JP2009043682A - Organic-inorganic hybrid electrolyte and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing an organic-inorganic hybrid electrolyte which has a wide range of selections in materials and mixing conditions. <P>SOLUTION: The method has a process in which a reformed inorganic material is made by introducing into an inorganic material a modification group having a mutual electrostatic operation with an ion conductive group held by an organic polymer material and then the same is mixed/dispersed in an organic polymer material. By introducing the modification group, affinity between the organic polymer material and the reformed organic material can be raised very high, and even under the condition that mixture/dispersion cannot be conducted conventionally, an organic-inorganic hybrid electrolyte can be manufactured. Specifically, the method has a mixing process in which the organic polymer material having the ion conductive group, a polarorganic solvent having affinity with the organic polymer material, a surface reforming agent introducing an organic material having affinity with the polarorganic solvent, and a reformed inorganic material which can be obtained by making a surface modification agent, which introduces a modification group having cation which generates an attraction force against the ion conductive group, contact with an inorganic material precursor are mixed. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an organic-inorganic hybrid electrolyte in which an organic polymer material having proton conductivity and an inorganic material are highly mixed and dispersed, and a method for producing the same.

  Conventionally, attention has been focused on fuel cells as clean energy sources from the viewpoint of dealing with environmental problems. Here, organic-inorganic hybrid electrolytes, which are materials obtained by combining an organic material and an inorganic material, have been developed as electrolyte membranes used in fuel cells (Patent Documents 1 to 4). The organic-inorganic hybrid electrolyte has characteristics such as high ion conductivity and high thermal stability at high temperatures.

  By the way, the inorganic material and the organic material may not have sufficient affinity. In such a case, it is difficult to uniformly mix and disperse the inorganic material and the organic material. If the inorganic material and the organic material are not uniformly mixed / dispersed, the performance of each material is often lower than the performance of each material alone.

Therefore, as a method for producing an electrolyte material in which an organic material and an inorganic material are uniformly mixed and dispersed, Patent Document 1 discloses that a precursor of an inorganic component is infiltrated into a polymer film, An organic / inorganic hybrid film in which a precursor is hydrolyzed and polymerized to form a hybrid is disclosed. Patent Document 4 discloses a technique for improving the affinity with an organic material by modifying the periphery of the inorganic material with a chemical modifier, which is an organic substance. It was hard to say that was realized.
JP 2007-18778 A (Claim 2 etc.) JP 2004-119072 A JP 2005-166486 A International Publication No. 2007/029346 Pamphlet (0117 paragraph etc.)

  By the way, in order to realize the required performance in the organic-inorganic hybrid electrolyte, each of the organic material and the inorganic material can be compounded under various conditions such as various materials and various mixing ratios. desired. However, as described above, there are cases where the inorganic material and the organic material do not have sufficient affinity. Therefore, the desired hybrid electrolyte may not be obtained by the prior art method. The range of selection of the mixing conditions was not sufficient.

  The present invention has been completed in view of the above circumstances, and in producing an organic-inorganic hybrid electrolyte formed by mixing and dispersing an organic polymer material having an ion conductivity and an inorganic material, the material and the mixing conditions It is a problem to be solved to provide a manufacturing method with a wide range of choices for the setting. Another object of the present invention is to provide an organic-inorganic hybrid electrolyte that has been produced in this manner and has not been realized in the past.

  As a result of intensive investigations aimed at solving the above problems, the present inventors have come up with a method of mixing and dispersing an organic polymer material and an inorganic material using an ion conductive group of the organic polymer material. did. Specifically, a modified inorganic material in which a modifying group that electrostatically interacts with the ion conductive group of the organic polymer material is introduced into the inorganic material, and then mixed and dispersed in the organic polymer material It is. By introducing the modifying group, the affinity between the organic polymer material and the modified inorganic material can be made extremely high, and the organic-inorganic hybrid electrolyte can be used even under conditions that could not be mixed and dispersed. It became possible to manufacture.

The method for producing an organic-inorganic hybrid electrolyte according to claim 1 has been completed based on the above findings, and the characteristics thereof include an organic polymer material having an ion conductive group,
A solvent for the mixing process that is one or more polar organic solvents having affinity for the organic polymer material;
A surface modifier for introducing a modifying organic material having an affinity for the polar organic solvent to the surface and a surface modifying agent for introducing a modifying group that causes attraction to the ion conductive group by electrostatic interaction to the surface A modified inorganic material obtained by contacting an inorganic material precursor with
A mixing step of mixing and dispersing the components.

