JP2006040587A - Proton conductor and its manufacturing method - Google Patents

Proton conductor and its manufacturing method Download PDF

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JP2006040587A
JP2006040587A JP2004214881A JP2004214881A JP2006040587A JP 2006040587 A JP2006040587 A JP 2006040587A JP 2004214881 A JP2004214881 A JP 2004214881A JP 2004214881 A JP2004214881 A JP 2004214881A JP 2006040587 A JP2006040587 A JP 2006040587A
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JP3905899B2 (en
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Shoji Yamanaka
昭司 山中
Akira Kubo
章 久保
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Abstract

<P>PROBLEM TO BE SOLVED: To simply manufacture a proton conductor of a solid electrolyte having high heat resistance and high proton conductivity. <P>SOLUTION: The proton conductor is manufactured in processes (A) to (C). (A) is a process obtaining AlPO<SB>4</SB>-B<SB>2</SB>O<SB>3</SB>-R<SB>2</SB>glass having AlPO<SB>4</SB>, B<SB>2</SB>O<SB>3</SB>, and R<SB>2</SB>O (R is an alkali metal) as the main component. (B) is a process eluting at least a part of B<SB>2</SB>O<SB>3</SB>component and R<SB>2</SB>O component from the glass into water, a weak acidic aqueous solution, or a weak alkaline aqueous solution until the glass becomes an ion exchange meso pore porous body in a state that a part of the R<SB>2</SB>O component is left. (C) is a process exchanging at least a part of R ions of the R<SB>2</SB>O component of the meso pore porous body with protons. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は燃料電池のセパレーター、センサー、固体酸触媒などに用いられるプロトン伝導体とその製造方法に関する。   The present invention relates to a proton conductor used for a separator, a sensor, a solid acid catalyst and the like of a fuel cell and a method for producing the same.

燃料電池のセパレーターとして用いられるプロトン伝導性固体電解質には、パーフルオロスルフォン酸膜（例えば、デュポン社のＮＡＦＩＯＮ（登録商標））などのフッ素系ポリマーがよく知られているが、有機ポリマーであるため、耐熱性と耐久性に問題がある。   Fluoropolymers such as perfluorosulfonic acid membranes (eg, DuPont NAFION (registered trademark)) are well known as proton conductive solid electrolytes used as fuel cell separators, but are organic polymers. There are problems with heat resistance and durability.

耐熱性に優れる無機固体電解質として、種々のリン酸塩が研究されているが、性能的には、改善の必要がある。
最近、ゾル−ゲル法で多孔質のＳｉＯ2−Ｐ2Ｏ5系ガラスが合成されており、高い伝導性が報告されているが、合成が複雑であり、製造に時間がかかる。
特開２００２−２２６２８３号公報 Various phosphates have been studied as inorganic solid electrolytes having excellent heat resistance, but performance needs to be improved.
Recently, porous SiO 2 —P 2 O 5 -based glass has been synthesized by a sol-gel method, and high conductivity has been reported, but the synthesis is complicated and takes time to manufacture.
JP 2002-226283 A

高いプロトン伝導度を有する耐熱性の高い物質の開発には、プロトン濃度が高く、高いプロトン移動度を有する無機物質を開発することが必要である。
本発明の第１の目的は、耐熱性が高く、高いプロトン伝導度を有する固体電解質のプロトン伝導体を提供することである。
本発明の第２の目的は、そのようなプロトン伝導体の簡便な製造方法を提供することである。 In order to develop a material having high proton conductivity and high heat resistance, it is necessary to develop an inorganic material having a high proton concentration and high proton mobility.
A first object of the present invention is to provide a solid electrolyte proton conductor having high heat resistance and high proton conductivity.
The second object of the present invention is to provide a simple method for producing such a proton conductor.

本発明者らは、先に製造が簡単な分相ガラスを利用し、メソポア多孔体の合成に成功している（特許文献１参照。）。そして、そのメソポア多孔体の特性を研究している過程で、イオン交換によってプロトンをメソポア導入することにより、ガラスに高いプロトン伝導性を付与できることを見いだし、本発明をなしたものである。   The present inventors have succeeded in synthesizing a porous mesopore by using a phase-separated glass that is easy to produce (see Patent Document 1). In the course of studying the characteristics of the porous mesopores, the present inventors have found that high proton conductivity can be imparted to glass by introducing protons into the mesopores by ion exchange.

すなわち、本発明のプロトン伝導体は、ＡｌＰＯ4を主成分とし、孔径が２ｎｍ以上の細孔をもつＡｌＰＯ4系イオン交換性メソポア多孔体であって、その細孔壁がプロトンとイオン交換されているものである。 That is, the proton conductor of the present invention is mainly composed of AlPO 4, pore size a AlPO 4 based ion exchange mesoporous material having a pore over 2 nm, the pores wall is a proton and ion exchange It is what.

