JPH0533179A - Production of cell for steam electrolysis - Google Patents

Production of cell for steam electrolysis

Info

Publication number
JPH0533179A
JPH0533179A JP3216132A JP21613291A JPH0533179A JP H0533179 A JPH0533179 A JP H0533179A JP 3216132 A JP3216132 A JP 3216132A JP 21613291 A JP21613291 A JP 21613291A JP H0533179 A JPH0533179 A JP H0533179A
Authority
JP
Japan
Prior art keywords
hydrogen electrode
cell
molding
electrolyte
solid electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP3216132A
Other languages
Japanese (ja)
Inventor
Ryoichi Okuyama
良一 奥山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yuasa Corp
Original Assignee
Yuasa Corp
Yuasa Battery Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yuasa Corp, Yuasa Battery Corp filed Critical Yuasa Corp
Priority to JP3216132A priority Critical patent/JPH0533179A/en
Publication of JPH0533179A publication Critical patent/JPH0533179A/en
Pending legal-status Critical Current

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

PURPOSE:To simplify the process for production by pouring a slurry containing a metal oxide or metal onto an electrolyte molding 5, thereby forming a combination body having a hydrogen electrode molding 6 on the electrolyte molding 5. CONSTITUTION:The slurry contg. zirconia mixed with a stabilizer is poured into a mold 4 having water absorptivity to form the electrolyte molding 5; thereafter, the slurry contg. the metal oxide or metal is poured onto this electrolyte molding 5 to constitute the hydrogen molding 6. The molding is dried and after the mold 4 is removed, the molding is calcined to form the solid electrolyte-hydrogen electrode combination body having the hydrogen electrode 7 on the inner side and the solid electrolyte film 8 on the outer side. The solid electrolyte film 8 and the hydrogen electrode 7 can integrally be constituted and since the thickness thereof can arbitrarily be controlled, the performance of the cell for steam electrolysis is enhanced. Since the electrolyte molding 5 and the hydrogen electrode molding 6 are formed by pouring the slurry into the mold 4, the process for production is simplified.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、水蒸気電解用セルの製
造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a cell for steam electrolysis.

【０００２】[0002]

【従来の技術】水蒸気電解用セルとしては、電解質にア
ルカリ水溶液を用いるアルカリ型、高分子固体電解質膜
を用いる高分子膜型の一部が実用化され、室温から１０
０℃程度までの温度下での電解に用いられている。2. Description of the Related Art As a cell for steam electrolysis, a part of an alkaline type using an aqueous alkaline solution as an electrolyte and a polymer membrane type using a polymer solid electrolyte membrane has been put into practical use.
It is used for electrolysis at temperatures up to about 0 ° C.

【０００３】このような水蒸気電解用セルでは、電極反
応に伴う分極を抑制するために白金やパラジウムのよう
な貴金属の触媒を必要とし、また電解に要する分解電圧
が高いためにエネルギーロスが大きいという問題があっ
た。In such a steam electrolysis cell, a catalyst of a noble metal such as platinum or palladium is required to suppress polarization associated with an electrode reaction, and the decomposition voltage required for electrolysis is high, resulting in a large energy loss. There was a problem.

【０００４】上記のような問題を解消しうるものとし
て、安定化ジルコニアを電解質として用い１０００℃程
度の温度下で電解を行うものが独国のドルニエ社、米国
のウェスティングハウス社等で開発されているが、緻密
な固体電解質膜を必要とし、その方法として、押し出し
成形法、プレズマ溶射法、電気化学蒸着法（ＥＶＤ）が
用いられていた。In order to solve the above-mentioned problems, a method of using stabilized zirconia as an electrolyte and performing electrolysis at a temperature of about 1000 ° C. was developed by Dornier in Germany and Westinghouse in the United States. However, a dense solid electrolyte membrane is required, and as a method therefor, an extrusion molding method, a plasma spraying method, and an electrochemical vapor deposition method (EVD) have been used.

【０００５】さらに、上記のような緻密な固体電解質膜
を作成する方法としては、図８のように安定化ジルコニ
ア粉末３をスラリーにし、基材１上に塗布して焼成する
試みもなされている。Further, as a method of forming the dense solid electrolyte membrane as described above, it has been attempted to make the stabilized zirconia powder 3 into a slurry, apply it to the base material 1 and fire it as shown in FIG. .