The method for producing an organic-inorganic hybrid electrolyte according to claim 2 is characterized in that, in claim 1, the mixing step comprises:
An organic polymer material dissolving step for dissolving the organic polymer material in a part of the solvent for the mixing step;
A modification / modification step of obtaining the modified inorganic material by reacting the surface modifier and the surface modifier with the inorganic material precursor;
A modified inorganic material dissolving step for dissolving the modified inorganic material in the remainder of the solvent for the mixing step;
A solution mixing step of mixing the organic polymer material solution and the modified inorganic material solution;
It is in having.

The method for producing an organic-inorganic hybrid electrolyte according to claim 3 is characterized in that, in claim 1 or 2, the solvent removal step of removing the solvent for the mixing step after the mixing step,
And an activation step of removing the modifying organic material and / or the modifying group.

  The method for producing an organic-inorganic hybrid electrolyte according to claim 4 is characterized in that, in any one of claims 1 to 3, the ion conductive group of the organic polymer material is a proton donating group. is there.

  The method for producing an organic-inorganic hybrid electrolyte according to claim 5 is characterized in that, in any one of claims 1 to 4, the ion conductive group is a sulfo group, and the modifying group is an amino group. is there.

  A feature of the method for producing an organic-inorganic hybrid electrolyte according to claim 6 is that in any one of claims 1 to 5, the surface modifier is a silane coupling agent.

  A feature of the method for producing an organic-inorganic hybrid electrolyte according to claim 7 is that, in claim 6, the surface modifier is 3-aminopropyldimethylethoxysilane.

The method for producing an organic-inorganic hybrid electrolyte according to claim 8 is characterized in that, in claim 6 or 7, the inorganic material precursor is composed of zirconium, titanium, cerium, uranium, tin, vanadium, niobium, antimony and calcium. A metal alkoxide containing at least one element selected from
The modification / modification step is a step of hydrolyzing the metal alkoxide in the presence of the silane coupling agent.

  The method for producing an organic-inorganic hybrid electrolyte according to claim 9 is characterized in that, in any one of claims 1 to 8, the surface modifier comprises acetoacetic acid esters, 1,3-diketone and acetoacetamides. It is to be at least one compound selected from the group.

  The method for producing an organic-inorganic hybrid electrolyte according to claim 10 is characterized in that, in any one of claims 3 to 9, the activation step comprises phosphoric acid, sulfuric acid, fuming sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, It is a step of contacting an acid which is at least one selected from the group consisting of sulfurous acid and nitrous acid.

  The method for producing an organic-inorganic hybrid electrolyte according to claim 11 is characterized in that in any one of claims 1 to 10, the inorganic material precursor is a zirconium compound, a titanium compound, a cerium compound, a uranium compound, a tin compound, It is at least one selected from the group consisting of vanadium compounds, niobium compounds, antimony compounds, calcium hydroxyapatite and hydrated calcium hydroxyapatite.

  The method for producing an organic-inorganic hybrid electrolyte according to claim 12 is characterized in that in any one of claims 1 to 11, the polar organic solvent is N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone, N -One or more compounds selected from the group consisting of methylacetamide and N, N-dimethylacetamide.

The organic-inorganic hybrid electrolyte according to claim 13, which is the organic-inorganic hybrid electrolyte of the present invention that solves the above problems, is characterized in that an organic polymer material having an ion conductive group that is an anion,
Surface modifying agent for introducing a modifying organic material on the surface and surface modifying agent for introducing a modifying group having a cation that generates an attractive force by electrostatic interaction with the ion conductive group on the surface is used as an inorganic material precursor. A modified inorganic material obtained by contact and mixed and dispersed in the organic polymer material;
It is in having.

  In the method for producing an organic-inorganic hybrid electrolyte according to claim 1 configured as described above, the modifying group introduced into the modified inorganic material exhibits an electrostatic interaction with the ion conductive group of the organic polymer material. This has succeeded in improving the interaction between the organic polymer material and the modified inorganic material, making it possible to highly mix and disperse the two. Therefore, by applying the manufacturing method of the present invention, it is possible to realize sufficient mixing / dispersion even in the case of a combination of materials that has been difficult to mix and disperse in the past. And it became possible to greatly expand the range of selection of mixing conditions. In addition, since sufficient mixing / dispersion between the organic polymer material and the modified inorganic material is possible, even a combination of materials that can be mixed / dispersed by the conventional method, It is conceivable that unexpected properties are newly developed or that higher performance is exhibited.

