceramic material having hydroxide ion conductivity. For example, a layered double hydroxide (LDH) having the above-described composition is used. It may be comprised of.

  According to another preferred embodiment of the present invention, the porous substrate may be made of a material that does not have hydroxide ion conductivity. In this case, as shown in FIG. 3, the porous substrate 18 is provided on the fuel electrode 14 side of the inorganic solid electrolyte body 16, and a mixed solution of the liquid fuel and the alkali metal hydroxide aqueous solution is formed on the fuel electrode 14. It is desired to be supplied. That is, in this embodiment, since the porous substrate 18 does not have hydroxide ion conductivity, a mixed solution that can pass through the porous substrate 18 by mixing the alkali metal hydroxide aqueous solution with the liquid fuel. Thus, it is possible to ensure the conductivity of hydroxide ions between the fuel electrode 14 and the inorganic solid electrolyte body 16. In this case, the porous substrate can be composed of various materials including ceramic materials such as alumina and zirconia. Examples of the alkali metal hydroxide aqueous solution include a potassium hydroxide aqueous solution, a sodium hydroxide aqueous solution, a lithium hydroxide aqueous solution, and an ammonium hydroxide aqueous solution, and a potassium hydroxide aqueous solution is more preferable.

Method for Producing LDH Dense Plate A preferred form of the plate-like inorganic solid electrolyte is a layered double hydroxide (LDH) dense body. Although the LDH dense body may be produced by any method, an embodiment of a preferable production method will be described below. This production method is carried out by forming and firing LDH raw material powder typified by hydrotalcite to form an oxide fired body, regenerating it into a layered double hydroxide, and then removing excess water. . According to this method, a high-quality layered double hydroxide dense body having a relative density of 88% or more can be provided and produced easily and stably.

(1) as prepared raw material powder of the raw material powder, preferably the general ^{_{formula: M 2+ 1-x M 3+}} x (OH) 2 A n- x / n · mH 2 O ( ^{wherein, M 2+} is a divalent cation , ^{M 3+} is a trivalent ^{cation, a n-n-valent} anion, n is an integer of 1 or more, layered double hydroxide represented by x is 0.1-0.4) Prepare a powder. In the above general formula, M ²⁺ may be any divalent cation, and preferred examples include Mg ²⁺ , Ca ²⁺ and Zn ²⁺ , and more preferably Mg ²⁺ . M ³⁺ may be any trivalent cation, but preferred examples include Al ³⁺ or Cr ³⁺ , and more preferred is Al ³⁺ . A ^n- may be any anion, preferred examples OH ^- and _CO ^{3 2-} and the like. Accordingly, the general formula is at least ^{M 2+} is ^{Mg 2+,} include ^{M 3+} is ^{Al 3+, A n-is} OH ^- and / or _CO preferably contains ^{3 2-.} n is an integer of 1 or more, preferably 1 or 2. x is 0.1 to 0.4, preferably 0.2 to 0.35. Such a raw material powder may be a commercially available layered double hydroxide product, or may be a raw material produced by a known method such as a liquid phase synthesis method using nitrate or chloride. The particle size of the raw material powder is not limited as long as a desired layered double hydroxide dense body is obtained, but the volume-based D50 average particle size is preferably 0.1 to 1.0 μm, more preferably 0.3. ~ 0.8 μm. This is because if the particle size of the raw material powder is too fine, the powder tends to aggregate, and there is a high possibility that pores will remain during molding, and if it is too large, the moldability will deteriorate.

If desired, the raw material powder may be calcined to obtain an oxide powder. The calcining temperature at this time is somewhat different depending on the constituent M ²⁺ and M ³⁺ , but is preferably 500 ° C. or lower, more preferably 380 to 460 ° C., in a region where the raw material particle size does not change significantly.

(2) Production of molded body A raw material powder is molded to obtain a molded body. In this molding, a molded body after molding and before firing (hereinafter referred to as a molded body) is 43 to 65%, more preferably 45 to 60%, and even more preferably 47% to 58%. For example, it is preferably performed by pressure molding. The relative density of the molded body is calculated by calculating the density from the size and weight of the molded body and dividing by the theoretical density, but the weight of the molded body is affected by the adsorbed moisture. It is preferable to measure the relative density after the molded body using the raw material powder stored for 24 hours or more in a desiccator having a room temperature and a relative humidity of 20% or less, or after storing the molded body under the above conditions. However, when the raw material powder is calcined to form an oxide powder, the relative density of the compact is preferably 26 to 40%, more preferably 29 to 36%. The relative density in the case of using oxide powder is based on the assumption that each metal element constituting the layered double hydroxide has changed to oxide by calcining, and the converted density obtained as a mixture of each oxide is the denominator. As sought. The pressure forming described as an example may be performed by a uniaxial press of a mold, or may be performed by cold isostatic pressing (CIP). In the case of using cold isostatic pressing (CIP), it is preferable to put the raw material powder in a rubber container and vacuum-seal it or use a preformed one. In addition, you may shape | mold by well-known methods, such as slip casting and extrusion molding, and it does not specifically limit about a shaping | molding method. However, when the raw material powder is calcined to obtain an oxide powder, it is limited to the dry molding method. The relative density of these compacts not only affects the strength of the resulting compact, but also affects the degree of orientation of the layered double hydroxides that usually have a plate shape. The relative density is preferably set within the above range.

(3) Firing step The molded body obtained in the above step is fired to obtain an oxide fired body. This firing is preferably performed so that the oxide fired body has a weight of 57 to 65% of the weight of the compact and / or a volume of 70 to 76% or less of the volume of the compact. When it is 57% or more of the weight of the molded product, it is difficult to generate a heterogeneous phase that cannot be regenerated during regeneration to a layered double hydroxide in the subsequent step, and when it is 65% or less, sufficient firing is performed in the subsequent step. Densify. Further, when it is 70% or more of the volume of the molded body, it is difficult to generate a heterogeneous phase when regenerating into a layered double hydroxide in a subsequent process, and cracks are hardly generated. Done and fully densified in later steps. When the raw material powder is calcined to obtain an oxide powder, it is preferable to obtain an oxide fired body of 85 to 95% of the weight of the compact and / or 90% or more of the volume of the compact. Regardless of whether or not the raw material powder is calcined, the firing is preferably performed so that the oxide fired body has a relative density of 20 to 40% in terms of oxide, more preferably 20 to 35. %, More preferably 20-30%. Here, the relative density in terms of oxide means that each metal element constituting the layered double hydroxide is changed to an oxide by firing, and the converted density obtained as a mixture of each oxide is used as the denominator. It is the obtained relative density. A preferable baking temperature for obtaining the oxide fired body is 400 to 850 ° C, more preferably 700 to 800 ° C. It is preferable to hold | maintain for 1 hour or more with the calcination temperature in this range, and a more preferable holding time is 3 to 10 hours. Further, in order to prevent moisture and carbon dioxide from being released due to rapid temperature rise and cracking the molded body, the temperature rise for reaching the firing temperature is preferably performed at a rate of 100 ° C./h or less. Preferably it is 5-75 degreeC / h, More preferably, it is 10-50 degreeC / h. Therefore, it is preferable to secure a total firing time from temperature increase to temperature decrease (100 ° C. or lower) of 20 hours or more, more preferably 30 to 70 hours, and further preferably 35 to 65 hours.