本発明のプロトン伝導体製造方法は以下の工程（Ａ）から（Ｃ）を含んでいる。
（Ａ）ＡｌＰＯ4、Ｂ2Ｏ3及びＲ2Ｏ（Ｒはアルカリ金属）を主成分とするＡｌＰＯ4−Ｂ2Ｏ3−Ｒ2Ｏガラスを得る工程、
（Ｂ）前記ガラスがＲ2Ｏ成分の一部分を残した状態のイオン交換性メソポア多孔体となるまで、前記ガラスからＢ2Ｏ3成分及びＲ2Ｏ成分の少なくとも一部分を水又は弱酸もしくは弱アルカリの水溶液に溶出させる工程、並びに
（Ｃ）前記メソポア多孔体のＲ2Ｏ成分のＲイオンの少なくとも一部分をプロトンと交換させるイオン交換工程。 The proton conductor production method of the present invention includes the following steps (A) to (C).
(A) A step of obtaining an AlPO 4 —B 2 O 3 —R 2 O glass mainly composed of AlPO 4 , B 2 O 3 and R 2 O (R is an alkali metal),
(B) Until the glass becomes an ion-exchangeable mesopore porous body with a part of the R 2 O component remaining, at least a part of the B 2 O 3 component and the R 2 O component is removed from the glass with water, weak acid or weak alkali. And (C) an ion exchange step of exchanging at least a part of R ions of the R 2 O component of the mesopore porous body with protons.

ＡｌＰＯ4−Ｂ2Ｏ3−Ｒ2Ｏガラスの好ましい組成は、アルカリ金属ＲとしてＮａを使用し、ＡｌＰＯ4をｘ、Ｂ2Ｏ3をｙ、Ｒ2Ｏをｚとするとき、モル％で表してｘが１０〜５０％、ｙが７５〜１５％、ｚが１５〜４０％である。 The preferred composition of the AlPO 4 —B 2 O 3 —R 2 O glass is as follows: Na is used as the alkali metal R, AlPO 4 is x, B 2 O 3 is y, and R 2 O is z. In this case, x is 10 to 50%, y is 75 to 15%, and z is 15 to 40%.

ＡｌＰＯ4−Ｂ2Ｏ3−Ｒ2Ｏガラスを得る工程では、アルカリ金属酸化物、アルカリ土類金属酸化物、ＩＩＩ族酸化物、ＩＶ族酸化物、Ｖ族酸化物及びＶＩ族酸化物からなる酸化物群のうちの１成分又は複数成分を修飾酸化物として、ＡｌＰＯ4−Ｂ2Ｏ3−Ｒ2Ｏガラスに対して０．５〜８モル％の範囲で添加するのが好ましい。 In the step of obtaining AlPO 4 —B 2 O 3 —R 2 O glass, the glass comprises an alkali metal oxide, an alkaline earth metal oxide, a group III oxide, a group IV oxide, a group V oxide, and a group VI oxide. It is preferable to add one or more components in the oxide group as a modified oxide in a range of 0.5 to 8 mol% with respect to the AlPO 4 —B 2 O 3 —R 2 O glass.

修飾酸化物を適度に添加することにより機械的強度が増大するだけでなく、耐水性の向上を図ることができ、高いプロトン伝導に必要なプロトン濃度が増大する。修飾酸化物濃度が０．５モル％より低い場合はその効果が現れにくく、逆に８モル％より多くなると
ガラス化範囲外となり、細孔容量が減少するため、伝導度が低下し、好ましくない。 By appropriately adding the modified oxide, not only the mechanical strength increases, but also the water resistance can be improved, and the proton concentration necessary for high proton conduction increases. When the concentration of the modified oxide is lower than 0.5 mol%, the effect is hardly exhibited. Conversely, when the concentration is higher than 8 mol%, it is outside the vitrification range, and the pore volume is decreased. .

修飾酸化物として使用するのに適する酸化物は、アルカリ金属酸化物としてはＫ2Ｏ、アルカリ土類金属酸化物としてはＣａＯ、ＭｇＯ及びＢａＯ、ＩＩＩ族酸化物としてはＡｌ2Ｏ3、Ｙ2Ｏ3及びＧａ2Ｏ3、ＩＶ族酸化物としてはＴｉＯ2、ＺｒＯ2、ＨｆＯ2、ＳｉＯ2、ＧｅＯ2、ＳｎＯ2及びＰｂＯ2、Ｖ族酸化物としてはＶ2Ｏ5、Ｎｂ2Ｏ5、Ｐ2Ｏ5、Ｓｂ2Ｏ5及びＢｉ2Ｏ3、ＶＩ族酸化物としてはＣｒ2Ｏ3、ＭｏＯ3及びＷＯ3を挙げることができる。 Suitable oxides for use as modified oxides are K 2 O for alkali metal oxides, CaO, MgO and BaO for alkaline earth metal oxides, Al 2 O 3 , Y 2 for group III oxides. O 3 and Ga 2 O 3 , TiO 2 , ZrO 2 , HfO 2 , SiO 2 , GeO 2 , SnO 2 and PbO 2 as group IV oxides, V 2 O 5 , Nb 2 O 5 as group V oxides P 2 O 5 , Sb 2 O 5 and Bi 2 O 3 , and Group VI oxides include Cr 2 O 3 , MoO 3 and WO 3 .

