JP5678383B2 - Proton conductor and electrochemical device using the same - Google Patents
Proton conductor and electrochemical device using the same Download PDFInfo
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Description
本発明は、プロトン（Ｈ+）を伝導イオン種とするプロトン伝導体及びそれを用いた燃料電池用や水素ポンプ用、水蒸気電解用の固体電解質等の電気化学素子に関するものである。 The present invention relates to a proton conductor having proton (H + ) as a conductive ion species, and an electrochemical element such as a solid electrolyte for a fuel cell, a hydrogen pump, or a steam electrolysis using the proton conductor.
従来、この種のプロトン伝導体として、例えば、リン酸塩系ガラスからなる組成構造のものが知られている。 Conventionally, as this type of proton conductor, for example, one having a composition structure made of phosphate glass is known.
しかしながらこれらリン酸塩系ガラスからなる組成構造の場合、一般に吸湿性や潮解性が激しく、水に対して非常に弱く、溶けてしまい、安定したガラス状態を保持できず、水分が存在する状況では、僅かの水分と反応してバルク状態を保つことができず、化学的耐久性が低く、機械的強度も低くなり、大面積化、高精度化等の障害となることがあるという不都合を有している。 However, in the case of a composition structure composed of these phosphate glasses, in general, hygroscopicity and deliquescence is intense, very weak against water, melts, cannot maintain a stable glass state, and there is moisture However, the bulk state cannot be maintained by reacting with a small amount of moisture, the chemical durability is low, the mechanical strength is also low, and there is a disadvantage that it may be an obstacle to increase in area and accuracy. doing.
本発明はこのような不都合を解決することを目的とするもので、本発明のうち、請求項１記載の発明は、プロトンを含むゼオライトを原料とし、該プロトンを含むゼオライトの粉末を機械加圧及び加熱により焼結してなり、該焼結により該ゼオライトの微細孔を圧潰し、この圧潰により組織を緻密化し、プロトンを保持可能なサイトをもつアルミノ珪酸系のガラスからなることを特徴とするプロトン伝導体にある。 The present invention aims to solve such disadvantages. Among the present inventions, the invention according to claim 1 uses a zeolite containing protons as a raw material, and mechanically pressurizes the powder of the zeolite containing protons. And sintered by heating, crushing the fine pores of the zeolite by the sintering, densifying the structure by the crushing, and comprising an aluminosilicate glass having sites capable of holding protons. Proton conductor.
又、請求項２記載の発明は、上記プロトンを含むゼオライトの粉末を放電プラズマ焼結法（以下、「ＳＰＳ法」ともいう。）により焼結することを特徴とするものである。 The invention described in claim 2 is characterized in that the zeolite powder containing protons is sintered by a discharge plasma sintering method (hereinafter also referred to as “SPS method”).
又、請求項３記載の発明は、上記請求項１又は２記載のプロトン伝導体を用いたことを特徴とする電気化学素子にある。 A third aspect of the present invention is an electrochemical device using the proton conductor according to the first or second aspect.