  The method for producing an organic-inorganic hybrid electrolyte according to claim 2 configured as described above includes a step of dissolving an organic polymer material and a modification by an organic polymer material dissolution step and a modified inorganic material dissolution step. By separating the step of dissolving the inorganic material, the organic polymer material and the modified inorganic material are separately dissolved in the polar organic solvent as the solvent for the mixing step. By dissolving separately, it is possible to dissolve in a state in which the interaction between the organic polymer material and the modified inorganic material is excluded, and it is possible to employ a polar organic solvent suitable for each, so both It can be completely dissolved. Therefore, the organic polymer material and the modified inorganic material can be more uniformly mixed and dispersed by mixing the two solutions after completely dissolving them.

  The method for producing an organic-inorganic hybrid electrolyte according to claim 3 configured as described above employs a solvent removal step of removing the solvent for the mixing step after the mixing step, so that the solvent is maintained while maintaining the mixed and dispersed state. Can be removed. The mixed / dispersed state can be maintained as it is due to the process of removing the solvent, the electrostatic interaction between the organic polymer material and the modified inorganic material, or the increase in viscosity accompanying the removal of the solvent even after the solvent is removed. After that, the organic material for modification and / or the modifying group that has realized high-level mixing / dispersion between the organic polymer material and the modified inorganic material is removed by the activation process. Since the movement of molecules is limited in both the organic polymer material and the modified inorganic material, the mixed and dispersed state can be maintained as it is. Therefore, if the modifying organic material or modifying group introduced into the modified inorganic material is left as it is, it may cause undesirable effects on the electrolyte performance, while maintaining the mixed and dispersed state as it is. Organic materials and modifying groups can be removed.

  For example, the reforming step is selected from the group consisting of phosphoric acid, sulfuric acid, fuming sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, sulfurous acid and nitrous acid, as in the method for producing an organic-inorganic hybrid electrolyte according to claim 9. A step of contacting at least one acid can be employed. By contacting these acids, the introduced modifying group and the modifying organic material can be removed by hydrolysis or the like, and the surface of the inorganic material after removing the modifying group and the modifying organic material can be removed. An ion conductive group derived from an acid (phospho group derived from phosphoric acid, sulfo group derived from sulfuric acid or fuming sulfuric acid, etc.) can be introduced to improve ion conductivity.

  The method for producing an organic-inorganic hybrid electrolyte according to claim 4 configured as described above employs a proton-donating group as the ion-conducting group, so that a space between the organic polymer material and the modified inorganic material can be obtained. Can be mixed and dispersed reliably. In particular, this effect is remarkable by adopting a sulfo group as the ion conductive group as in the invention according to claim 5 and adopting an amino group as the modifying group.

  In the method for producing an organic-inorganic hybrid electrolyte according to claim 6 configured as described above, a modified inorganic material into which a modifying group has been introduced by adopting a silane coupling agent as the surface modifier is relatively easy. It can be obtained by operation. In particular, the silane coupling agent is preferably 3-aminopropyldimethylethoxysilane as described in claim 7.

  The method for producing an organic-inorganic hybrid electrolyte according to claim 8 configured as described above employs the metal alkoxide and hydrolyzes the metal alkoxide in the presence of the silane coupling agent described above, thereby modifying the metal-alkoxide. Uniform distribution of the modifying group introduced into the inorganic material, reliable introduction of the modifying group, and reliable control of the introduction amount of the modifying group can be realized. Accordingly, since the introduction of the modifying group that is the basis for realizing uniform mixing and dispersion in the production method of the present invention can be made uniform, the degree of mixing and dispersion between the organic polymer material and the modified inorganic material can be increased. become.

  The method for producing an organic-inorganic hybrid electrolyte according to claim 9 configured as described above is at least one selected from the group consisting of acetoacetate esters, 1,3-diketones and acetoacetamides as the surface modifier. By adopting this compound, it becomes possible to improve the affinity between the modified inorganic material and the organic polymer material, and it is possible to realize more advanced mixing and dispersion.

  The method for producing an organic-inorganic hybrid electrolyte according to claim 11 configured as described above provides an organic-inorganic hybrid electrolyte having higher ionic conductivity by employing the aforementioned compound as an inorganic material precursor. I can do it.

  The method for producing an organic-inorganic hybrid electrolyte according to claim 12 configured as described above dissolves both the organic polymer material and the modified inorganic material by employing the aforementioned compound as a polar organic solvent. It becomes possible to mix evenly.

  The organic-inorganic hybrid electrolyte according to claim 13 configured as described above employs a modified inorganic material in which a modifying organic material and a modifying group are introduced on the surface, so that the organic-inorganic hybrid electrolyte can be compared with the related art. Thus, it is possible to provide an organic-inorganic hybrid electrolyte in which more advanced mixing / dispersion is realized.

  The organic-inorganic hybrid electrolyte and the method for producing the same of the present invention will be described in detail below based on the embodiments.