(4) Regeneration step to layered double hydroxide The oxide fired body obtained in the above step is held in or directly above the aqueous solution containing the n-valent anion (A ⁿ⁻ ) and layered double hydroxide. It regenerates into a product, thereby obtaining a layered double hydroxide solidified body rich in moisture. That is, the layered double hydroxide solidified body obtained by this production method inevitably contains excess moisture. The anion contained in the aqueous solution may be the same kind of anion as that contained in the raw material powder, or may be a different kind of anion. It is preferable that the oxide fired body is held in an aqueous solution or immediately above the aqueous solution by a hydrothermal synthesis method in a sealed container, and an example of such a sealed container is a sealed container made of Teflon (registered trademark). More preferably, it is a closed container provided with a jacket made of stainless steel or the like on the outside thereof. The layered double hydroxide is preferably formed by maintaining the oxide fired body at 20 ° C. or more and less than 200 ° C. so that at least one surface of the oxide fired body is in contact with the aqueous solution, and a more preferable temperature is 50 to 180. And a more preferable temperature is 100 to 150 ° C. It is preferable that the oxide sintered body is maintained at such a layered double hydroxide formation temperature for 1 hour or more, more preferably 2 to 50 hours, and further preferably 5 to 20 hours. With such a holding time, it is possible to avoid or reduce the occurrence of a heterogeneous phase by sufficiently regenerating the layered double hydroxide. The holding time is not particularly problematic if it is too long, but it may be set in a timely manner with emphasis on efficiency.

  When carbon dioxide (carbonate ion) in the air is assumed as an anion species of an aqueous solution containing an n-valent anion used for regeneration into a layered double hydroxide, ion-exchanged water can be used. In the hydrothermal treatment in the sealed container, the fired oxide body may be submerged in the aqueous solution, or the treatment may be performed in a state where at least one surface is in contact with the aqueous solution using a jig. When the treatment is carried out in a state where at least one surface is in contact with the aqueous solution, the amount of excess water is small compared to complete submersion, and the subsequent steps may be completed in a short time. However, if the amount of the aqueous solution is too small, cracks are likely to occur. Therefore, it is preferable to use moisture equal to or greater than the weight of the fired body.

(5) Dehydration process Excess water is removed from the water-rich layered double hydroxide solidified product obtained in the above process. Thus, the layered double hydroxide dense body of the present invention is obtained. The step of removing excess water is preferably performed in an environment of 300 ° C. or lower and an estimated relative humidity of 25% or higher at the maximum temperature of the removal step. In order to prevent rapid evaporation of moisture from the layered double hydroxide solidified body, when dehydrating at a temperature higher than room temperature, it should be re-enclosed in the sealed container used in the regeneration process to the layered double hydroxide. preferable. The preferable temperature in that case is 50-250 degreeC, More preferably, it is 100-200 degreeC. Moreover, the more preferable relative humidity at the time of spin-drying | dehydration is 25 to 70%, More preferably, it is 40 to 60%. Dehydration may be performed at room temperature, and there is no problem as long as the relative humidity is within a range of 40 to 70% in a normal indoor environment.

LDH dense layer with porous substrate As described above, the inorganic solid electrolyte body may be in the form of a film or a layer. In this case, it is preferable to use an inorganic solid electrolyte body with a porous substrate, in which a film-like or layered inorganic solid electrolyte body is formed on or in the porous substrate. A particularly preferable inorganic solid electrolyte body with a porous substrate comprises a porous substrate and an inorganic solid electrolyte layer formed on and / or in the porous substrate. The layer comprises layered double hydroxide (LDH) as described above. The inorganic solid electrolyte layer containing LDH (hereinafter referred to as LDH layer) preferably has no liquid permeability and air permeability. That is, the porous material may have liquid permeability and air permeability due to the presence of pores, but the LDH layer is preferably densified with LDH to such an extent that it does not have liquid permeability and air permeability. The LDH layer is preferably formed on a porous substrate. For example, as shown in FIG. 4, the LDH layer 20 is preferably formed as an LDH dense film on the porous substrate 28. In this case, needless to say, LDH may also be formed on the surface of the porous substrate 28 and in the pores in the vicinity thereof as shown in FIG. 4 due to the nature of the porous substrate 28. Alternatively, as shown in FIG. 5, LDH is densely formed in the porous substrate 28 (for example, the surface of the porous substrate 28 and the pores in the vicinity thereof), whereby at least one of the porous substrates 28 is formed. The portion may constitute the LDH layer 20 ′. In this regard, the embodiment shown in FIG. 5 has a configuration in which the film-corresponding portion in the LDH layer 20 of the embodiment shown in FIG. 4 is removed, but is not limited to this, and is parallel to the surface of the porous substrate 28. The LDH layer should just exist. In any case, since the LDH layer is densified with LDH to such an extent that it does not have liquid permeability and air permeability, it has hydroxide ion conductivity but does not have liquid permeability and air permeability (that is, basic). Thus, it has a unique function of passing only hydroxide ions.

  The porous substrate is preferably capable of forming an LDH layer on and / or in the porous substrate, and the material and the porous structure are not particularly limited. Typically, an LDH layer is formed on and / or in a porous substrate, but the LDH layer is formed on the nonporous substrate, and then the nonporous substrate is formed by various known methods. It may be made porous. In any case, the porous substrate preferably has a porous structure having liquid permeability and air permeability.

  The porous substrate is preferably composed of at least one selected from the group consisting of ceramic materials, metal materials, and polymer materials. More preferably, the porous substrate is made of a ceramic material. In this case, preferable examples of the ceramic material include alumina, zirconia, titania, magnesia, spinel, calcia, cordierite, zeolite, mullite, ferrite, zinc oxide, silicon carbide, aluminum nitride, silicon nitride, and any combination thereof. More preferred are alumina, zirconia, titania, and any combination thereof, particularly preferred are alumina and zirconia, and most preferred is alumina. When these porous ceramics are used, it is easy to form an LDH layer having excellent denseness. Preferable examples of the metal material include aluminum and zinc. Preferred examples of the polymer material include polystyrene, polyethersulfone, polypropylene, epoxy resin, polyphenylene sulfide, and any combination thereof. It is more preferable to appropriately select a material excellent in alkali resistance as the resistance to the battery electrolyte from the various preferable materials described above.

  The porous substrate preferably has an average pore diameter of 0.001 to 1.5 μm, more preferably 0.001 to 1.25 μm, still more preferably 0.001 to 1.0 μm, and particularly preferably 0.001. It is -0.75 micrometer, Most preferably, it is 0.001-0.5 micrometer. By setting it within these ranges, it is possible to form an LDH layer that is so dense that the porous substrate does not have liquid permeability while ensuring desired liquid permeability. In the present invention, the average pore diameter can be measured by measuring the longest distance of the pores based on an electron microscope (SEM) image of the surface of the porous substrate. The magnification of the electron microscope (SEM) image used for this measurement is 20000 times, and all obtained pore diameters are arranged in order of size, and the top 15 points and the bottom 15 points from the average value, with 30 points per field of view in total. The average pore diameter can be obtained by calculating an average value for two visual fields. For the length measurement, a length measurement function of SEM software, image analysis software (for example, Photoshop, manufactured by Adobe) or the like can be used.