【０００６】[0006]

【発明が解決しようとする課題】上記した前者の製造方
法では、高価な製造装置を必要とするうえに、固体電解
質膜を必要とする部分と必要としない部分とを構成する
マスキングに時間がかかるため、電池の量産性に問題が
あった。In the former manufacturing method described above, an expensive manufacturing apparatus is required, and it takes a long time to perform masking for forming a portion requiring the solid electrolyte membrane and a portion not requiring the solid electrolyte membrane. Therefore, there was a problem in mass productivity of the battery.

【０００７】また、後者の製造方法では、焼成時に安定
化ジルコニア粉末３が収縮するため、基材１の上に構成
された固体電解質膜８に割れ２を生じたり、固体電解質
膜８が剥離するという問題があった。Further, in the latter manufacturing method, the stabilized zirconia powder 3 shrinks during firing, so that cracks 2 occur in the solid electrolyte membrane 8 formed on the base material 1 or the solid electrolyte membrane 8 peels off. There was a problem.

【０００８】[0008]

【課題を解決するための手段】上記課題を解決するた
め、本発明は、安定化剤を添加したジルコニアを含有す
るスラリーを成形して電解質成形体とする工程と、前記
電解質成形体の一方の面に、金属もしくは金属酸化物を
含有するスラリーを成形して水素極成形体を構成し、電
解質成形体と水素極成形体とを一体化した複合成形体を
得る工程と、この複合成形体を焼成して固体電解質−水
素極複合体を得る工程と、この固体電解質−水素極複合
体の固体電解質側に空気極を形成することを特徴とする
ものである。In order to solve the above-mentioned problems, the present invention provides a step of forming a slurry containing a zirconia to which a stabilizer is added to form an electrolyte molded body, and one of the above-mentioned electrolyte molded bodies. A step of forming a slurry containing a metal or a metal oxide on the surface to form a hydrogen electrode formed body, and obtaining a composite formed body in which an electrolyte formed body and a hydrogen electrode formed body are integrated; The method is characterized by comprising a step of firing to obtain a solid electrolyte-hydrogen electrode composite, and forming an air electrode on the solid electrolyte side of the solid electrolyte-hydrogen electrode composite.

【０００９】[0009]

【作用】上記のように、本発明は、スラリーを成形して
電解質成形体と水素極成形体とを構成してこれらを同時
に焼成しているので、緻密な固体電解質膜と多孔性の水
素極とを容易に形成することができ、その厚みもスラリ
ーを流す時間によって任意にコントロールすることがで
きる。As described above, according to the present invention, a slurry is formed to form an electrolyte formed body and a hydrogen electrode formed body, and these are fired at the same time. Therefore, a dense solid electrolyte membrane and a porous hydrogen electrode are formed. And can be easily formed, and the thickness thereof can be arbitrarily controlled by the time during which the slurry flows.

【００１０】一方、スラリー中に添加された金属酸化物
は、水素と接触して還元され、水素極としての作用をす
る。また前記スラリーから構成される水素極成形体は、
焼成することによって水素極の強度が高まり基材として
の作用もする。On the other hand, the metal oxide added to the slurry comes into contact with hydrogen to be reduced and acts as a hydrogen electrode. Further, the hydrogen electrode molded body composed of the slurry,
The firing increases the strength of the hydrogen electrode and also acts as a base material.

【００１１】[0011]

【実施例】図１は、本発明の水蒸気電解用セルの製造方
法に使用するスラリーを成形するための型４の断面図
で、石膏のような吸水性を有する材料からなる。EXAMPLE FIG. 1 is a cross-sectional view of a mold 4 for molding a slurry used in the method for producing a cell for steam electrolysis according to the present invention, which is made of a material having a water absorbing property such as gypsum.