  The organic-inorganic hybrid electrolyte produced by the method for producing an organic-inorganic hybrid electrolyte of the present embodiment is an electrolyte formed by mixing and dispersing an organic polymer material and an inorganic material. The organic polymer material is not particularly limited except that it has a carbon atom in the polymer skeleton and an ion conductive group in its chemical structure. The ion conductive group is an anion, and examples thereof include those in which a sulfo group, a phospho group, a carbonyl group or the like is used alone or in combination of two or more. The ion conductive group may be directly bonded to the main chain of the polymer constituting the organic polymer material, or may be bonded to the side chain, or a combination of both. I do not care.

  As the basic skeleton of the organic polymer material, one or more of a group consisting of a hydrocarbon polymer, a fluorine polymer, and a fluorine / hydrocarbon mixed polymer can be employed. Examples thereof include perfluoroalkylsulfone polymers such as Nafion (trademark), aromatic polyethersulfone polymers, and polyetherketone polymers. Specifically, a polymer material (hereinafter referred to as “SPES”) in which a sulfo group is introduced into poly (arylene ether sulfone) is exemplified.

  The inorganic material is not particularly limited, but is selected from the group consisting of zirconium compound, titanium compound, cerium compound, uranium compound, tin compound, vanadium compound, niobium compound, antimony compound, calcium hydroxyapatite and hydrated calcium hydroxyapatite. At least one of them can be exemplified. In particular, an oxide is mentioned. Moreover, inorganic materials can also contribute to ionic conductivity by introducing an anion such as a phospho group or a sulfo group into these compounds. It is desirable that the inorganic material forms fine particles on the order of nanometers and is mixed and dispersed with the aforementioned organic polymer material at the molecular level.

ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ) ₂ , Zr (HSO ₃ ) ₂ .nH ₂ O Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr (O ₃ P—R ² —SO ₃ H) _{2− X} (O ₃ P—R ³ —COOH) _X , and Zr (O ₃ P—R ² —SO ₃ H) _2−X (O ₃ P—R ³ —COOH) _X · nHO (wherein R ¹ , R ² and R ³ each independently represent a divalent aromatic group, preferably R ¹ and R ² each independently represent a divalent aromatic group and R ³ represents an alkylene group, X is 0 It is desirable that it is at least one selected from the group consisting of (super, less than 2).

Titanium compounds include TiO ₂ , TiO ₂ · nH ₂ O, Ti (HP0 ₄ ) ₂ , Ti (HPO ₄ ) ₂ · nH ₂ O, Ti (HSO ₃ ) ₂ and Ti (HSO ₃ ) ₂ · nH ₂ O. It is desirable that it is at least one selected from the group consisting of (N is about 1 to 10. The same applies hereinafter)

The cerium compound is desirably at least one selected from the group consisting of CeO ₂ , CeO ₂ .nH ₂ O, Ce (HPO ₄ ) ₂ and Ce (HPO ₄ ) ₂ .nH ₂ O.

Uranium compounds are _{H 3 OUO 4 PO 4, H} 3 OUO 4 PO 4 · nH 2 O, H 3 OUO 2 AsO 4 and H ₃ OUO ₂ AsO least one selected from the group consisting of ₄ · nH ₂ O It is desirable.

The tin compound is desirably SnO ₂ or SnO ₂ .nH ₂ O. The vanadium compound is desirably V ₂ O ₅ or V ₂ O ₅ .nH ₂ O. The niobium compound is desirably Nb ₂ O ₅ or Nb ₂ O ₅ .nH ₂ O. Antimony compounds include Sb ₂ 0 ₅ , Sb ₂ O ₅ .nH ₂ O, HSbO ₃ , HSbO ₃ .nH ₂ O, H ₂ SbO ₁₁ , H ₂ SbO ₁₁ .nH ₂ O, H _X Sb _X P ₂ O ₃ And at least one selected from the group consisting of H _x Sb _x P ₂ O ₃ .nH ₂ O (wherein X is 1, 3 or 5 and n is 2 to 10).

Calcium hydroxyapatite and hydrated calcium hydroxyapatite are Ca ₁₀ (PO ₄ ) X ₂ and Ca ₁₀ (PO ₄ ) X ₂ .nH ₂ O (wherein X represents —OH and / or —F). It is desirable that it is at least one selected from the group consisting of

(Method for producing organic-inorganic hybrid electrolyte)
The manufacturing method of the organic-inorganic hybrid electrolyte of the present embodiment includes a mixing step and other necessary steps. The mixing step is a step of mixing the organic polymer material, the modified inorganic material, and the solvent for the mixing step.