  The surface of the porous substrate preferably has a porosity of 10 to 60%, more preferably 15 to 55%, and still more preferably 20 to 50%. By setting it within these ranges, it is possible to form an LDH layer that is so dense that the porous substrate does not have liquid permeability while ensuring desired liquid permeability. Here, the porosity of the surface of the porous substrate is adopted because it is easy to measure the porosity using the image processing described below, and the porosity of the surface of the porous substrate. This is because it can be said that it generally represents the porosity inside the porous substrate. That is, if the surface of the porous substrate is dense, the inside of the porous substrate can be said to be dense as well. In the present invention, the porosity of the surface of the porous substrate can be measured as follows by a technique using image processing. That is, 1) An electron microscope (SEM) image of the surface of the porous substrate (acquisition of 10,000 times or more) is obtained, and 2) a grayscale SEM image is read using image analysis software such as Photoshop (manufactured by Adobe). 3) Create a monochrome binary image by adjusting the threshold value of the histogram by the procedure of [Image] → [Tone Correction] → [Turn Tone], and 4) The number of pixels occupied by the black part of the image The value divided by the total number of pixels is the porosity (%). The porosity measurement by this image processing is preferably performed for a 6 μm × 6 μm region on the surface of the porous substrate. In order to obtain a more objective index, three arbitrarily selected regions are used. It is more preferable to employ the average value of the obtained porosity.

  The LDH layer is formed on the porous substrate and / or in the porous substrate, preferably on the porous substrate. For example, as shown in FIG. 4, when the LDH layer 20 is formed on the porous substrate 28, the LDH layer 20 is in the form of an LDH dense film, which is typically made of LDH. Become. Further, when the LDH layer 20 ′ is formed in the porous substrate 28 as shown in FIG. 5, the surface of the porous substrate 28 (typically the surface of the porous substrate 28 and the vicinity thereof). Since LDH is densely formed in the pores), the LDH layer 20 ′ is typically composed of at least a part of the porous substrate 28 and LDH. The LDH layer 20 ′ shown in FIG. 5 can be obtained by removing a portion corresponding to the film in the LDH layer 20 shown in FIG. 4 by a known method such as polishing or cutting.

  The LDH layer preferably does not have liquid permeability and air permeability. For example, the LDH layer does not allow water to permeate even if one side of the LDH layer is brought into contact with water at 25 ° C. for 1 week, and does not allow hydrogen gas to permeate even if hydrogen gas is pressurized on the one side with an internal / external differential pressure of 0.5 atm. . That is, the LDH layer is preferably densified with LDH to such an extent that it does not have liquid permeability and air permeability. However, when a defect that has liquid permeability locally and / or accidentally exists in the functional membrane, it is water-impermeable by filling the defect with an appropriate repair agent (for example, epoxy resin) and repairing it. And gas impermeability may be ensured, and such repair agents need not necessarily have hydroxide ion conductivity. In any case, the surface of the LDH layer (typically the LDH dense film) preferably has a porosity of 20% or less, more preferably 15% or less, still more preferably 10% or less, particularly preferably 7%. It is as follows. The lower the porosity of the surface of the LDH layer, the higher the density of the LDH layer (typically the LDH dense film), which is preferable. Here, the reason why the porosity of the surface of the LDH layer is adopted is that the porosity of the surface of the LDH layer is easily measured by using the image processing described below. It is because it can be said that the porosity of is generally expressed. That is, if the surface of the LDH layer is dense, the inside of the LDH layer can be said to be dense as well. In the present invention, the porosity of the surface of the LDH layer can be measured as follows by a technique using image processing. That is, 1) An electron microscope (SEM) image (10,000 times or more magnification) of the surface of the LDH layer is acquired, and 2) a grayscale SEM image is read using image analysis software such as Photoshop (manufactured by Adobe). ) Adjust the histogram threshold value by the procedure of [Image] → [Tone Correction] → [Turn Tone] to create a black and white binary image, 4) The number of pixels occupied by the black part is the total number of pixels in the image The value divided by the number is the porosity (%). Note that the porosity measurement by this image processing is preferably performed for a 6 μm × 6 μm region on the surface of the LDH layer. In order to obtain a more objective index, it is obtained for three arbitrarily selected regions. It is more preferable to adopt the average value of the porosity.

  The layered double hydroxide is composed of an aggregate of a plurality of plate-like particles (that is, LDH plate-like particles), and the plurality of plate-like particles are substantially the same as the surface of the porous substrate (substrate surface). It is preferably oriented in a direction that intersects perpendicularly or diagonally. As shown in FIG. 4, this embodiment is a particularly preferable and feasible embodiment when the LDH layer 20 is formed as an LDH dense film on the porous substrate 28. As shown in FIG. LDH is densely formed in the porous substrate 28 (typically in the surface of the porous substrate 28 and in the vicinity thereof), whereby at least a part of the porous substrate 28 forms the LDH layer 20 ′. This can be realized even in the case of configuration.

  That is, the LDH crystal is known to have the form of a plate-like particle having a layered structure as shown in FIG. 6, but the above-mentioned substantially vertical or oblique orientation is used for an LDH layer (for example, an LDH dense film). This is a very advantageous property. This is because, in an oriented LDH layer (for example, an oriented LDH dense film), hydroxide ion conductivity in the direction in which the LDH plate-like particles are oriented (ie, in a direction parallel to the LDH layer) is perpendicular to this. This is because there is a conductivity anisotropy that is much higher than the conductivity. In fact, the present applicant has obtained knowledge that the conductivity (S / cm) in the alignment direction is one order of magnitude higher than the conductivity (S / cm) in the direction perpendicular to the alignment direction in the LDH oriented bulk body. ing. That is, the substantially vertical or oblique alignment in the LDH layer of the present embodiment causes the conductivity anisotropy that the LDH alignment body can have in the layer thickness direction (that is, the direction perpendicular to the surface of the LDH layer or the porous substrate). As a result, the conductivity in the layer thickness direction can be maximized or significantly increased. In addition, since the LDH layer has a layer form, lower resistance than the bulk form LDH can be realized. An LDH layer having such an orientation easily conducts hydroxide ions in the layer thickness direction. In addition, since it is densified, it does not have liquid permeability or air permeability, and therefore, it is possible to prevent permeation of fuel to the air electrode side and suppress a decrease in electromotive force.