本発明は上述の如く、請求項１又は請求項３記載の発明にあっては、プロトンを含むゼオライトを原料とし、プロトンを含むゼオライトの粉末を機械加圧及び加熱により焼結して製造され、この焼結によりゼオライトの微細孔は圧潰され、この圧潰により組織が緻密化し、プロトンを保持可能なサイトをもつアルミノ珪酸系のガラスからなるプロトン伝導体を得ることができ、ゼオライトはプロトンを取り込みやすい構造と性質を有し、このゼオライトを焼結によりガラス状態とすることで、プロトンを保持できるサイトを有した状態を保持でき、このサイトを用いることでプロトンのみによる伝導が可能となり、良好なプロトン伝導度を発揮することができ、かつ、ゼオライトを原料としたガラスは、シリカ、アルミナで三次元の組織を維持するため、非常に強固な機械的強度を有し、水溶液中や高温等の様々な条件で使用することが可能となり、化学的耐久性に優れ、強い機械的強度を有したプロトン伝導体を得ることができ、このようなプロトン伝導体を燃料電池用や水素ポンプ用、水蒸気電解用の固体電解質等の各種の電気化学素子として用いることができる。 As described above, the present invention is the invention according to claim 1 or claim 3, wherein a zeolite containing proton is used as a raw material, and the zeolite containing proton is sintered by mechanical pressure and heating, Due to this sintering, the micropores of the zeolite are crushed, the structure is densified by this crushing, and a proton conductor made of aluminosilicate glass having sites capable of holding protons can be obtained. This zeolite has a structure and properties, and by sintering this zeolite into a glass state, it can maintain a state having sites capable of holding protons. By using this site, conduction only by protons is possible, and good protons are obtained. Glass that can exhibit conductivity and that uses zeolite as a raw material maintains a three-dimensional structure with silica and alumina. Therefore, it has a very strong mechanical strength, can be used in various conditions such as aqueous solution and high temperature, and obtains a proton conductor having excellent chemical durability and strong mechanical strength. Such proton conductors can be used as various electrochemical elements such as solid electrolytes for fuel cells, hydrogen pumps, and steam electrolysis.
又、請求項２記載の発明にあっては、ゼオライトの粉末を放電プラズマ焼結法を用いて焼結するようにしているから、焼結加工を容易に行うことができる。 In the invention according to claim 2, since the zeolite powder is sintered using the discharge plasma sintering method, the sintering process can be easily performed.
図１は本発明の実施の形態例であって、図１において、その製造方法を説明すると、先ず、原料として、プロトン（Ｈ+）（水素の陽イオン）を含むゼオライトＺの粉末を用意することになり、ここに、ゼオライトＺはシリカとアルミナからなるアルミノ珪酸塩系鉱物質であって、プロトンを含むゼオライトＺは、例えば、ゼオライトＺのもつイオン交換作用によりアルミノ珪酸塩のナトリウムの陽イオン（Ｎａ+）をアンモニウムイオン（ＮＨ４ +）で交換し、その後、焼成してプロトン（Ｈ+）を残し、これによりプロトンを含むゼオライトＺ（プロトンタイプのゼオライト）を得ることができ、ゼオライトＺの結晶構造中に、図１中（ａ）の断面図及び（ｂ）の側断面図の如く、原子サイズレベルの決まった大きさの多数の微細孔ｈを有しており、図１中（ｃ）の説明図の如く、プロトンを含むゼオライトＺの粉末を、真空チャンバＣ内の焼結ダイＤ中に充填して上下の焼結パンチＰ・Ｐにより挟み、ゼオライトＺの粉末を、例えば、放電プラズマ焼結法（以下、「ＳＰＳ法」という。）により機械加圧及び加熱を行って焼結し、これによりゼオライトＺの粉末の焼結体が製造され、図１中（ｄ）の断面図、（ｅ）側断面図の如く、この焼結体は微細孔ｈが圧潰されて組織が緻密化し、これによりプロトン（Ｈ+）を保持可能な不規則的な配置状態のサイト（ｓｉｔｅ）（おそらくサイトの配置状態は不規則的な配置となると思われる。）をもつアルミノ珪酸のガラスからなるプロトン伝導体Ｓが製造されることになる。尚、焼結法として、機械加圧及び加熱を同時に行う構造に限らず、ゼオライトＺの粉末を先ず機械加圧し、そして、機械加圧した状態において加熱して焼結する方法を採用することもある。 FIG. 1 shows an embodiment of the present invention. In FIG. 1, the production method will be described. First, a zeolite Z powder containing proton (H + ) (hydrogen cation) is prepared as a raw material. Zeolite Z is an aluminosilicate mineral composed of silica and alumina. Proton-containing zeolite Z is, for example, a sodium cation of aluminosilicate due to the ion exchange action of zeolite Z. (Na + ) is exchanged with ammonium ions (NH 4 + ), and then calcined to leave protons (H + ), whereby a proton-containing zeolite Z (proton-type zeolite) can be obtained. In the crystal structure of FIG. 1, a number of fine holes h having a predetermined atomic size level are formed as shown in the sectional view of FIG. As shown in FIG. 1C, the zeolite Z powder containing protons is filled in a sintering die D in a vacuum chamber C and sandwiched between upper and lower sintering punches P and P. The zeolite Z powder is sintered by, for example, mechanical pressurization and heating by a discharge plasma sintering method (hereinafter referred to as “SPS method”), thereby producing a sintered body of the zeolite Z powder. As shown in the sectional view of FIG. 1 (d) and the sectional side view of FIG. 1 (e), this sintered body is irregular in that the fine holes h are crushed and the structure becomes dense, thereby holding protons (H + ). Proton conductors S made of aluminosilicate glass with a site in a typical arrangement (probably the site arrangement is likely to be irregular) will be produced. The sintering method is not limited to a structure in which mechanical pressurization and heating are performed at the same time, and it is also possible to employ a method in which the zeolite Z powder is first mechanically pressurized and then heated and sintered in the mechanically pressurized state. is there.