イオン交換工程はプロトンを提供するブレンステッド酸溶液中で行う。ブレンステッド酸には、塩酸、硫酸、硝酸などの無機酸のほか、酢酸などのブレンスデッド有機酸を用いることもできる。溶液は水を溶媒として用いる他に、アセトンやホルムアミド、アセトニトリル、テトラヒドロフラン、アルコールなどの有機溶媒を用いることができる。ブレンステッド酸性の水溶液でイオン交換を行うと、多孔質ガラスは一部溶液に溶解するため、細孔表面積の低下により、高い伝導度を有する多孔体が得られないことがあるが、有機溶媒を用いることにより、ガラスの溶解を抑制して、プロトンとのイオン交換を効率的に行うことができ、高いプロトン伝導度を有する多孔体が得られる。汎用溶媒のアセトンを用いるのが、便利であり、イオン交換は室温で数時間以内に完了する。   The ion exchange step is performed in a Bronsted acid solution that provides protons. As the Bronsted acid, in addition to inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, Bronsted organic acids such as acetic acid can also be used. In addition to using water as a solvent, the solution can be an organic solvent such as acetone, formamide, acetonitrile, tetrahydrofuran, or alcohol. When ion exchange is performed with a Bronsted acidic aqueous solution, the porous glass partially dissolves in the solution. Therefore, a porous body having high conductivity may not be obtained due to a decrease in the pore surface area. By using it, dissolution of the glass can be suppressed, ion exchange with protons can be performed efficiently, and a porous body having high proton conductivity can be obtained. It is convenient to use the general-purpose solvent acetone, and the ion exchange is completed within a few hours at room temperature.

本発明のプロトン伝導体は、イオン交換性メソポア多孔体の細孔壁をプロトンとイオン交換するので、プロトンを高濃度で導入することができる。そして、２〜１０ｎｍの貫通した細孔直径を有するメソポア多孔体の細孔内壁近傍のプロトンは高い移動度を有し、高いプロトン濃度と相まって、高いプロトン伝導度を示す。   Since the proton conductor of the present invention ion-exchanges the pore walls of the ion-exchangeable mesopore porous body with protons, protons can be introduced at a high concentration. And the proton near the pore inner wall of the mesopore porous body having a through-pore diameter of 2 to 10 nm has a high mobility, and exhibits a high proton conductivity combined with a high proton concentration.

本発明の製造方法は、ＡｌＰＯ4−Ｂ2Ｏ3−Ｒ2Ｏを主成分とするガラスからＲ2Ｏ成分の一部分を残すようにＢ2Ｏ3成分及びＲ2Ｏ成分の少なくとも一部分を溶出させてイオン交換性メソポア多孔体とし、そのＲ2Ｏ成分のＲイオンの少なくとも一部分をプロトンと交換させることにより製造するので、工程が簡便である。 In the production method of the present invention, at least a part of the B 2 O 3 component and the R 2 O component are eluted so as to leave a part of the R 2 O component from the glass mainly composed of AlPO 4 —B 2 O 3 —R 2 O. Therefore, the process is simple because it is produced by exchanging at least a part of R ions of the R 2 O component with protons.

ＡｌＰＯ4，Ｂ2Ｏ3及びＲ2Ｏを主成分とするガラスを生成し、これを出発物質として、熱処理による結晶化した後、又はそのような熱処理を行わずに非晶質のままで、熱水、例えば６０〜１５０℃の水を用いてＢ2Ｏ3成分とＲ2Ｏ成分の一部又は大部分を溶出することにより、メソポア多孔体を合成する（特許文献１参照。）。ＡｌＰＯ4はＡｌ2Ｏ3とＰ2Ｏ5から生成することができる。その際、Ａｌ2Ｏ3とＰ2Ｏ5のモル比（Ａｌ2Ｏ3／Ｐ2Ｏ5）比はほぼ１を中心に、０．６〜１．４の範囲で変化させることができる。 A glass mainly composed of AlPO 4 , B 2 O 3 and R 2 O is produced, and this is used as a starting material, after crystallization by heat treatment, or remains amorphous without such heat treatment, A mesopore porous body is synthesized by eluting part or most of the B 2 O 3 component and the R 2 O component using hot water, for example, water at 60 to 150 ° C. (see Patent Document 1). AlPO 4 can be produced from Al 2 O 3 and P 2 O 5 . At that time, the molar ratio (Al 2 O 3 / P 2 O 5 ) ratio between Al 2 O 3 and P 2 O 5 can be changed in the range of 0.6 to 1.4, centered at about 1.