  The modified inorganic material is a material obtained by bringing a surface modifier and a surface modifier into contact with an inorganic material precursor, and is an inorganic material in an organic-inorganic hybrid electrolyte that is finally produced in an activation process described later. It is a material that can be converted into The inorganic material precursor is modified by contacting with the surface modifier and the surface modifier. The conditions for contact will be described in detail later. Examples of the conditions include leaving or stirring under acidic conditions and standing or stirring under heating conditions. As the solvent to be used, the solvent for the mixing step can be employed as it is, or water, alcohol or the like can be employed and then removed. The surface modifier and the surface modifier may be simultaneously contacted with the inorganic material precursor, or may be independently contacted with the inorganic material precursor. When contacting independently, the order of contacting does not matter.

  Examples of the inorganic material precursor include metal alkoxides containing elements (zirconium, titanium, cerium, uranium, tin, vanadium, niobium, antimony, calcium, etc.) contained in the inorganic material. By hydrolyzing the metal alkoxide (so-called sol-gel method), oxide fine particles of the respective elements contained can be obtained. And the modified inorganic material which introduce | transduced efficiently the organic material for modification and a modification group can be obtained by making it hydrolyze in presence of a surface modifier and a surface modifier. In addition, when oxides are used as inorganic materials, fine particles of oxides of elements (zirconium, titanium, cerium, uranium, tin, vanadium, niobium, antimony, calcium, etc.) contained therein (nanometer-order minute) It is also possible to employ particles.

  The surface modifier is a compound that can introduce a modifying organic material onto the surface of the inorganic material precursor. The modifying organic material is a compound having an affinity for the solvent for the mixing process described later, and enables the modified inorganic material to be dissolved in the solvent for the mixing process. The modifying organic material may be bonded to the surface of the inorganic material precursor by a covalent bond or may be bonded by an ionic bond, but can be easily removed in the activation step described later. It is desirable to employ a bond. Examples thereof include acetoacetic esters (such as ethyl acetoacetate), 1,3-diketone (such as acetylacetone), and acetoacetamides (such as N, N-dimethylaminoacetoacetamide).

  The surface modifier is a compound that can introduce a modifying group having a cation that generates an attractive force by electrostatic interaction with an ion conductive group of the organic polymer material. The modifying group is preferably a basic functional group, and includes nitrogen-containing functional groups such as an amino group, a guanidino group, and a group containing a pyridine ring, and it is particularly desirable to employ an amino group. Although it does not specifically limit as a surface modifier which can introduce | transduce these modification groups, It is desirable to employ | adopt the coupling | bonding which can be removed easily in the activation process mentioned later. For example, it is desirable to employ a silane coupling agent having these modifying groups in the chemical structure. As the silane coupling agent, a monofunctional compound, that is, a monoalkoxysilane compound that does not proceed with a crosslinking reaction is desirable. An example of a silane coupling agent capable of introducing an amino group is 3-aminopropyldimethylethoxysilane.

  The solvent for the mixing process is one or more polar organic solvents having affinity for the organic polymer material, and can dissolve the organic polymer material. Therefore, the type of polar organic solvent that can be employed varies depending on the type of organic polymer material. For example, when SPES is adopted as the organic polymer material, the solvent for the mixing process includes N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone, N-methylacetamide and N, N-dimethylacetamide. One or more compounds selected from:

  The mixing step desirably employs a step of mixing a solution in which the organic polymer material is dissolved in the solvent for the mixing step and a solution in which the modified inorganic material is dissolved in the solvent for the mixing step. The organic polymer material and the modified inorganic material can be dissolved more reliably by dissolving separately in the organic polymer material dissolving step and the modified inorganic material dissolving step. And it has the modification | reformation and modification process which is a process of making a surface modification agent and a surface modification agent contact an inorganic material precursor, and obtaining a modification inorganic material before a modification | reformation inorganic material melt | dissolution process.

  It is desirable to have a solvent removal step and an activation step as other steps. Furthermore, it is desirable to have a step of forming the mixture / dispersion into a form suitable for the state of use. Although it does not specifically limit as the method of making into a film form, The method of casting on an appropriate plate-like body, the method of being immersed in the film | membrane which consists of an appropriate porous body, and making a pore filling electrolyte membrane etc. are mentioned. Moreover, when adopting for the catalyst layer of a fuel cell, there exists the method of impregnating the porous body (carbon paper etc.) which forms a catalyst layer.

  A solvent removal process is a process of removing the solvent for mixing processes used in the mixing process. As a method for removing the solvent for the mixing process, it is desirable that the method does not adversely affect the dispersion state of the inorganic material and the organic polymer material. Removal by evaporation, poor solvent for the organic polymer material and the modified inorganic material Substituting by soaking in can be mentioned.