  Particularly preferably, the LDH plate-like particles are highly oriented in a substantially vertical direction in the LDH layer (typically an LDH dense film). This high degree of orientation is confirmed by the fact that when the surface of the LDH layer is measured by X-ray diffraction, the peak of the (003) plane is not substantially detected or smaller than the peak of the (012) plane. (However, when a porous substrate in which a diffraction peak is observed at the same position as the peak due to the (012) plane is used, the peak of the (012) plane due to the LDH plate-like particle is used. This is not the case). This characteristic peak characteristic indicates that the LDH plate-like particles constituting the LDH layer are oriented in a substantially vertical direction (that is, a vertical direction or an oblique direction similar thereto, preferably a vertical direction) with respect to the LDH layer. That is, the peak of the (003) plane is known as the strongest peak observed when X-ray diffraction is performed on non-oriented LDH powder. In the oriented LDH layer, the LDH plate-like particles are formed in the LDH layer. On the other hand, the (003) plane peak is not substantially detected or is smaller than the (012) plane peak because of being oriented in a substantially vertical direction. This is because the c-axis direction (00l) plane (l is 3 and 6) to which the (003) plane belongs is a plane parallel to the layered structure of the LDH plate-like particle. On the other hand, when oriented in the substantially vertical direction, the LDH layered structure also faces in the substantially vertical direction. As a result, when the surface of the LDH layer is measured by the X-ray diffraction method, the (00l) plane (l is 3 and 6). This is because the peak of) does not appear or becomes difficult to appear. In particular, the peak of the (003) plane tends to be stronger than the peak of the (006) plane when it exists, so it is easier to evaluate the presence / absence of orientation in the substantially vertical direction than the peak of the (006) plane. I can say that. Therefore, it is preferable that the oriented LDH layer is detected so that the peak of the (003) plane is substantially not detected or smaller than the peak of the (012) plane because it suggests a high degree of orientation in the vertical direction. I can say that.

  The LDH layer preferably has a thickness of 100 μm or less, more preferably 75 μm or less, still more preferably 50 μm or less, particularly preferably 25 μm or less, and most preferably 5 μm or less. Such thinness can realize low resistance of the inorganic solid electrolyte body. The LDH layer is preferably formed as an LDH dense film on the porous substrate. In this case, the thickness of the LDH layer corresponds to the thickness of the LDH dense film. When the LDH layer is formed in the porous substrate, the thickness of the LDH layer corresponds to the thickness of the composite layer composed of at least a part of the porous substrate and LDH, and the LDH layer is porous. When formed over and in the substrate, this corresponds to the total thickness of the LDH dense film and the composite layer. In any case, when the thickness is as described above, a desired low resistance suitable for practical use in battery applications and the like can be realized. The lower limit of the thickness of the LDH alignment film is not particularly limited because it varies depending on the application, but in order to ensure a certain degree of rigidity desired as an inorganic solid electrolyte body, the thickness is preferably 1 μm or more, more preferably Is 2 μm or more.

The inorganic solid electrolyte body with a porous base material described above includes (1) a porous base material, and (2) 0.20 to 0.40 mol / L of magnesium ions (Mg ²⁺ ) and aluminum ions (Al ³⁺ ). The porous base material is immersed in a raw material aqueous solution containing urea at a total concentration of (3), and (3) the porous base material is hydrothermally treated in the raw material aqueous solution to contain the layered double hydroxide. The LDH layer can be produced by forming it on and / or in the porous substrate.

(1) Preparation of porous substrate The porous substrate is as described above, and is preferably composed of at least one selected from the group consisting of ceramic materials, metal materials, and polymer materials. More preferably, the porous substrate is made of a ceramic material. In this case, preferable examples of the ceramic material include alumina, zirconia, titania, magnesia, spinel, calcia, cordierite, zeolite, mullite, ferrite, zinc oxide, silicon carbide, aluminum nitride, silicon nitride, and any combination thereof. More preferred are alumina, zirconia, titania, and any combination thereof, particularly preferred are alumina and zirconia, and most preferred is alumina. When these porous ceramics are used, the density of the LDH layer tends to be improved. When using a porous substrate made of a ceramic material, it is preferable to subject the porous substrate to ultrasonic cleaning, cleaning with ion exchange water, and the like.

(2) Immersion in raw material aqueous solution Next, the porous substrate is immersed in the raw material aqueous solution in a desired direction (for example, horizontally or vertically). When the porous substrate is held horizontally, the porous substrate may be suspended, floated, or disposed so as to be in contact with the bottom of the container. For example, the porous substrate is suspended from the bottom of the container in the raw material aqueous solution. The material may be fixed. When the porous substrate is held vertically, a jig that can set the porous substrate vertically on the bottom of the container may be placed. In any case, LDH is substantially perpendicular to or close to the porous substrate (that is, the LDH plate-like particles have their plate surfaces intersecting the surface (substrate surface) of the porous substrate substantially perpendicularly or obliquely. It is preferable to adopt a configuration or arrangement in which growth is performed in such a direction. The raw material aqueous solution contains magnesium ions (Mg ²⁺ ) and aluminum ions (Al ³⁺ ) at a predetermined total concentration, and contains urea. By the presence of urea, ammonia is generated in the solution by utilizing hydrolysis of urea, so that the pH value increases, and the coexisting metal ions form hydroxides to obtain LDH. Further, since carbon dioxide is generated in the hydrolysis, LDH in which the anion is carbonate ion type can be obtained. The total concentration (Mg ²⁺ + Al ³⁺ ) of magnesium ions and aluminum ions contained in the raw material aqueous solution is preferably 0.20 to 0.40 mol / L, more preferably 0.22 to 0.38 mol / L, still more preferably 0.24 to 0.36 mol / L, particularly preferably 0.26 to 0.34 mol / L. When the concentration is within such a range, nucleation and crystal growth can proceed in a well-balanced manner, and an LDH layer excellent not only in orientation but also in denseness can be obtained. That is, when the total concentration of magnesium ions and aluminum ions is low, crystal growth becomes dominant compared to nucleation, and the number of particles decreases and particle size increases. It is considered that the generation becomes dominant, the number of particles increases, and the particle size decreases.

Preferably, magnesium nitrate and aluminum nitrate are dissolved in the raw material aqueous solution, so that the raw material aqueous solution contains nitrate ions in addition to magnesium ions and aluminum ions. In this case, the molar ratio (urea / NO ₃ ⁻ ) of urea to nitrate ions (NO ₃ ⁻ ) in the raw material aqueous solution is preferably 2 to 6, and more preferably 4 to 5.

(3) Formation of LDH layer by hydrothermal treatment Then, the porous substrate is hydrothermally treated in the raw material aqueous solution to form an LDH layer containing LDH on and / or in the porous substrate. . This hydrothermal treatment is preferably performed at 60 to 150 ° C. in a closed container, more preferably 65 to 120 ° C., still more preferably 65 to 100 ° C., and particularly preferably 70 to 90 ° C. The upper limit temperature of the hydrothermal treatment may be selected so that the porous substrate (for example, the polymer substrate) is not deformed by heat. The rate of temperature increase during the hydrothermal treatment is not particularly limited and may be, for example, 10 to 200 ° C./h, preferably 100 to 200 ° C./h, more preferably 100 to 150 ° C./h. The hydrothermal treatment time may be appropriately determined according to the target density and thickness of the LDH layer.