Ａｌ2Ｏ3の原料としては、酸化アルミニウム、各種水酸化アルミニウム又はベーマイトを用いることができる。Ｐ2Ｏ5原料としては、リン酸、各種アルカリもしくはアンモニウムリン酸塩、又はこれらの混合物を用いることができる。Ｂ2Ｏ3の原料としては、ホウ酸又は各種アルカリホウ酸塩を用いることができる。Ｒ2Ｏの原料としては、各種炭酸塩又は炭酸水素塩を用いることができる。 As the raw material for Al 2 O 3 , aluminum oxide, various aluminum hydroxides, or boehmite can be used. As the P 2 O 5 raw material, phosphoric acid, various alkali or ammonium phosphates, or a mixture thereof can be used. As a raw material for B 2 O 3 , boric acid or various alkali borates can be used. As the raw material of R 2 O, various carbonates or hydrogen carbonates can be used.

少量添加する修飾酸化物についても、酸化物を直接添加するか、焼成により酸化物となる炭酸塩、アンモニウム塩、水酸化物又は硝酸塩を用いることもできる。
原料を所定の混合比となるように混合し、白金又は磁性ルツボを用いて、加熱分解後、溶融するまで焼成し、急冷して溶融ガラスを得る。 As for the modified oxide to be added in a small amount, a carbonate, ammonium salt, hydroxide or nitrate that becomes an oxide by firing can be added directly.
Raw materials are mixed so as to have a predetermined mixing ratio, and after pyrolysis using platinum or a magnetic crucible, they are fired until they are melted, and rapidly cooled to obtain molten glass.

ここで、ガラス化域の決定を行なうために種々の組成で溶融ガラスを作成した。リン酸二水素アンモニウム、ベーマイト、酸化ホウ素、炭酸ナトリウムを種々の比に混合し、これを１２００〜１５００℃で約１時間加熱し、完全に融解したのち、水中に投じて急冷した。合成した試料の酸化物モル組成とガラス化の状態を表１に示す。Ａｌ／Ｐは１となるように原料を混合し、調製した。
○は透明なガラス、△は一部失透したガラス、×は結晶化して上記の方法ではガラス化できなかったことを示す。 Here, molten glass was prepared with various compositions in order to determine the vitrification zone. Ammonium dihydrogen phosphate, boehmite, boron oxide and sodium carbonate were mixed in various ratios, heated at 1200 to 1500 ° C. for about 1 hour, completely melted, and then poured into water to quench. Table 1 shows the oxide molar composition and vitrification state of the synthesized samples. The raw materials were mixed and prepared so that Al / P was 1.
○ indicates transparent glass, Δ indicates partially devitrified glass, and x indicates crystallization and cannot be vitrified by the above method.

Figure 2006040587
Figure 2006040587

これらのデータを基に求めた、ガラス化範囲を図１に示す。図１の結果から、ＡｌＰＯ4−Ｂ2Ｏ3−Ｎａ2Ｏ系のガラスのガラス化する組成は、ＡｌＰＯ4をｘ，Ｂ2Ｏ3をｙ，Ｎａ2Ｏをｚとするとき、モル％で表わしてｘが１０〜５０％、ｙが７５〜１５％、ｚが１５−４０％である。 The vitrification range determined based on these data is shown in FIG. From the results of FIG. 1, the composition of vitrification of AlPO 4 —B 2 O 3 —Na 2 O glass is mol% when AlPO 4 is x, B 2 O 3 is y, and Na 2 O is z. X is 10 to 50%, y is 75 to 15%, and z is 15 to 40%.