  The activation step is a step of removing the modifying organic material and / or modifying group introduced on the surface of the modified inorganic material. The method for removing the modifying organic material and / or modifying group may be selected according to the properties of the modifying organic material and modifying group. For example, when acetoacetic acid esters, 1,3-diketones, and acetoacetamides are used as the organic material for modification, and a silane coupling agent is used as the surface modifying agent for introducing the modifying group, it can be obtained in the mixing step. The mixture / dispersion is made into a state suitable for the form of use (molded into a membrane or impregnated into a porous body. The solvent for the mixing process has been removed) and then immersed in an aqueous acid solution. Then, the hydrolysis reaction proceeds and the organic material for modification and the modifying group can be removed. Here, as the acid, it is desirable to employ an acid that is at least one selected from the group consisting of phosphoric acid, sulfuric acid, fuming sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, sulfurous acid, and nitrous acid. In particular, when phosphoric acid is employed, it becomes possible to introduce a phospho group that contributes to improving ion conductivity to the surface of the modified inorganic material after removing the modifying organic material and / or modifying group, This is desirable because it can be converted into a metal phosphate group having conductivity. When the organic-inorganic hybrid electrolyte of this embodiment is employed in a fuel cell, a reaction similar to the activation step proceeds depending on the atmosphere in the fuel cell, and the introduced organic material for modification and the modifying group introduced. It is also conceivable that is removed. In addition, depending on the amount of the modifying organic material and / or the modifying group introduced, the performance of the electrolyte in the usage state may not be affected. In this case, the activation step is not necessary. Performance can be demonstrated.

(Manufacture of modified inorganic materials)
Tetrabutoxyzirconium (Zr (OBt) ₄ ) as an inorganic material precursor was placed in 200 mL of isopropyl alcohol and mixed for 30 minutes. Thereafter, acetylacetone (AcAc) as a surface modifier was added and stirred for 3 hours. Further, 3-aminopropyldimethylethoxysilane (APS) as a surface modifier was added and stirred for 30 minutes.

  Thereafter, 1N nitric acid is added and stirred for 12 hours to hydrolyze tetrabutoxyzirconium, and acetylacetone as a modifying organic material and a 3-aminopropyldimethylsilyl group (siloxy group) having an amino group as a modifying group (Modified / modifying step: the obtained powder was colored deep yellow due to the presence of AcAc and APS).

After completion of the stirring, the mixture was heated at 110 ° C. to evaporate and remove the solvent, and then thoroughly washed with toluene and vacuum dried. The obtained powder was used as the inorganic material (modified inorganic material) of this example. Confirmation that the ZrO ₂ APS had reacted was confirmed by FT-IR peak derived from the amino group near 3300 cm ^-1, the presence of a peak derived from C-N bond at around 1250 cm ^-1.

The mixing ratio of Zr (OBt) ₄ , AcAc, HNO ₃ , and APS is based on the number of moles, and Zr (OBt) ₄ is 1, AcAc is 1 or 2, HNO ₃ is 0.4, APS is 0, 0.5, 0.75 and 1.0.

As an inorganic material of a comparative example, an inorganic material prepared without adding APS (amount of APS added is 0) (Comparative Example 1: treated with AcAc and not treated with APS: due to the presence of AcAc A light yellow color) and an inorganic material prepared without adding both APS and AcAc (Comparative Example 2: Inorganic material in which neither AcAc nor APS were treated) were prepared. When neither was added, ZrO ₂ was formed and turned into white particles. Since there was no AcAC, the particles became coarse and on the order of 10 nm.

(Synthesis of organic polymer materials (SPES))
SPES was synthesized by condensation polymerization of three types of monomers. As the three types of monomers, (A) 3,3′-disulfonated-4,4′-dichloro-diphenylsulfone sodium salt, (B) 4,4′-dichloro-diphenylsulfone, (C) 4,4 '-Dihydroxydiphenyl was adopted. The compounds (B) and (C) were used after purifying commercially available products. The compound (A) was synthesized by treating the compound (B) with fuming sulfuric acid and introducing a sulfo group.

  The polymerization reaction of the organic polymer material was performed by mixing so that the sum of the number of moles of (A) and (B) was equal to the number of moles of (C). The degree of sulfonation was adjusted by changing the mixing ratio of (A) and (B). Here, the degree of sulfonation when (A) was 100% and (B) was 0% was 1, and the degree of sulfonation when (A) was 0% and (B) was 100% was 0. Organic polymer materials having several degrees of sulfonation were prepared.