この実施の形態例は上記のとおり、プロトン（Ｈ+）を含むゼオライトＺを原料とし、プロトンを含むゼオライトＺの粉末を機械加圧及び加熱により焼結して製造され、この焼結によりゼオライトＺの微細孔ｈは圧潰され、この圧潰により組織が緻密化し、プロトン（Ｈ+）が容易に他のイオンに置き換わらず、プロトンのみが通過できるガラス状態に保持可能なサイトをもつアルミノ珪酸系のガラスからなるプロトン伝導体Ｓを得ることができ、ゼオライトＺはプロトンを取り込みやすい構造及び性質を有し、このゼオライトＺを焼結によりガラス状態とすることで、プロトンを保持できるサイトを有した状態を保持でき、このサイトを用いることでプロトンのみによる伝導が可能となり、良好なプロトン伝導度を発揮することができ、かつ、ゼオライトＺを原料としたガラスは、シリカ、アルミナで三次元の組織を維持するため、非常に強固な機械的強度を有し、水溶液中や高温等の様々な条件で使用することが可能となり、化学的耐久性に優れ、強い機械的強度を有したプロトン伝導体Ｓを得ることができる。 In this embodiment, as described above, zeolite Z containing proton (H + ) is used as a raw material, and the powder of zeolite Z containing proton is sintered by mechanical pressure and heating. Of the aluminosilicate system having a site capable of maintaining a glass state in which only protons can pass therethrough without protons (H + ) being easily replaced with other ions. Proton conductor S made of glass can be obtained, and zeolite Z has a structure and properties that make it easy to take in protons, and this zeolite Z is made into a glass state by sintering, thereby having a site that can hold protons. By using this site, it is possible to conduct only by protons, and can exhibit good proton conductivity. Glass made from zeolite Z, which maintains a three-dimensional structure with silica and alumina, has extremely strong mechanical strength and can be used in various conditions such as aqueous solutions and high temperatures. The proton conductor S having excellent chemical durability and strong mechanical strength can be obtained.
この場合、プロトンを含むゼオライトＺの粉末を放電プラズマ焼結法（以下、「ＳＰＳ法」ともいう。）を用いて焼結するようにしているから、焼結加工を容易に行うことができる。 In this case, since the powder of zeolite Z containing protons is sintered using a discharge plasma sintering method (hereinafter also referred to as “SPS method”), the sintering process can be easily performed.
そして、このようなプロトン伝導体Ｓを燃料電池用や水素ポンプ用、水蒸気電解用の固体電解質等の各種の電気化学素子として用いることができる。 Such proton conductor S can be used as various electrochemical elements such as solid electrolytes for fuel cells, hydrogen pumps, and steam electrolysis.
尚、ゼオライトＺは、強固なケイ素イオンとアルミニウムイオンを骨格構造としており、さらに、ケイ素イオンとアルミニウムイオンの割合を変化させることで、骨格構造を変化させることができ、プロトン伝導度を制御することもできる。 Zeolite Z has strong silicon ions and aluminum ions as a skeleton structure, and by changing the ratio of silicon ions and aluminum ions, the skeleton structure can be changed, and proton conductivity can be controlled. You can also.