この方法により得られる多孔質体の孔径分布をみるために、表１中の試料６のガラスを、熱処理を行なわず、非晶質のままで、蒸留水と共にオートクレーブに入れ、１５０℃で２時間処理した。得られた多孔質体を真空中、２００℃で２時間乾燥し、窒素吸着曲線を測定した。図２に窒素吸着曲線から求めた細孔径分布を示す。オートクレーブ処理を行なう前のガラスの比表面積は無視できる程度に小さいが、オートクレーブ処理により、大部分のホウ酸成分とナトリウム成分が溶出し、比表面積が２３６ｍ2／ｇで、細孔径５−１０ｎｍに主な分布を有するメソポア多孔質体が得られた。ガラスを結晶化した後に熱水中に保持してメソポア多孔質体とした場合も同様の細孔分布が得られた。 In order to observe the pore size distribution of the porous body obtained by this method, the glass of Sample 6 in Table 1 was not heat-treated and remained amorphous and was placed in an autoclave with distilled water at 150 ° C. for 2 hours. Processed. The obtained porous body was dried in vacuum at 200 ° C. for 2 hours, and a nitrogen adsorption curve was measured. FIG. 2 shows the pore size distribution obtained from the nitrogen adsorption curve. Although the specific surface area of the glass before the autoclave treatment is negligibly small, most of the boric acid component and sodium component are eluted by the autoclave treatment, the specific surface area is 236 m 2 / g, and the pore diameter is 5-10 nm. A mesoporous material having a main distribution was obtained. A similar pore distribution was obtained when the glass was crystallized and then retained in hot water to form a mesopore porous body.

多孔質化処理のために、上記のガラスを熱水中で処理すると、一部分又は大部分のＲ2Ｏ及びＢ2Ｏ3成分が溶出し、ＡｌＰＯ4を主成分とするメソポア多孔体が得られる。このとき、Ｒ2Ｏ成分の一部が残存するので、メソポア多孔体はイオン交換性を有する。このメソポア多孔体を塩酸、硫酸、酢酸又は硝酸などの酸で洗浄することにより、Ｒ2Ｏ成分のＲイオンの一部がプロトン交換してプロトン伝導体となる。 When the above glass is treated in hot water for the porosification treatment, a part or most of the R 2 O and B 2 O 3 components are eluted, and a mesopore porous body mainly composed of AlPO 4 is obtained. . At this time, a part of the R 2 O component remains, so that the mesoporous material has ion exchange properties. By washing this mesoporous material with an acid such as hydrochloric acid, sulfuric acid, acetic acid or nitric acid, a part of R ions of the R 2 O component is proton-exchanged to become a proton conductor.

イオン交換はＲイオンをプロトンと直接交換することもできるが、アンモニウムと交換後、プロトン体に変換することもできる。イオン交換は水溶液中だけでなく、アセトンやホルムアミド、アセトニトリル、テトラヒドロフラン、アルコールなどの有機溶媒を用いることもできる。   In the ion exchange, R ions can be directly exchanged with protons, but can also be converted into proton bodies after exchange with ammonium. The ion exchange can be performed not only in an aqueous solution but also using an organic solvent such as acetone, formamide, acetonitrile, tetrahydrofuran, or alcohol.

以下、本発明の詳細を実施例により説明する。
（実施例１）
ベーマイト（ＡｌＯＯＨ）、リン酸２水素アンモニウム、酸化ホウ素及び炭酸ナトリウムを原料として、モル比がＡｌＰＯ4：Ｂ2Ｏ3：Ｎａ2Ｏ＝２５：５６：１９となるように混合し、白金ルツボを用いて１３００℃で溶融した。 Hereinafter, the details of the present invention will be described by way of examples.
Example 1
Using boehmite (AlOOH), ammonium dihydrogen phosphate, boron oxide and sodium carbonate as raw materials, the molar ratio is AlPO 4 : B 2 O 3 : Na 2 O = 25: 56: 19, and a platinum crucible is mixed. Used and melted at 1300 ° C.

その後、室温で急冷して透明なガラスを得た。これを９０℃の温水中で約５時間処理した。この処理により、殆どのＢ2Ｏ3成分と約６０％のＮａ2Ｏ成分が溶出して多孔体を得た。この多孔体は、２００℃で真空排気後、液体窒素温度で窒素ガス吸着を測定すると、比表面積が３３０ｍ2／ｇ、細孔容量０.３４ｍｌ／ｇのメソポア多孔体であった。
そのメソポア多孔体を０．１Ｍ濃度の塩酸水溶液中に約２０時間室温で放置し、水洗することにより、残存するＮａイオンの一部をプロトンと交換してプロトン伝導体であるプロトン交換メソポア多孔体を得た。 Then, it cooled rapidly at room temperature and obtained the transparent glass. This was treated in warm water at 90 ° C. for about 5 hours. By this treatment, most of the B 2 O 3 component and about 60% of the Na 2 O component were eluted to obtain a porous body. The porous body was a mesopore porous body having a specific surface area of 330 m 2 / g and a pore volume of 0.34 ml / g as measured by adsorption of nitrogen gas at a liquid nitrogen temperature after evacuation at 200 ° C.
The mesopore porous body is left in an aqueous 0.1M hydrochloric acid solution at room temperature for about 20 hours and washed with water, whereby a part of the remaining Na ions are exchanged with protons to be a proton exchange mesopore porous body that is a proton conductor. Got.