  The molar amount of the mixture in which the molar ratio of (A) and (B) is adjusted to a predetermined degree of sulfonation and the molar amount of (C) are adjusted to 1: 1, A polymerization reaction was carried out at 180 ° C. for about 40 hours while bubbling nitrogen under an inert atmosphere by adding 1.25 times the amount of potassium carbonate (C). As a solvent, 1-methyl-2-pyrrolidone (NMP) was used, and the compounds of (A), (B) and (C) were adjusted to 15% by mass.

  An excess amount of 8.2 M hydrochloric acid was added to the obtained product to perform ion exchange. The product was put into isopropyl alcohol, reprecipitated, dried, washed with purified water, and then vacuum dried to obtain an organic polymer material.

(Manufacture of organic-inorganic hybrid electrolyte)
Each of the inorganic materials and SPES of each Example and Comparative Example was dissolved in NMP so as to be 20% and 0.5% on a mass basis to obtain a solution (organic polymer material dissolving step, modified inorganic material Dissolution step). Here, NMP is used as a solvent for the mixing step, and the polar organic solvent that dissolves the organic polymer material and the polar organic solvent that dissolves the modified inorganic material are the same.

  The SPES solution was dispersed by adding an equal mass of the inorganic material solution of each example and comparative example and mixing.

(Evaluation)
(Volume average particle size of inorganic material)
Based on the molar amount of Zr (OBt) ₂ , the volume average particle diameter in NMP when the AcAc addition amount ratio is 1.2 is 1.0 nm and 0.5 nm when the APS addition amount ratio is 0. Was 2.2 nm, 0.75 when 0.75, and 2.5 nm when 1.0.

  Further, in the experimental results of other days, the volume average particle size of the particles contained in the inorganic material solution before mixing with SPES is 2.2 nm when APS is not added, and 2 when APS is added. The volume average particle size after mixing the SPES solution was 12.2 nm when no APS was added, and 4.8 nm when 1.0 APS was added. That is, by introducing APS, it is considered that the interaction with SPES is strengthened and the particle size is reduced.

(Observation of mixing / dispersion after mixing process)
When the inorganic material of the example added with APS of 0.5, 0.75, 1.0 is used, even if the solution concentration is 20% by mass or 0.5% by mass, it is transparent and uniform after mixing. Solution was obtained. Moreover, a transparent and uniform solution was obtained after mixing irrespective of the sulfonation degree of SPES.

  On the other hand, when the inorganic material of Comparative Example 1 is used, a transparent uniform solution can be obtained when the concentration of the solution is 20% by mass. However, when the concentration of the solution is 0.5% by mass, aggregates are precipitated and are transparent. A homogeneous solution was not obtained. Further, depending on the degree of SPES sulfonation, aggregates may precipitate and a transparent uniform solution may not be obtained. That is, when the inorganic material of this example was used, it was possible to prepare a transparent uniform solution in a wide range of sulfonation degrees. Moreover, although the case where the molecular weight of SPES was changed was also examined, when the inorganic material of this example was employed, a transparent uniform solution could be prepared in a molecular weight range wider than that of Comparative Example 1. As for the performance of the electrolyte, the example showed higher performance than the comparative example 1.

  That is, the range of conditions for the inorganic material of each example brought into contact with APS to become a transparent uniform solution when mixed with the SPES solution is broader than that of Comparative Example 1 in which treatment with APS is not performed. In addition, it has been clarified that even when a transparent uniform solution is obtained in the same manner, a higher dispersion state is realized by performing the treatment with APS.

  Here, when the inorganic material of Comparative Example 2 in which neither AcAc nor APS is treated is used, the range of conditions under which a transparent uniform solution can be prepared is narrower than when the inorganic material of Comparative Example 1 is used. It was.

(Creation of electrolyte membrane)
The uniformly mixed solution of each example and comparative example was thinly spread on a glass plate having a smooth surface. Then, it formed into a film by making it dry at 90 degreeC for 3 hours or more. The obtained film was immersed in a 2M phosphoric acid aqueous solution, reacted at 80 ° C. for 12 hours or more, and then thoroughly washed with water. In addition, compared with the film | membrane produced from the mixed solution of the comparative examples 1 and 2, it became clear that the film | membrane produced from the mixed solution of the Example was excellent in the performance as an electrolyte. This is considered to be due to the fact that the mixing and dispersion of the inorganic material and the organic polymer material in the examples can be realized to a higher degree than in Comparative Examples 1 and 2. For example, in the electrolyte of the example, an electrolyte exhibiting higher performance than the electrolytes of Comparative Example 1 and Comparative Example 2 may be obtained without performing the activation step.