  After the hydrothermal treatment, the porous substrate is preferably taken out from the sealed container and washed with ion exchange water.

  The LDH layer in the LDH-containing composite material produced as described above is one in which LDH plate-like particles are highly densified and oriented in a substantially vertical direction advantageous for conduction.

  By the way, the LDH layer obtained by the said manufacturing method can be formed in both surfaces of a porous base material. For this reason, in order to make the LDH-containing composite material suitable for use as an inorganic solid electrolyte body for fuel cells, the LDH layer on one side of the porous substrate is mechanically scraped after film formation, or the film is formed. Sometimes it is desirable to take measures to prevent the formation of an LDH layer on one side.

  The present invention is more specifically described by the following examples.

Example 1 : Preparation and evaluation of inorganic solid electrolyte body (LDH dense body) (1) Preparation of LDH dense body First, as a raw material powder, a hydrotalcite powder (DHT-4H, Kyowa Chemical) which is a commercially available layered double hydroxide. Industrial Co., Ltd.) powder was prepared. The composition of this raw material powder was Mg ²⁺ _0.68 Al ³⁺ _0.32 (OH) ₂ CO ₃ ^{2 −} _0.16 · mH ₂ O. The raw material powder was filled into a 16 mm diameter mold and uniaxial press molding was performed at a molding pressure of 500 kgf · cm ² to obtain a molded body having a relative density of 53% and a thickness of about 2 mm. The relative density was measured on a molded article stored at room temperature and a relative humidity of 20% or less for 24 hours. The obtained molded body was fired in an alumina sheath. This firing is performed at a rate of 100 ° C./h or less to prevent moisture and carbon dioxide from being released due to a sudden rise in temperature, and when the temperature reaches a maximum temperature of 750 ° C., 5 After holding for a period of time, cooling was performed. The total firing time from the temperature increase to the temperature decrease (100 ° C. or less) was 62 hours, and the weight, volume and relative density of the obtained sintered body were 59% by weight, 72% by volume and 23%, respectively. It was. The “weight” and “volume” are relative values (%) calculated with the compact before firing as 100%, and the “relative density” is the constituent metal elements of hydrotalcite, Mg and Al. It is a relative density in terms of oxide obtained using the theoretical density calculated as an oxide. The fired body thus obtained was sealed in a sealed container made of Teflon (registered trademark) with a stainless steel jacket on the outside together with ion-exchanged water in the atmosphere, and kept at 100 ° C. for 5 hours (regeneration conditions (temperature and its temperature). The sample was obtained by performing a hydrothermal treatment with the retention time at (5). Since the sample cooled to room temperature contained excess moisture, the moisture on the surface was gently wiped off with a filter paper or the like. The sample thus obtained was naturally dehydrated (dried) in a room at 25 ° C. and a relative humidity of about 50% to obtain an LDH dense sample.

(2) Measurement of relative density The density was calculated by calculating the density from the size and weight of the LDH dense body sample, and dividing this density by the theoretical density, and it was 91%. In calculating the theoretical density, JCPDS card No. 1 was used as the theoretical density of Mg / Al = 2 hydrotalcite. 2.09 g / cm ³ described in 70-2151 was used.

(3) Determination of cracks When the LDH dense body sample was observed with the naked eye, no cracks were observed.

(4) Identification of crystal phase The crystal phase of the LDH dense body sample was measured with an X-ray diffractometer (D8 ADVANCE, manufactured by Bulker AXS) under the measurement conditions of voltage: 40 kV, current value: 40 mA, measurement range: 5-70 °. JCPDS card NO. It was identified using the hydrotalcite diffraction peak described in 35-0965. As a result, only peaks due to hydrotalcite were observed.

(5d) Denseness determination test I
In order to confirm that the LDH dense body sample has a denseness that does not have liquid permeability, a denseness determination test was conducted as follows. First, as shown in FIG. 7A, the sample 120 obtained in (1) above (cut out to 1 cm × 1 cm square) was provided with an opening 122a of 0.5 cm × 0.5 cm square in the center. Silicon rubber 122 was bonded, and the resulting laminate was bonded between two acrylic containers 124 and 126. The bottom of the acrylic container 124 disposed on the silicon rubber 122 side is pulled out, whereby the silicon rubber 122 is bonded to the acrylic container 124 with the opening 122a open. On the other hand, the acrylic container 126 disposed in the sample 120 has a bottom, and the container 126 contains liquid fuel 128 in which pure water and ethanol are mixed at a weight ratio of 100: 20. In other words, the components are arranged so that the liquid fuel 128 is in contact with one surface of the sample 120 by turning upside down after assembly. After assembling these components, the total weight was measured. Needless to say, the container 126 has a closed vent hole (not shown) and is opened after being turned upside down. The assembly was placed upside down as shown in FIG. 7B and held at 25 ° C. for 1 week, and then the total weight was measured again. At this time, when a droplet adhered to the inner side surface of the acrylic container 124, the droplet was wiped off. Then, the density was determined by calculating the difference in the total weight before and after the test. As a result, no change was observed in the weight of the liquid fuel even after holding at 25 ° C. for 1 week. From this, it was confirmed that the LDH dense body sample has high density so as not to have liquid permeability.

(5e) Denseness determination test II
In order to confirm that the LDH dense body sample does not have air permeability, a denseness determination test was performed as follows. First, as shown in FIGS. 8A and 8B, an acrylic container 130 without a lid and an alumina jig 132 having a shape and size that can function as a lid for the acrylic container 130 were prepared. The acrylic container 130 is formed with a gas supply port 130a for supplying gas therein. The alumina jig 132 is formed with an opening 132a having a diameter of 5 mm, and a sample placement recess 132b is formed along the outer periphery of the opening 132a. An epoxy adhesive 134 was applied to the depression 132b of the alumina jig 132, and a sample 136 was placed on the depression 132b and adhered to the alumina jig 132 in an airtight and liquid-tight manner (Example 2 described later in FIG. 8A). A sample 136 composed of a two-layer structure 136a and 136b corresponding to the composite material sample is drawn, but in Example 1, it means an LDH dense body sample 136 having a one-layer structure). Then, the alumina jig 132 to which the sample 136 is bonded is adhered to the upper end of the acrylic container 130 in a gas-tight and liquid-tight manner using a silicone adhesive 138 so as to completely close the open portion of the acrylic container 130 for measurement. A sealed container 140 was obtained. The measurement sealed container 140 was placed in a water tank 142, and the gas supply port 130 a of the acrylic container 130 was connected to a pressure gauge 144 and a flow meter 146 so that hydrogen gas could be supplied into the acrylic container 130. Water 143 was put into the water tank 142 and the measurement sealed container 140 was completely submerged. At this time, the inside of the measurement sealed container 140 is sufficiently airtight and liquid-tight, and one side of the sample 136 is exposed to the internal space of the measurement sealed container 140, while the other side of the composite material sample 136 is exposed. The side is in contact with the water in the aquarium 142. In this state, hydrogen gas was introduced into the measurement sealed container 140 into the acrylic container 130 through the gas supply port 130a. The pressure gauge 144 and the flow meter 146 are controlled so that the differential pressure inside and outside the sample 136 is 0.5 atm (that is, the pressure applied to the side in contact with hydrogen gas is 0.5 atm higher than the water pressure applied to the opposite side). Whether or not bubbles of hydrogen gas were generated in the water from the sample 136 was observed. As a result, generation of bubbles due to hydrogen gas was not observed. Therefore, it was confirmed that the sample 136 has high density so as not to have air permeability.