このプロトン交換メソポア多孔体を板状のペレットに成形し、インピーダンスアナライザー（ヒューレットパッカード社ＨＰ−６４２０）により、複素インピーダンスを測定し、Ｃｏｌｅ−Ｃｏｌｅプロットから、イオン伝導度を測定した。Ｃｏｌｅ−Ｃｏｌｅプロットでは、実数軸と円弧の切片から抵抗が求められる。この実施例では、図３に示されるように、その抵抗値は室温で６００ｋΩであり、試料の形状を考慮すると、伝導度は２.２×１０-6Ｓ／ｃｍとなった。 This proton exchange mesopore porous body was formed into a plate-like pellet, the complex impedance was measured with an impedance analyzer (Hewlett-Packard Company HP-6420), and the ionic conductivity was measured from the Cole-Cole plot. In the Cole-Cole plot, the resistance is obtained from the real axis and the intercept of the arc. In this example, as shown in FIG. 3, the resistance value was 600 kΩ at room temperature, and the conductivity was 2.2 × 10 −6 S / cm considering the shape of the sample.

（実施例２）
ベーマイト（ＡｌＯＯＨ）、リン酸２水素アンモニウム、酸化ホウ素、炭酸ナトリウム及び酸化ジルコニウムを原料として、モル比がＡｌＰＯ4：Ｂ2Ｏ3：Ｎａ2Ｏ：ＺｒＯ2＝２５：５６：１９：２となるように混合し、白金ルツボを用いて１３００℃で溶融した。実施例１と同様に温水処理により、メソポア多孔体を得た。そのメソポア多孔体は、実施例１と同様に測定すると、比表面積が３４０ｍ2／ｇ、細孔容積が０.４３ｍｌ／ｇ、細孔径分布のピークが６.６ｎｍであった。これを０．１Ｍ濃度の塩酸水溶液中に約２０時間室温で放置し、水洗して得たプロトン伝導体のプロトン伝導度は、実施例１と同様にインピーダンスアナライザーを用いて測定すると、室温での伝導度が３.９×１０-5Ｓ／ｃｍであった。 (Example 2)
Using boehmite (AlOOH), ammonium dihydrogen phosphate, boron oxide, sodium carbonate and zirconium oxide as a raw material, the molar ratio is AlPO 4 : B 2 O 3 : Na 2 O: ZrO 2 = 25: 56: 19: 2. And melted at 1300 ° C. using a platinum crucible. A mesoporous material was obtained by hot water treatment in the same manner as in Example 1. When the mesopore porous material was measured in the same manner as in Example 1, the specific surface area was 340 m 2 / g, the pore volume was 0.43 ml / g, and the peak of the pore size distribution was 6.6 nm. The proton conductivity of the proton conductor obtained by leaving it in a 0.1 M hydrochloric acid aqueous solution at room temperature for about 20 hours and washing with water was measured using an impedance analyzer in the same manner as in Example 1. The conductivity was 3.9 × 10 −5 S / cm.

（実施例３）
ベーマイト（ＡｌＯＯＨ）、リン酸２水素アンモニウム、酸化ホウ素、炭酸ナトリウム及び酸化ジルコニウムを原料として、モル比がＡｌＰＯ4：Ｂ2Ｏ3：Ｎａ2Ｏ：ＺｒＯ2：Ｐ2Ｏ5＝２５：５６：１９：２：１０となるように混合し、白金ルツボを用いて１３００℃で溶融した。実施例１と同様に温水で処理し、メソポア多孔体を得た。これをアセトンに濃塩酸を加えて調製した０．１Ｍ濃度の塩酸/アセトン溶液中に室温で２０時間保持し、その後、アセトンで洗浄して、プロトン伝導体を得た。このプロトン伝導体のプロトン伝導度は、実施例１と同様にインピーダンスアナライザーを用いて測定すると、図３に示されるように、室温での抵抗値が４．４ｋΩであり、試料の形状を考慮すると、伝導度は４．８×１０-4Ｓ／ｃｍであった。 (Example 3)
Using boehmite (AlOOH), ammonium dihydrogen phosphate, boron oxide, sodium carbonate and zirconium oxide as a raw material, the molar ratio is AlPO 4 : B 2 O 3 : Na 2 O: ZrO 2 : P 2 O 5 = 25: 56: It mixed so that it might become 19: 2: 10, and it fuse | melted at 1300 degreeC using the platinum crucible. It processed with warm water like Example 1, and obtained the mesopore porous body. This was kept in a 0.1 M hydrochloric acid / acetone solution prepared by adding concentrated hydrochloric acid to acetone for 20 hours at room temperature, and then washed with acetone to obtain a proton conductor. The proton conductivity of this proton conductor is measured using an impedance analyzer in the same manner as in Example 1. As shown in FIG. 3, the resistance value at room temperature is 4.4 kΩ, and the shape of the sample is taken into consideration. The conductivity was 4.8 × 10 −4 S / cm.