【００１２】図２は、前記型４に安定化剤としてのイッ
トリアを添加したジルコニア粉末、水、分散材、バイン
ダー、消泡剤からなるスラリーを流し込んで一定時間放
置して電解質成形体５とした後、余剰のスラリーを除去
した状態の断面図である。In FIG. 2, a slurry comprising zirconia powder containing yttria as a stabilizer, water, a dispersant, a binder and a defoaming agent is poured into the mold 4 and left for a certain period of time to prepare an electrolyte molded body 5. After that, it is a cross-sectional view of a state in which excess slurry is removed.

【００１３】図３は、前記スラリーに金属酸化物として
の酸化ニッケルを添加したスラリーを、前記電解質成形
体５が乾燥するまでに、その上に流し込んで一定時間放
置して水素極成形体６とした後、余剰のスラリーを除去
した状態の断面図である。なお、この水素極成形体６を
形成するためのスラリーと電解質成形体５を形成するた
めのスラリーとは同一のものでなくてもよいことは言う
までもない。In FIG. 3, a slurry prepared by adding nickel oxide as a metal oxide to the slurry is poured onto the electrolyte molded body 5 and left for a certain period of time until the electrolyte molded body 5 dries, and a hydrogen electrode molded body 6 is formed. FIG. 4 is a cross-sectional view of a state in which a surplus slurry has been removed after the process. It goes without saying that the slurry for forming the hydrogen electrode molded body 6 and the slurry for forming the electrolyte molded body 5 do not have to be the same.

【００１４】図４は、図３の状態のものを乾燥させて型
４を除去した後焼成して得た固体電解質−水素極複合体
の断面図で、内側に多孔性の水素極７が形成され、外側
に緻密な固体電解質膜８が形成される。FIG. 4 is a sectional view of a solid electrolyte-hydrogen electrode composite obtained by drying the state of FIG. 3 to remove the mold 4 and then firing it. A porous hydrogen electrode 7 is formed inside. As a result, a dense solid electrolyte membrane 8 is formed on the outside.

【００１５】図５は、前記固体電解質−水素極複合体の
固体電解質膜８の外側に空気極９として、ストロンチウ
ムをドープしたＬａＭｎＯ3 をデイッピング法によって
形成した状態の断面図、すなわち本発明の製造方法によ
って得られた水蒸気電解用セルの断面図である。なお、
空気極９の形成方法としては、デイッピング法以外にス
ラリー塗布法、溶射法等がある。FIG. 5 is a cross-sectional view of a state in which strontium-doped LaMnO 3 is formed by the dipping method as an air electrode 9 on the outside of the solid electrolyte membrane 8 of the solid electrolyte-hydrogen electrode composite, that is, the production of the present invention. FIG. 3 is a cross-sectional view of a steam electrolysis cell obtained by the method. In addition,
As a method for forming the air electrode 9, there are a slurry coating method, a thermal spraying method and the like other than the dipping method.

【００１６】こうして得られた図５のような水蒸気電解
用セルを作動温度である７００℃から１０００℃に昇温
し、水素極７側に水素を、空気極９側に空気を供給する
と、水素によって水素極７中の酸化ニッケルが還元され
る。When the thus obtained cell for steam electrolysis as shown in FIG. 5 is heated from the operating temperature of 700 ° C. to 1000 ° C. and hydrogen is supplied to the hydrogen electrode 7 side and air to the air electrode 9 side, hydrogen is supplied. Thereby, nickel oxide in the hydrogen electrode 7 is reduced.

【００１７】そして、図５の水素極７に水蒸気を供給
し、この水素極７を負極、空気極９を正極にして約１Ｖ
の電圧を印加すると、水素極７で水蒸気が電解され、外
部回路から供給される電子を取り込んで酸素イオンと水
素とを生成し、この酸素イオンは固体電解質膜８を通っ
て固体電解質膜８と空気極９との界面に到達し、この界
面で酸素イオンは外部回路に電子を放出して酸素とな
り、空気極９中に放出される。Then, water vapor is supplied to the hydrogen electrode 7 in FIG.
When the voltage is applied, the water vapor is electrolyzed at the hydrogen electrode 7, and the electrons supplied from the external circuit are taken in to generate oxygen ions and hydrogen. The oxygen ions pass through the solid electrolyte membrane 8 and the solid electrolyte membrane 8 When it reaches the interface with the air electrode 9, oxygen ions release electrons to the external circuit at this interface to become oxygen, which is released into the air electrode 9.