Example 2 : Production and evaluation of inorganic solid electrolyte body (LDH dense membrane) with porous substrate (1) Production of porous substrate Boehmite (manufactured by Sasol, DISPAL 18N4-80), methylcellulose, and ion-exchanged water, After weighing so that the weight ratio of (boehmite) :( methylcellulose) :( ion exchanged water) was 10: 1: 5, the mixture was kneaded. The obtained kneaded product was subjected to extrusion molding using a hand press and molded into a plate shape having a size sufficiently exceeding 5 cm × 8 cm and a thickness of 0.5 cm. The obtained molded body was dried at 80 ° C. for 12 hours and then calcined at 1150 ° C. for 3 hours to obtain an alumina porous substrate. The porous substrate thus obtained was cut into a size of 5 cm × 8 cm.

  With respect to the obtained porous substrate, the porosity on the surface of the porous substrate was measured by a technique using image processing, and it was 24.6%. The porosity is measured by 1) observing the surface microstructure using a scanning electron microscope (SEM, JSM-6610LV, manufactured by JEOL) at an acceleration voltage of 10 to 20 kV, and an electron microscope on the surface of the porous substrate ( SEM) image (magnification of 10,000 times or more) is obtained, 2) a grayscale SEM image is read using image analysis software such as Photoshop (manufactured by Adobe), etc. 3) [Image] → [Tone Correction] → [2 The threshold value of the histogram is adjusted in the procedure of [gradation] to create a black and white binary image, and 4) the value obtained by dividing the number of pixels occupied by the black portion by the total number of pixels of the image is the porosity (%) It was done by doing. This porosity measurement was performed on a 6 μm × 6 μm region on the surface of the porous substrate. FIG. 9 shows an SEM image of the porous substrate surface.

  Moreover, it was about 0.1 micrometer when the average hole diameter of the porous base material was measured. In the present invention, the average pore diameter was measured by measuring the longest distance of the pores based on an electron microscope (SEM) image of the surface of the porous substrate. The magnification of the electron microscope (SEM) image used for this measurement is 20000 times, and all the obtained pore diameters are arranged in order of size, and the top 15 points and the bottom 15 points from the average value, and 30 points per visual field in total. The average value for two visual fields was calculated to obtain the average pore diameter. For length measurement, the length measurement function of SEM software was used.

(2) Cleaning of porous substrate The obtained porous substrate was ultrasonically cleaned in acetone for 5 minutes, ultrasonically cleaned in ethanol for 2 minutes, and then ultrasonically cleaned in ion-exchanged water for 1 minute.

(3) As the manufacturing raw material of the raw aqueous solution, magnesium nitrate hexahydrate _{(Mg (NO 3) 2 ·} 6H 2 O, manufactured by Kanto Chemical Co., Inc.), aluminum nitrate nonahydrate (Al _{(NO 3)} 3 · 9H ₂ O, manufactured by Kanto Chemical Co., Ltd.) and urea ((NH ₂ ) ₂ CO, manufactured by Sigma-Aldrich) were prepared. Weigh magnesium nitrate hexahydrate and aluminum nitrate nonahydrate so that the cation ratio (Mg ²⁺ / Al ³⁺ ) is 2 and the total metal ion molar concentration (Mg ²⁺ + Al ³⁺ ) is 0.320 mol / L. In a beaker, ion exchange water was added to make a total volume of 600 ml. After stirring the obtained solution, urea weighed at a ratio of urea / NO ₃ ⁻ = 4 was added to the solution, and further stirred to obtain a raw material aqueous solution.

(4) Film formation by hydrothermal treatment The Teflon (registered trademark) sealed container (with an internal volume of 800 ml, the outside is a stainless steel jacket), the raw material aqueous solution prepared in (3) above and the porous substrate washed in (2) above Both were enclosed. At this time, the base material was fixed by being floated from the bottom of a Teflon (registered trademark) sealed container, and placed horizontally so that the solution was in contact with both surfaces of the base material. Thereafter, a hydrothermal treatment was performed at a hydrothermal temperature of 70 ° C. for 168 hours (7 days) to form a layered double hydroxide alignment film (solid electrolyte body) on the substrate surface. After the elapse of a predetermined time, the substrate is taken out from the sealed container, washed with ion-exchanged water, dried at 70 ° C. for 10 hours, and a dense layer of layered double hydroxide (hereinafter referred to as LDH) (hereinafter referred to as a membrane sample). ) Was obtained on a substrate. The thickness of the obtained film sample was about 1.5 μm. Thus, a layered double hydroxide-containing composite material sample (hereinafter referred to as a composite material sample) was obtained. Although the LDH film was formed on both surfaces of the porous substrate, the LDH film on one surface of the porous substrate was mechanically scraped.

(5) Various evaluations (5a) Identification of membrane sample Membrane sample was measured with X-ray diffractometer (RINT TTR III manufactured by Rigaku Corporation) under the measurement conditions of voltage: 50 kV, current value: 300 mA, measurement range: 10-70 °. As a result, the XRD profile shown in FIG. 10 was obtained. About the obtained XRD profile, JCPDS card NO. It identified using the diffraction peak of the layered double hydroxide (hydrotalcite compound) described in 35-0964. As a result, it was confirmed that the film sample was a layered double hydroxide (LDH, hydrotalcite compound). In addition, in the XRD profile shown in FIG. 10, a peak (a peak marked with a circle in the figure) due to alumina constituting the porous substrate on which the film sample is formed is also observed. .

(5b) Observation of microstructure The surface microstructure of the film sample was observed at an acceleration voltage of 10 to 20 kV using a scanning electron microscope (SEM, JSM-6610LV, manufactured by JEOL). FIG. 11 shows an SEM image (secondary electron image) of the surface microstructure of the obtained film sample.

  Further, the cross section of the composite material sample was polished by CP polishing to form a polished cross section, and the microstructure of the polished cross section was observed at an acceleration voltage of 10 to 20 kV using a scanning electron microscope (SEM). An SEM image of the polished cross-sectional microstructure of the composite material sample thus obtained is shown in FIG.

(5c) Measurement of porosity The porosity of the surface of the membrane was measured for the membrane sample by a technique using image processing. The porosity is measured by 1) observing the surface microstructure using a scanning electron microscope (SEM, JSM-6610LV, manufactured by JEOL) at an acceleration voltage of 10 to 20 kV, and an electron microscope (SEM) on the surface of the film. An image (magnification of 10,000 times or more) is acquired, 2) a grayscale SEM image is read using image analysis software such as Photoshop (manufactured by Adobe), and 3) [image] → [tone correction] → [2 gradations] The threshold value of the histogram is adjusted to create a monochrome binary image, and 4) the value obtained by dividing the number of pixels occupied by the black portion by the total number of pixels in the image is the porosity (%). It went by. This porosity measurement was performed on a 6 μm × 6 μm region of the alignment film surface. As a result, the porosity of the film surface was 19.0%. Further, using the porosity of the film surface, the density D when viewed from the film surface (hereinafter referred to as the surface film density) was calculated by D = 100% − (porosity of the film surface). %Met.