実施例１においては、モルデナイト型ゼオライトを原料とし、このモルデナイト型ゼオライトは、１次元に開かれた微細孔ｈを有しており、ナトリウムタイプ、アンモニアタイプ、プロトンタイプ（プロトンを含むタイプのゼオライトＺ）があり、このプロトンを含むプロトンタイプのゼオライトＺの粉末をＳＰＳ法を用い、焼結条件として、４０ＭＰａの圧力下において、１，２５０℃の焼結温度で焼結し、試料１のプロトン伝導体Ｓを得た。 In Example 1, mordenite-type zeolite is used as a raw material, and this mordenite-type zeolite has one-dimensionally open micropores h, and is sodium-type, ammonia-type, proton-type (zeolite-containing zeolite Z The proton-type zeolite Z powder containing protons was sintered at a sintering temperature of 1,250 ° C. under a pressure of 40 MPa as a sintering condition using the SPS method. Body S was obtained.
この試料１のプロトン伝導体ＳをＸ線回折により構造解析をした結果、図２のＸ線回折図のとおり、ほぼガラスであることがわかった。また、この試料１では、図３のとおり、４５０℃から６５０℃の温度範囲で、１０−８（Ｓｃｍ−１)から１０−4（Ｓｃｍ−１)の電気伝導度を有することがわかった。 As a result of structural analysis of the proton conductor S of Sample 1 by X-ray diffraction, it was found that it was almost glass as shown in the X-ray diffraction diagram of FIG. In addition, as shown in FIG. 3, Sample 1 was found to have an electric conductivity of 10 −8 (Scm −1 ) to 10 −4 (Scm −1 ) in the temperature range of 450 ° C. to 650 ° C.
実施例２においては、フォージャサイト型ゼオライトを原料とし、このフォージャサイト型ゼオライトには、シリカとアルミナの比の違いによりＹタイプ（ＳｉＯ２／Ａｌ２Ｏ３＝６以上）とＸタイプ（ＳｉＯ２／Ａｌ２Ｏ３＝６以下）とがあり、どちらのタイプも３次元に開かれた微細孔ｈを有しており、ナトリウムタイプ、アンモニアタイプ、プロトンタイプがあり、このＳｉＯ２／Ａｌ２Ｏ３比１４のフォージャサイト型ＹタイプゼオライトのプロトンタイプをＳＰＳ法を用い、４０ＭＰａの圧力下において、１，２００℃の焼結温度で焼結し、試料２のプロトン伝導体Ｓを得た。 In Example 2, a faujasite type zeolite is used as a raw material, and this faujasite type zeolite has a Y type (S i O 2 / Al 2 O 3 = 6 or more) and X depending on the ratio of silica and alumina. There are types (S i O 2 / Al 2 O 3 = 6 or less), and both types have micropores h that are three-dimensionally open, and there are sodium types, ammonia types, and proton types. The proton type of a faujasite type Y type zeolite with a S i O 2 / Al 2 O 3 ratio of 14 was sintered at a sintering temperature of 1,200 ° C. under a pressure of 40 MPa using a SPS method. Proton conductor S was obtained.
このプロトン伝導体ＳをＸ線回折により構造解析をした結果、図４のＸ線回折図のとおり、ほぼガラスであることがわかった。又、この試料２では、図５のとおり、４００℃から６５０℃の温度範囲で、１０−６（Ｓｃｍ−１)から１０−4（Ｓｃｍ−１)の電気伝導度を有することがわかった。 As a result of structural analysis of the proton conductor S by X-ray diffraction, it was found that the proton conductor S was almost glass as shown in the X-ray diffraction diagram of FIG. Further, as shown in FIG. 5, this sample 2 was found to have an electric conductivity of 10 −6 (Scm −1 ) to 10 −4 (Scm −1 ) in the temperature range of 400 ° C. to 650 ° C.