【００１８】以上の説明は、型４が円筒型複合成形体を
製造するためのものであったが、図６のような型４を使
用すれば平板型の複合成形体を、図７のような型４を使
用すればモノリシック型の複合成形体を製造できること
は言うまでもない。In the above description, the mold 4 is for producing a cylindrical composite molded body. However, if the mold 4 as shown in FIG. 6 is used, a flat type composite molded body can be obtained as shown in FIG. It is needless to say that a monolithic type composite molded body can be manufactured by using the mold 4.

【００１９】[0019]

【発明の効果】上記した如く、本発明は緻密な固体電解
質膜８と多孔性の水素極７とが容易に形成でき、その厚
みもスラリーを流す時間によって任意にコントロールす
ることができるので、容易に固体電解質膜８の抵抗と機
械的強度とをコントロールすることができ、高性能な水
蒸気電解用セルが得られる。As described above, according to the present invention, the dense solid electrolyte membrane 8 and the porous hydrogen electrode 7 can be easily formed, and the thickness thereof can be arbitrarily controlled by the time of flowing the slurry. Moreover, the resistance and mechanical strength of the solid electrolyte membrane 8 can be controlled, and a high-performance cell for steam electrolysis can be obtained.

【００２０】また、吸水性を有する型４にスラリーを流
し込んで電解質成形体５と水素極成形体６とを構成して
焼成しているので、製造工程の簡素化を図ることができ
る。Further, the slurry is poured into the water-absorbing mold 4 to form the electrolyte molded body 5 and the hydrogen electrode molded body 6 and fired, so that the manufacturing process can be simplified.

【図面の簡単な説明】[Brief description of drawings]

【図１】本発明の水蒸気電解用セルの製造方法に使用す
る型４の断面図である。FIG. 1 is a cross-sectional view of a mold 4 used in the method for manufacturing a cell for steam electrolysis according to the present invention.

【図２】図１の型４にスラリーを流し込んで一定時間放
置して電解質成形体５とした後、余剰のスラリーを除去
した状態の断面図である。FIG. 2 is a cross-sectional view showing a state in which a slurry is poured into a mold 4 of FIG. 1 and left for a certain period of time to form an electrolyte molded body 5, and then excess slurry is removed.

【図３】図２の電解質成形体５の上にスラリーを流し込
んで一定時間放置して水素極成形体６とした後、余剰の
スラリーを除去して複合成形体とした状態の断面図であ
る。FIG. 3 is a cross-sectional view showing a state where a slurry is poured onto the electrolyte molded body 5 of FIG. 2 and left for a certain period of time to form a hydrogen electrode molded body 6, and then excess slurry is removed to form a composite molded body. .

【図４】図３の複合成形体から型４を除去した後焼成し
て得た固体電解質−水素極複合体の断面図である。4 is a cross-sectional view of a solid electrolyte-hydrogen electrode composite obtained by firing after removing the mold 4 from the composite formed body of FIG.

【図５】固体電解質−水素極複合体の外側に空気極９を
形成した状態の断面図である。FIG. 5 is a cross-sectional view showing a state in which an air electrode 9 is formed outside the solid electrolyte-hydrogen electrode composite.

【図６】本発明の他の実施例に係る複合成形体とした状
態の断面図である。FIG. 6 is a cross-sectional view of a composite molded body according to another embodiment of the present invention.

【図７】本発明の他の実施例に係る複合成形体とした状
態の断面図である。FIG. 7 is a cross-sectional view of a composite molded body according to another embodiment of the present invention.

【図８】従来の水蒸気電解用セルの製造方法により製造
された固体電解質膜８の断面図である。FIG. 8 is a cross-sectional view of a solid electrolyte membrane 8 manufactured by a conventional method for manufacturing a cell for steam electrolysis.