  Further, the porosity of the polished cross section of the film sample was also measured. The measurement of the porosity of the polished cross section is the same as that described above except that an electron microscope (SEM) image (magnification of 10,000 times or more) of the cross-section polished surface in the thickness direction of the film was obtained according to the procedure shown in (5b) above. It carried out similarly to the porosity of the film | membrane surface. The measurement of the porosity was performed on the film portion of the alignment film cross section. Thus, the porosity calculated from the cross-sectional polished surface of the film sample is 3.5% on average (average value of the three cross-sectional polished surfaces), and a very high-density film is formed on the porous substrate. It was confirmed that

(5d) Denseness determination test I
In order to confirm that the membrane sample was dense enough not to have liquid permeability, a denseness determination test was performed as follows. First, as shown in FIG. 7A, the composite material sample 120 obtained in (1) above (cut to 1 cm × 1 cm square) is 0.5 cm × 0.5 cm square in the center on the film sample side. The silicon rubber 122 provided with the opening 122a was adhered, and the obtained laminate was adhered between two acrylic containers 124 and 126. The bottom of the acrylic container 124 disposed on the silicon rubber 122 side is pulled out, whereby the silicon rubber 122 is bonded to the acrylic container 124 with the opening 122a open. On the other hand, the acrylic container 126 disposed on the porous substrate side of the composite material sample 120 has a bottom, and the liquid fuel 128 in which pure water and ethanol are mixed at a weight ratio of 100: 20 is contained in the container 126. Is included. In other words, the constituent members are arranged so that the liquid fuel 128 is in contact with the porous base material side of the composite material sample 120 by turning upside down after assembly. After assembling these components, the total weight was measured. Needless to say, the container 126 has a closed vent hole (not shown) and is opened after being turned upside down. The assembly was placed upside down as shown in FIG. 7B and held at 25 ° C. for 1 week, and then the total weight was measured again. At this time, when a droplet adhered to the inner side surface of the acrylic container 124, the droplet was wiped off. Then, the density was determined by calculating the difference in the total weight before and after the test. As a result, no change was observed in the weight of the liquid fuel even after holding at 25 ° C. for 1 week. From this, it was confirmed that the membrane sample (that is, the solid electrolyte body) has a high density so as not to have liquid permeability.

(5e) Denseness determination test II
In order to confirm that the film sample has a denseness that does not have air permeability, a denseness determination test was performed as follows. First, as shown in FIGS. 8A and 8B, an acrylic container 130 without a lid and an alumina jig 132 having a shape and size that can function as a lid for the acrylic container 130 were prepared. The acrylic container 130 is formed with a gas supply port 130a for supplying gas therein. The alumina jig 132 is formed with an opening 132a having a diameter of 5 mm, and a depression 132b for placing a film sample is formed along the outer periphery of the opening 132a. An epoxy adhesive 134 was applied to the depression 132 b of the alumina jig 132, and the film sample 136 b side of the composite material sample 136 was placed in the depression 132 b and adhered to the alumina jig 132 in an air-tight and liquid-tight manner. Then, the alumina jig 132 to which the composite material sample 136 is bonded is adhered to the upper end of the acrylic container 130 in a gas-tight and liquid-tight manner using a silicone adhesive 138 so as to completely close the open portion of the acrylic container 130. A measurement sealed container 140 was obtained. The measurement sealed container 140 was placed in a water tank 142, and the gas supply port 130 a of the acrylic container 130 was connected to a pressure gauge 144 and a flow meter 146 so that hydrogen gas could be supplied into the acrylic container 130. Water 143 was put into the water tank 142 and the measurement sealed container 140 was completely submerged. At this time, the inside of the measurement sealed container 140 is sufficiently airtight and liquid tight, and the membrane sample 136b side of the composite material sample 136 is exposed to the internal space of the measurement sealed container 140, while the composite material sample The porous substrate 136 a side of 136 is in contact with the water in the water tank 142. In this state, hydrogen gas was introduced into the measurement sealed container 140 into the acrylic container 130 through the gas supply port 130a. The pressure gauge 144 and the flow meter 146 are controlled so that the differential pressure inside and outside the membrane sample 136b is 0.5 atm (that is, the pressure applied to the side in contact with hydrogen gas is 0.5 atm higher than the water pressure applied to the opposite side). Then, it was observed whether or not hydrogen gas bubbles were generated in the water from the composite material sample 136. As a result, generation of bubbles due to hydrogen gas was not observed. Therefore, it was confirmed that the membrane sample 136b has high density so as not to have air permeability.

Example 3 Production of Solid Alkaline Fuel Cell (1) Production of Solid Electrolyte Body Diameter was changed in the same manner as in Example 1 except that the size of the mold and the thickness of the molded article produced using the mold were changed. A disk-shaped LDH dense body having a thickness of 20 mm and a thickness of 0.3 mm is obtained as a solid electrolyte body. As shown in FIG. 14, the obtained solid electrolyte body 216 was fitted into a circular opening 218a (diameter 20 mm) of the electrolyte fixing jig 218, and a circular opening 220a having a diameter of 19 mm was formed at the center. Fix using PTFE tape 220. Thus, the solid electrolyte body 16 is securely fixed in the opening 218a of the electrolyte fixing jig 218.

(2) Production of air electrode and fuel electrode Commercially available platinum-supported carbon (Pt support amount 20 wt%) is prepared. The platinum-supporting carbon (hereinafter referred to as Pt / C) is mixed with carboxymethyl cellulose (hereinafter referred to as CMC binder) and water as binders, and the weight ratio of (Pt / C) :( CMC binder) :( water) is 9 wt%: 0. .9 wt%: Mix to a ratio of 90 wt% to make a paste. The obtained paste is printed on one surface of the inorganic solid electrolyte body 216 to form the air electrode 212, and printed on the other surface to form the fuel electrode 214.

(3) Battery assembly Using the thus obtained inorganic solid electrolyte body 216, air electrode 212, fuel electrode 214, etc., a solid alkaline fuel cell is produced as follows. FIG. 13 is an exploded perspective view of the solid alkaline fuel cell manufactured in this example. The air electrode 212 and the fuel electrode 214 are printed on the inorganic solid electrolyte body 16, but in FIG. 13, the air electrode 212 and the fuel electrode 214 are separated from the solid electrolyte body 216 for the purpose of clarifying the constituent members. . Then, as shown in FIG. 13, a gasket 222 (made of PTFE) having an opening 222a formed on the air electrode 212 side of the laminate of the fuel electrode 214 / inorganic solid electrolyte body 216 / air electrode 212, and humidified air. An air supply member 213 (made of carbon) and a current collector plate 226 (made of gold-plated copper) for supply are laminated, while a gasket 224 (made of PTFE) having an opening 224a formed on the fuel electrode 214 side of the laminate, A fuel supply member 215 (made of carbon) and a current collector plate 228 (made of gold-plated copper) for supplying fuel are stacked. The air supply member 213 includes a channel 213a for passing humidified air and a slit (not shown) for supplying the humidified air to the air electrode 212, while the fuel supply member 215 has a channel 215a for passing fuel. And a slit 215b for supplying fuel to the fuel electrode. In this way, the laminate in which the respective constituent members are laminated is fastened and fixed with screws 230 through screw holes 226a and 228a formed at the four corners of the two current collector plates 226 and 228. Thus, a solid alkaline fuel cell according to the present invention is obtained.