（実施例４）
実施例３で合成した試料を用いて、水蒸気中、１５０℃まで、イオン伝導度を測定した。伝導度は、室温から６０℃まで、温度と共に増大し、約１×１０-3Ｓ／ｃｍに達し、その後、ほぼ一定値を保持した。 Example 4
Using the sample synthesized in Example 3, ion conductivity was measured up to 150 ° C. in water vapor. The conductivity increased with temperature from room temperature to 60 ° C. and reached about 1 × 10 −3 S / cm, after which it remained almost constant.

本発明は燃料電池のセパレーター、センサー、センサー、固体酸触媒などに利用することができる。   The present invention can be used for fuel cell separators, sensors, sensors, solid acid catalysts, and the like.

一実施例におけるＡｌＰＯ4−Ｂ2Ｏ3−Ｎａ2Ｏ系ガラスのガラス化範囲を示す図である。Is a diagram showing an AlPO 4 -B 2 O 3 -Na 2 vitrification range of O-based glass in one embodiment. 一実施例で得られた多孔質体の細孔径分布を示す図である。It is a figure which shows the pore size distribution of the porous body obtained by one Example. 実施例１によるプロトン伝導体の抵抗を求めるためのＣｏｌｅ−Ｃｏｌｅプロットを示す図であり、横軸は実数軸、縦軸は虚数軸である。It is a figure which shows the Cole-Cole plot for calculating | requiring the resistance of the proton conductor by Example 1, a horizontal axis is a real number axis, and a vertical axis | shaft is an imaginary number axis | shaft. 実施例３によるプロトン伝導体の抵抗を求めるためのＣｏｌｅ−Ｃｏｌｅプロットを示す図である。FIG. 6 is a diagram showing a Cole-Cole plot for determining the resistance of a proton conductor according to Example 3.

Claims (8)