実施例３においては、フォージャサイト型Ｙタイプゼオライトを原料とし、ＳｉＯ２／Ａｌ２Ｏ３比６のフォージャサイト型ＹタイプゼオライトのプロトンタイプをＳＰＳ法を用い、４０ＭＰａの圧力下において、１，３００℃の焼結温度で焼結し、試料３のプロトン伝導体Ｓを得た。 In Example 3, the faujasite type Y type zeolite is used as a raw material, and the proton type of the faujasite type Y type zeolite having a S i O 2 / Al 2 O 3 ratio of 6 is used under the pressure of 40 MPa using the SPS method. The proton conductor S of Sample 3 was obtained by sintering at a sintering temperature of 1,300 ° C.
このプロトン伝導体ＳをＸ線回折により構造解析をした結果、図６のＸ線回折図のとおり、ガラス相に微細な結晶を含む構造であることがわかった。又、試料３では、図７のとおり、電気伝導度は、４５０℃から６５０℃の温度範囲で、１０−５（Ｓｃｍ−１)から１０−３（Ｓｃｍ−１)の電気伝導度を有することがわかった。 As a result of structural analysis of the proton conductor S by X-ray diffraction, it was found that the proton conductor S had a structure containing fine crystals in the glass phase as shown in the X-ray diffraction diagram of FIG. Moreover, in the sample 3, as shown in FIG. 7, the electric conductivity has an electric conductivity of 10 −5 (Scm −1 ) to 10 −3 (Scm −1 ) in the temperature range of 450 ° C. to 650 ° C. I understood.
尚、他の実施例として、上記プロトンを含むゼオライトＺにガラス成分を添加した混合物を原料とし、このプロトンを含むゼオライトＺにガラス成分を添加した混合物の粉末を機械加圧及び加熱により焼結し、この焼結によりゼオライトＺの微細孔ｈを圧潰し、この圧潰により組織が緻密化し、プロトンを保持可能なサイトをもつアルミノ珪酸系のガラスからなるプロトン伝導体Ｓとすることもできる。 As another example, a mixture of the above-described zeolite Z containing protons with a glass component added is used as a raw material, and the powder of the mixture obtained by adding a glass component to zeolite Z containing protons is sintered by mechanical pressure and heating. The fine pores h of the zeolite Z can be crushed by this sintering, the structure can be densified by the crushing, and the proton conductor S made of an aluminosilicate glass having sites capable of holding protons can be obtained.
この具体的な試料４として、例えば、上記モルデナイト型ゼオライトのプロトンタイプ、又は、上記フォージャサイト型ゼオライトのプロトンタイプに酸化鉛、酸化ビスマス等の低融点化合物を含むガラス成分を添加した混合物を原料とし、この混合物をＳＰＳ法を用い、４０ＭＰａの圧力下において、１,２００℃の焼結温度で焼結し、試料４のプロトン伝導体Ｓを得ることができる。 As this specific sample 4, for example, a raw material is a mixture in which a glass component containing a low melting point compound such as lead oxide or bismuth oxide is added to the proton type of the mordenite zeolite or the proton type of the faujasite type zeolite. Then, this mixture is sintered at a sintering temperature of 1,200 ° C. under a pressure of 40 MPa using the SPS method, and the proton conductor S of Sample 4 can be obtained.
この試料４においては、比較的低温下におけるＳＰＳ法において、プロトン伝導体Ｓを得ることができる。 In this sample 4, the proton conductor S can be obtained by the SPS method at a relatively low temperature.
尚、本発明は上記実施の形態例に限られるものではなく、ゼオライトＺの種類や焼結の方法等は適宜変更して設計されるものである。 Note that the present invention is not limited to the above embodiment, and the type of zeolite Z, the sintering method, and the like are appropriately changed and designed.
以上、所期の目的を充分達成することができる。 As described above, the intended purpose can be sufficiently achieved.
Ｚ ゼオライト
ｈ 微細孔
Ｓ プロトン伝導体
Z Zeolite h Micropore S Proton conductor
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