The present invention includes the following aspects.
[Claim 1]
An air electrode supplied with oxygen;
An anode supplied with liquid fuel and / or gaseous fuel;
An inorganic solid electrolyte body interposed between the fuel electrode and the air electrode and having hydroxide ion conductivity;
A solid alkaline fuel cell comprising:
The inorganic solid electrolyte is M ²⁺ _1-x M ³⁺ _x (OH) ₂ A ⁿ⁻ _{x / n} · mH ₂ O (wherein M ²⁺ is a divalent cation and M ³⁺ is a trivalent cation). it is a cation, a ^n-is the n-valent anion, n is an integer of 1 or more, x is made of a layered double hydroxide having a basic composition of 0.1 to 0.4) A solid alkaline fuel cell in which the inorganic solid electrolyte body is densified by hydrothermal treatment.
[Section 2]
Item 2. The solid alkaline fuel cell according to Item 1, wherein the inorganic solid electrolyte body does not have liquid permeability and air permeability.
[Section 3]
Item 3. The solid alkaline fuel cell according to Item 1 or 2, wherein the inorganic solid electrolyte body has a relative density of 90% or more.
[Claim 4]
Among the general ^formula, the ^{M 2+} is ^{Mg 2+,} include ^{M 3+} is ^{Al 3+, A n-is} OH ^- and / or _CO ³ includes ^2-, according to any one of claims 1 to 3 Solid Alkaline fuel cell.
[Section 5]
Item 5. The solid alkaline fuel cell according to any one of Items 1 to 4, wherein the inorganic solid electrolyte body has a plate shape, a film shape, or a layer shape.
[Claim 6]
Item 6. The solid alkaline fuel cell according to any one of Items 1 to 5, further comprising a porous substrate on one surface or both surfaces of the inorganic solid electrolyte body.
[Claim 7]
Item 7. The solid alkali according to Item 6, wherein the inorganic solid electrolyte is in the form of a film or layer, and the film or layer of inorganic solid electrolyte is formed on or in the porous substrate. Fuel cell.
[Section 8]
Item 8. The solid alkaline fuel cell according to Item 6 or 7, wherein the porous substrate is composed of a material having hydroxide ion conductivity.
[Claim 9]
The porous substrate is made of a material having no hydroxide ion conductivity, and is provided on the surface of the inorganic solid electrolyte body on the fuel electrode side, and the liquid fuel and alkali metal water are provided on the fuel electrode. Item 8. The solid alkaline fuel cell according to Item 6 or 7, wherein a mixed solution with an aqueous oxide solution is supplied.
[Section 10]
Item 10. The solid alkaline fuel cell according to any one of Items 1 to 9, wherein liquid fuel is supplied to the fuel electrode.
[Section 11]
Item 11. The solid alkaline fuel cell according to any one of Items 1 to 10, wherein the liquid fuel is a liquid containing water and / or alcohol.
[Claim 12]
Item 12. The solid alkaline fuel cell according to any one of Items 1 to 11, wherein the liquid fuel contains at least one selected from the group consisting of ethanol, methanol, ethylene glycol, hydrazine hydrate, and ammonia.

DESCRIPTION OF SYMBOLS 10 Solid alkaline fuel cell 12 Air electrode 13 Air supply means 14 Fuel electrode 15 Fuel supply means 16 Inorganic solid electrolyte body 20 LDH layer 28 Porous base material

Claims (14)

An air electrode supplied with oxygen;
An anode supplied with liquid fuel and / or gaseous fuel;
An inorganic solid electrolyte body interposed between the fuel electrode and the air electrode and having hydroxide ion conductivity;
A solid alkaline fuel cell comprising:
A solid alkaline fuel cell, wherein the inorganic solid electrolyte body is composed of a layered double hydroxide, and the inorganic solid electrolyte body is densified by hydrothermal treatment.   The solid alkaline fuel cell according to claim 1, wherein the inorganic solid electrolyte body does not have liquid permeability and air permeability.   The solid alkaline fuel cell according to claim 1 or 2, wherein the inorganic solid electrolyte body has a relative density of 90% or more. The layered double hydroxide is M ²⁺ _1-x M ³⁺ _x (OH) ₂ A ⁿ⁻ _{x / n} · mH ₂ O (wherein M ²⁺ is a divalent cation, and M ³⁺ is trivalent. A ⁿ⁻ is an n-valent anion, n is an integer of 1 or more, x is 0.1 to 0.4, and a part or all of M ³⁺ is tetravalent or The solid alkaline fuel cell according to any one of claims 1 to 3, which has a basic composition (which may be replaced by a cation having a higher valence).   The solid alkaline fuel cell according to any one of claims 1 to 4, wherein the inorganic solid electrolyte body has a plate shape, a membrane shape, or a layer shape.   The solid alkaline fuel cell according to any one of claims 1 to 5, further comprising a porous substrate on one side or both sides of the inorganic solid electrolyte body.   The solid according to claim 6, wherein the inorganic solid electrolyte is in the form of a film or a layer, and the film or layer of the inorganic solid electrolyte is formed on or in the porous substrate. Alkaline fuel cell.   The solid alkaline fuel cell according to claim 6 or 7, wherein the porous substrate is made of a polymer material, and the inorganic solid electrolyte is formed in the porous substrate.   The solid alkaline fuel cell according to claim 8, wherein the polymer material is selected from the group consisting of polystyrene, polyethersulfone, polypropylene, epoxy resin, and polyphenylene sulfide.   The solid alkaline fuel cell according to any one of claims 6 to 8, wherein the porous substrate is made of a material having hydroxide ion conductivity.   The porous substrate is made of a material having no hydroxide ion conductivity, and is provided on the surface of the inorganic solid electrolyte body on the fuel electrode side, and the liquid fuel and alkali metal water are provided on the fuel electrode. The solid alkaline fuel cell according to any one of claims 6 to 9, wherein a mixed solution with an aqueous oxide solution is supplied.   The solid alkaline fuel cell according to claim 1, wherein liquid fuel is supplied to the fuel electrode.   The solid alkaline fuel cell according to any one of claims 1 to 12, wherein the liquid fuel is a liquid containing water and / or alcohol. The solid alkaline fuel cell according to any one of claims 1 to 13, wherein the liquid fuel contains at least one selected from the group consisting of ethanol, methanol, ethylene glycol, hydrazine hydrate, and ammonia. .