ＡｌＰＯ4を主成分とし、孔径が２ｎｍ以上の細孔をもつＡｌＰＯ4系イオン交換性メソポア多孔体であって、その細孔壁がプロトンとイオン交換されているプロトン伝導体。 A main component AlPO 4, pore size a AlPO 4 based ion exchange mesoporous material having a pore over 2 nm, the proton conductor thereof pore walls are proton and ion exchange. 以下の工程（Ａ）から（Ｃ）を含むプロトン伝導体製造方法。
（Ａ）ＡｌＰＯ4、Ｂ2Ｏ3及びＲ2Ｏ（Ｒはアルカリ金属）を主成分とするＡｌＰＯ4−Ｂ2Ｏ3−Ｒ2Ｏガラスを得る工程、
（Ｂ）前記ガラスがＲ2Ｏ成分の一部分を残した状態のイオン交換性メソポア多孔体となるまで、前記ガラスからＢ2Ｏ3成分及びＲ2Ｏ成分の少なくとも一部分を水又は弱酸もしくは弱アルカリの水溶液に溶出させる工程、並びに
（Ｃ）前記メソポア多孔体のＲ2Ｏ成分のＲイオンの少なくとも一部分をプロトンと交換させるイオン交換工程。 A proton conductor production method comprising the following steps (A) to (C).
(A) A step of obtaining an AlPO 4 —B 2 O 3 —R 2 O glass mainly composed of AlPO 4 , B 2 O 3 and R 2 O (R is an alkali metal),
(B) Until the glass becomes an ion-exchangeable mesopore porous body with a part of the R 2 O component remaining, at least a part of the B 2 O 3 component and the R 2 O component is removed from the glass with water, weak acid or weak alkali. And (C) an ion exchange step of exchanging at least a part of R ions of the R 2 O component of the mesopore porous body with protons. ＡｌＰＯ4−Ｂ2Ｏ3−Ｒ2Ｏガラスの組成が、アルカリ金属ＲとしてＮａを使用し、ＡｌＰＯ4をｘ、Ｂ2Ｏ3をｙ、Ｒ2Ｏをｚとするとき、モル％で表してｘが１０〜５０％、ｙが７５〜１５％、ｚが１５〜４０％である請求項２に記載のプロトン伝導体製造方法。 The composition of the AlPO 4 —B 2 O 3 —R 2 O glass is expressed in mol% when Na is used as the alkali metal R, AlPO 4 is x, B 2 O 3 is y, and R 2 O is z. The method for producing a proton conductor according to claim 2, wherein x is 10 to 50%, y is 75 to 15%, and z is 15 to 40%. ＡｌＰＯ4−Ｂ2Ｏ3−Ｒ2Ｏガラスを得る工程では、アルカリ金属酸化物、アルカリ土類金属酸化物、ＩＩＩ族酸化物、ＩＶ族酸化物、Ｖ族酸化物及びＶＩ族酸化物からなる酸化物群のうちの１成分又は複数成分を修飾酸化物として、０．５〜８モル％の範囲で添加する請求項２又は３に記載のプロトン伝導体製造方法。 In the step of obtaining AlPO 4 —B 2 O 3 —R 2 O glass, the glass comprises an alkali metal oxide, an alkaline earth metal oxide, a group III oxide, a group IV oxide, a group V oxide, and a group VI oxide. The method for producing a proton conductor according to claim 2 or 3, wherein one component or a plurality of components in the oxide group is added as a modified oxide in a range of 0.5 to 8 mol%. 前記修飾酸化物に含まれるアルカリ金属酸化物はＫ2Ｏであり、アルカリ土類金属酸化物はＣａＯ、ＭｇＯ及びＢａＯであり、ＩＩＩ族酸化物はＡｌ2Ｏ3、Ｙ2Ｏ3及びＧａ2Ｏ3であり、ＩＶ族酸化物はＴｉＯ2、ＺｒＯ2、ＨｆＯ2、ＳｉＯ2、ＧｅＯ2、ＳｎＯ2及びＰｂＯ2であり、Ｖ族酸化物はＶ2Ｏ5、Ｎｂ2Ｏ5、Ｐ2Ｏ5、Ｓｂ2Ｏ5及びＢｉ2Ｏ3であり、ＶＩ族酸化物はＣｒ2Ｏ3、ＭｏＯ3及びＷＯ3である請求項４に記載のプロトン伝導体製造方法。 The alkali metal oxide contained in the modified oxide is K 2 O, the alkaline earth metal oxides are CaO, MgO and BaO, and the group III oxides are Al 2 O 3 , Y 2 O 3 and Ga 2. O 3 , group IV oxides are TiO 2 , ZrO 2 , HfO 2 , SiO 2 , GeO 2 , SnO 2 and PbO 2 , and group V oxides are V 2 O 5 , Nb 2 O 5 , P 2. 5. The method for producing a proton conductor according to claim 4, which is O 5 , Sb 2 O 5 and Bi 2 O 3 , and the Group VI oxides are Cr 2 O 3 , MoO 3 and WO 3 . 前記工程（Ｃ）のイオン交換工程はブレンステッド酸溶液中で行なう請求項２から５のいずれかに記載のプロトン伝導体製造方法。 6. The method for producing a proton conductor according to claim 2, wherein the ion exchange step of the step (C) is performed in a Bronsted acid solution. 前記工程（Ｃ）のイオン交換工程は有機溶媒中にブレンステッド酸を溶解した溶液中で行なう請求項６に記載のプロトン伝導体製造方法。 The method for producing a proton conductor according to claim 6, wherein the ion exchange step of the step (C) is performed in a solution in which Bronsted acid is dissolved in an organic solvent. 前記有機溶媒はアセトンである請求項７に記載のプロトン伝導体製造方法。
The method for producing a proton conductor according to claim 7, wherein the organic solvent is acetone.
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JP2013201115A (en) * 2012-02-22 2013-10-03 Kawazoe Frontier Technology Kk Proton conductive material, solid electrolyte film, and manufacturing method of proton conductive material
JP2016189241A (en) * 2015-03-30 2016-11-04 川副　博司 Proton conductive material, solid electrolyte membrane and method for manufacturing proton conductive material
JP2019087463A (en) * 2017-11-08 2019-06-06 国立大学法人広島大学 Proton conductor and production method thereof
JP2023065976A (en) * 2021-10-28 2023-05-15 日本碍子株式会社 Proton conductive material
JP2023065978A (en) * 2021-10-28 2023-05-15 日本碍子株式会社 Proton conductive material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013201115A (en) * 2012-02-22 2013-10-03 Kawazoe Frontier Technology Kk Proton conductive material, solid electrolyte film, and manufacturing method of proton conductive material
JP2016189241A (en) * 2015-03-30 2016-11-04 川副　博司 Proton conductive material, solid electrolyte membrane and method for manufacturing proton conductive material
JP2019087463A (en) * 2017-11-08 2019-06-06 国立大学法人広島大学 Proton conductor and production method thereof
JP6998586B2 (en) 2017-11-08 2022-02-10 国立大学法人広島大学 Proton conductor and its manufacturing method
JP2023065976A (en) * 2021-10-28 2023-05-15 日本碍子株式会社 Proton conductive material
JP2023065978A (en) * 2021-10-28 2023-05-15 日本碍子株式会社 Proton conductive material

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