【符号の説明】[Explanation of symbols]

４ 型 ５ 電解質成形体 ６ 水素極成形体 ７ 水素極 ８ 固体電解質膜 ９ 空気極 Type 4 5 Electrolyte compact 6 Hydrogen electrode molded body 7 Hydrogen electrode 8 Solid electrolyte membrane 9 air poles

Claims (5)

【特許請求の範囲】[Claims] 【請求項１】 安定化剤を添加したジルコニアを含有す
るスラリーを成形して電解質成形体とする工程と、前記
電解質成形体の一方の面に、金属もしくは金属酸化物を
含有するスラリーを成形して水素極成形体を構成し、電
解質成形体と水素極成形体とを一体化した複合成形体を
得る工程と、この複合成形体を焼成して固体電解質−水
素極複合体を得る工程と、この固体電解質−水素極複合
体の固体電解質側に空気極を形成することを特徴とする
水蒸気電解用セルの製造方法。1. A step of forming a slurry containing zirconia to which a stabilizer is added to form an electrolyte compact, and forming a slurry containing a metal or a metal oxide on one surface of the electrolyte compact. And forming a hydrogen electrode formed body, a step of obtaining a composite formed body that integrates the electrolyte formed body and the hydrogen electrode formed body, and a step of firing the composite formed body to obtain a solid electrolyte-hydrogen electrode composite, A method for producing a cell for steam electrolysis, which comprises forming an air electrode on the solid electrolyte side of this solid electrolyte-hydrogen electrode composite. 【請求項２】 安定化剤を添加したジルコニアは立方晶
ジルコニア、正方晶ジルコニア、部分安定化ジルコニア
の単独物もしくは複数種の混合物からなることを特徴と
する請求項第１項記載の水蒸気電解用セルの製造方法。2. The steam electrolysis according to claim 1, wherein the zirconia added with the stabilizer comprises cubic zirconia, tetragonal zirconia and partially stabilized zirconia alone or as a mixture of plural kinds. Cell manufacturing method. 【請求項３】 安定化剤は、イットリウム、カルシウ
ム、スカンジウム、イッテルビウム、ネオジウム、ガド
リニウムの酸化物であることを特徴とする請求項第１項
記載の水蒸気電解用セルの製造方法。3. The method for producing a cell for steam electrolysis according to claim 1, wherein the stabilizer is an oxide of yttrium, calcium, scandium, ytterbium, neodymium, or gadolinium. 【請求項４】 金属酸化物もしくは金属は、ニッケルま
たはコバルトの酸化物もしくは金属ニッケルまたは金属
コバルトであることを特徴とする請求項第１項記載の水
蒸気電解用セルの製造方法。4. The method for producing a cell for steam electrolysis according to claim 1, wherein the metal oxide or metal is an oxide of nickel or cobalt, or metal nickel or metal cobalt. 【請求項５】 空気極は、ストロンチウムもしくはカル
シウムをドープしたＬａＭｎＯ3 、ＬａＣｏＯ3 、Ｃａ
ＭｎＯ3 であることを特徴とする請求項第１項記載の水
蒸気電解用セルの製造方法。5. The air electrode comprises LaMnO 3 , LaCoO 3 , Ca doped with strontium or calcium.
The method for producing a cell for steam electrolysis according to claim 1, wherein the cell is MnO 3 .
JP3216132A 1991-07-31 1991-07-31 Production of cell for steam electrolysis Pending JPH0533179A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP3216132A JPH0533179A (en) 1991-07-31 1991-07-31 Production of cell for steam electrolysis

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3216132A JPH0533179A (en) 1991-07-31 1991-07-31 Production of cell for steam electrolysis

Publications (1)

Publication Number Publication Date
JPH0533179A true JPH0533179A (en) 1993-02-09

Family

ID=16683768

Family Applications (1)

Application Number Title Priority Date Filing Date
JP3216132A Pending JPH0533179A (en) 1991-07-31 1991-07-31 Production of cell for steam electrolysis

Country Status (1)

Country Link
JP (1) JPH0533179A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110791774A (en) * 2018-08-02 2020-02-14 国家能源投资集团有限责任公司 Method for producing hydrogen by electrolyzing water vapor

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110791774A (en) * 2018-08-02 2020-02-14 国家能源投资集团有限责任公司 Method for producing hydrogen by electrolyzing water vapor

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