(Evaluation of activation process)
It was confirmed that by immersing in a phosphoric acid aqueous solution, AcAc and APS introduced into ZrO ₂ were desorbed, and zirconium phosphate was produced. Specifically, the thermal decomposition behavior of the inorganic material of each example was examined by TG-MS for the washed sample and the sample as it was after being immersed in a phosphoric acid aqueous solution. In the sample not treated with the phosphoric acid aqueous solution, a peak derived from the elimination of AcAc was observed at about 200 to 300 ° C., and a peak derived from APS was observed around 400 ° C., whereas phosphoric acid was observed. In the sample treated with the aqueous solution, neither a peak derived from AcAc nor a peak derived from APS was observed. Furthermore, it has confirmed that the zirconium phosphate was producing | generating by evaluation by X-ray diffraction. Similarly, it is confirmed that AcAc and APS are desorbed and zirconium phosphate is formed by immersing the organic-inorganic hybrid electrolyte produced by mixing with SPES in an aqueous phosphoric acid solution.

Claims (13)

An organic polymer material having an ion conductive group;
A solvent for the mixing process that is one or more polar organic solvents having affinity for the organic polymer material;
A surface modifier for introducing a modifying organic material having an affinity for the polar organic solvent to the surface and a surface modifying agent for introducing a modifying group that causes attraction to the ion conductive group by electrostatic interaction to the surface A modified inorganic material obtained by contacting an inorganic material precursor with
The manufacturing method of the organic-inorganic hybrid electrolyte characterized by having the mixing process which mixes and disperse | distributes. The mixing step includes
An organic polymer material dissolving step for dissolving the organic polymer material in a part of the solvent for the mixing step;
A modification / modification step of obtaining the modified inorganic material by reacting the surface modifier and the surface modifier with the inorganic material precursor;
A modified inorganic material dissolving step for dissolving the modified inorganic material in the remainder of the solvent for the mixing step;
A solution mixing step of mixing the organic polymer material solution and the modified inorganic material solution;
The manufacturing method of the organic-inorganic hybrid electrolyte of Claim 1 which has these. After the mixing step, a solvent removing step for removing the solvent for the mixing step;
The method for producing an organic-inorganic hybrid electrolyte according to claim 1, further comprising an activation step of removing the modifying organic material and / or the modifying group.   The method for producing an organic-inorganic hybrid electrolyte according to any one of claims 1 to 3, wherein the ion conductive group of the organic polymer material is a proton donating group. The ion conductive group is a sulfo group,
The method for producing an organic-inorganic hybrid electrolyte according to any one of claims 1 to 4, wherein the modifying group is an amino group.   The method for producing an organic-inorganic hybrid electrolyte according to any one of claims 1 to 5, wherein the surface modifier is a silane coupling agent.   The method for producing an organic-inorganic hybrid electrolyte according to claim 6, wherein the surface modifier is 3-aminopropyldimethylethoxysilane. The inorganic material precursor is a metal alkoxide containing at least one element selected from the group consisting of zirconium, titanium, cerium, uranium, tin, vanadium, niobium, antimony and calcium,
The method for producing an organic-inorganic hybrid electrolyte according to claim 6 or 7, wherein the modifying / modifying step is a step of hydrolyzing the metal alkoxide in the presence of the silane coupling agent.   The organic-inorganic hybrid according to any one of claims 1 to 8, wherein the surface modifier is at least one compound selected from the group consisting of acetoacetic esters, 1,3-diketone and acetoacetamides. Manufacturing method of electrolyte.   The activation step is a step of contacting an acid which is at least one selected from the group consisting of phosphoric acid, sulfuric acid, fuming sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, sulfurous acid and nitrous acid. The manufacturing method of the organic-inorganic hybrid electrolyte of any one of Claims 1.   The inorganic material precursor is at least one selected from the group consisting of zirconium compounds, titanium compounds, cerium compounds, uranium compounds, tin compounds, vanadium compounds, niobium compounds, antimony compounds, calcium hydroxyapatite, and hydrated calcium hydroxyapatite. It is a seed | species, The manufacturing method of the organic-inorganic hybrid electrolyte of any one of Claims 1-10.   The polar organic solvent is one or more compounds selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone, N-methylacetamide and N, N-dimethylacetamide. The manufacturing method of the organic-inorganic hybrid electrolyte of any one of Claims 1. An organic polymer material having an ion conductive group which is an anion;
Surface modifying agent for introducing a modifying organic material on the surface and surface modifying agent for introducing a modifying group having a cation that generates an attractive force by electrostatic interaction with the ion conductive group on the surface is used as an inorganic material precursor. A modified inorganic material obtained by contact and mixed and dispersed in the organic polymer material;
An organic-inorganic hybrid electrolyte characterized by comprising: