JPH0737591A - Molten carbonate fuel cell cathode and its dissolution suppression method - Google Patents
Molten carbonate fuel cell cathode and its dissolution suppression methodInfo
- Publication number
- JPH0737591A JPH0737591A JP5178350A JP17835093A JPH0737591A JP H0737591 A JPH0737591 A JP H0737591A JP 5178350 A JP5178350 A JP 5178350A JP 17835093 A JP17835093 A JP 17835093A JP H0737591 A JPH0737591 A JP H0737591A
- Authority
- JP
- Japan
- Prior art keywords
- cathode
- molten carbonate
- fuel cell
- nickel
- oxide
- 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.)
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Classifications
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- 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
- Y02E60/50—Fuel cells
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Abstract
(57)【要約】
【目的】 溶融炭酸塩型燃料電池のカソード材料の電解
質への溶解を抑制すること。
【構成】 溶融炭酸塩型燃料電池のカソード材料として
ニッケルまたは酸化ニッケルからなるニッケル材料とコ
バルトまたは酸化コバルトからなるコバルト材料とを熱
処理して得られる固溶体を含む物質を使用する。得られ
たカソード中にはＮｉＯにＣｏＯが固溶状態で分散して
いる。このＣｏＯは電解質である炭酸塩と反応して、当
該炭酸塩に難溶性のＬｉＣｏＯ2を生成することからＮ
ｉＯを電解質である炭酸塩に溶解しにくいＬｉＣｏＯ2
の薄膜で被覆させることが可能となりカソードの溶解現
象を抑制しうる。こうして、燃料電池の耐用年数を伸ば
すことができる。(57) [Summary] [Purpose] To suppress the dissolution of the cathode material of a molten carbonate fuel cell into the electrolyte. As a cathode material of a molten carbonate fuel cell, a substance containing a solid solution obtained by heat-treating a nickel material made of nickel or nickel oxide and a cobalt material made of cobalt or cobalt oxide is used. CoO is dispersed in NiO in a solid solution state in the obtained cathode. This CoO reacts with a carbonate which is an electrolyte to form LiCoO 2 which is hardly soluble in the carbonate, so N
LiCoO 2 which is difficult to dissolve iO in carbonate as an electrolyte
It becomes possible to coat with a thin film, and it is possible to suppress the dissolution phenomenon of the cathode. In this way, the service life of the fuel cell can be extended.
Description
【０００１】[0001]
【産業上の利用分野】本発明は燃料電池、特に溶融炭酸
塩型燃料電池のカソードの溶解を抑制する方法及びその
ための新規なカソードに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for suppressing the dissolution of the cathode of a fuel cell, particularly a molten carbonate fuel cell, and a novel cathode therefor.
【０００２】[0002]
【従来の技術】従来、水素のように酸化されやすいガス
と、酸素のように酸化力のあるガスとを電池化学反応プ
ロセスを経て反応させることにより直流電力を得るよう
にした各種燃料電池が開発されており、そのうちの一つ
に電解質として溶融炭酸塩（主にアルカリ金属炭酸塩の
混合物）を用いる溶融炭酸塩型燃料電池がある。溶融炭
酸塩型燃料電池は第二世代の燃料電池と呼ばれ、第一世
代のリン酸型燃料電池に続き、開発が行われているもの
であり、この電池は、リン酸型燃料電池のような高価な
白金触媒を用いないので、触媒被毒を考慮することな
く、多様な種類の燃料を用いる事ができ、例えば一酸化
炭素を多量に含んだ石炭ガスの利用も可能である。さら
に、この電池は５５０℃以上、通常は６５０℃程度の高
い温度で運転されるので、排熱も高温で利用され易く、
比較的安価な材料で構成されていて電池の製造コストの
低減が図れることなどの多くの優れた特徴を有する発電
設備として期待されている。2. Description of the Related Art Conventionally, various fuel cells have been developed in which a direct current electric power is obtained by reacting a gas such as hydrogen which is easily oxidized with a gas having an oxidizing power such as oxygen through a cell chemical reaction process. Among them, there is a molten carbonate fuel cell which uses a molten carbonate (mainly a mixture of alkali metal carbonates) as an electrolyte. The molten carbonate fuel cell is called the second generation fuel cell, and is being developed following the phosphoric acid fuel cell of the first generation. Since no expensive platinum catalyst is used, various types of fuels can be used without considering poisoning of the catalyst, and for example, coal gas containing a large amount of carbon monoxide can be used. Furthermore, since this battery is operated at a high temperature of 550 ° C. or higher, usually about 650 ° C., exhaust heat is easily utilized at a high temperature,
It is expected to be a power generation facility that has many excellent features such as that it is made of a relatively inexpensive material and that the manufacturing cost of the battery can be reduced.
【０００３】通常の溶融炭酸塩型燃料電池の構成は、電
解質の溶融炭酸塩をアルミン酸リチウム（ＬｉＡｌ
Ｏ2）粒子で構成されたマトリックスに含浸させた電解
質板と、金属ニッケル（Ｎｉ）多孔質焼結体よりなるア
ノードと、酸化ニッケル（ＮｉＯ）多孔質焼結体を主体
とするカソードから成っており、前記アノードに水素を
主体とする燃料ガスが供給され、またカソードには空気
と炭酸ガスの混合ガスが供給される。カソードの酸化ニ
ッケル多孔質焼結体は、金属ニッケルの微粉末を薄板状
に焼結成型した多孔質体を酸化することによって製造さ
れることもあり、この酸化処理は電池を組み立ててから
電池に空気を流通させて実施することにより行われるこ
ともある。The structure of a normal molten carbonate fuel cell is such that the molten carbonate of the electrolyte is lithium aluminate (LiAl).
O 2 ): an electrolyte plate impregnated with a matrix composed of particles; an anode made of a porous metal nickel (Ni) sintered body; and a cathode mainly made of a nickel oxide (NiO) porous sintered body. The fuel gas mainly containing hydrogen is supplied to the anode, and the mixed gas of air and carbon dioxide is supplied to the cathode. The nickel oxide porous sintered body of the cathode may be manufactured by oxidizing a porous body obtained by sintering and molding fine powder of metallic nickel into a thin plate shape, and this oxidation treatment is performed on the battery after assembling the battery. It may be carried out by circulating air.
【０００４】一方、溶融炭酸塩型燃料電池の電解質とし
ては通常、炭酸リチウム（Ｌｉ2ＣＯ3）と炭酸カリウム
（Ｋ2ＣＯ3）との混合炭酸塩が用いられているので、高
温加熱時にはこの溶融塩からのリチウム酸化物の一部が
カソードの酸化ニッケルに固溶する。すなわち、通常の
運転条件では、カソードはニッケル原子９７〜９９．５
部に対して、リチウム原子０．５〜３部程度の比率で混
合された固溶体に変化している。また、高温加熱時にお
けるこのようなカソードの酸化ニッケルのリチウム化は
酸化ニッケルの電導性を飛躍的に改善することが知られ
ている。On the other hand, a mixed carbonate of lithium carbonate (Li 2 CO 3 ) and potassium carbonate (K 2 CO 3 ) is usually used as the electrolyte of the molten carbonate fuel cell, so that it is Part of the lithium oxide from the molten salt dissolves in the nickel oxide of the cathode. That is, under normal operating conditions, the cathode contains 97 to 99.5 nickel atoms.
The amount of the lithium atom is changed to 0.5 to 3 parts by weight relative to the parts. Further, it is known that such lithiation of nickel oxide on the cathode during heating at a high temperature dramatically improves the electrical conductivity of nickel oxide.
【０００５】[0005]
【発明が解決しようとする課題】ところで、上記溶融炭
酸塩型燃料電池のカソードの酸化ニッケルは運転中、電
解質の溶融炭酸塩へ微量溶解しだす。この酸化ニッケル
の溶融炭酸塩への溶解は電池を長時間、安定的に運転す
る上で大きな障害となることが知られている。すなわ
ち、溶解した酸化ニッケルはニッケルイオンとして溶融
炭酸塩中に拡散する。溶融炭酸塩中をアノードの方向に
拡散したニッケルイオンは溶融炭酸塩中に溶解している
水素によって還元されて金属ニッケルに変換される。こ
の金属ニッケルは溶融炭酸塩にはほとんど溶解しないた
めに電解質板中に粒子状に析出してしまうことになる。
電解質板中に析出した金属ニッケル粒子の量が増加して
くると、カソードとアノードの間が電気的に短絡しやす
くなり、電池を正常に運転することが不可能になる。そ
こで、電池を長時間、正常に運転するためにはカソード
の素材である酸化ニッケルの溶融炭酸塩への溶解を抑え
る対策を実施することが必要となってくる。本発明の目
的は溶融炭酸塩型燃料電池のカソード材料の電解質への
溶解を抑制することである。By the way, during operation, a small amount of nickel oxide in the cathode of the molten carbonate fuel cell begins to dissolve in the molten carbonate of the electrolyte. It is known that the dissolution of this nickel oxide in the molten carbonate causes a great obstacle to the stable operation of the battery for a long time. That is, the dissolved nickel oxide diffuses into the molten carbonate as nickel ions. Nickel ions that have diffused in the molten carbonate toward the anode are reduced by hydrogen dissolved in the molten carbonate and converted into metallic nickel. Since this metallic nickel is hardly dissolved in the molten carbonate, it will be deposited in the form of particles in the electrolyte plate.
When the amount of metallic nickel particles deposited in the electrolyte plate increases, an electrical short circuit easily occurs between the cathode and the anode, which makes it impossible to operate the battery normally. Therefore, in order to operate the battery normally for a long time, it is necessary to take measures to suppress the dissolution of nickel oxide, which is the material of the cathode, in the molten carbonate. An object of the present invention is to suppress the dissolution of the cathode material of a molten carbonate fuel cell in the electrolyte.
【０００６】[0006]
【課題を解決するための手段】本発明の上記目的は次の
構成によって達成される。すなわち、酸化ニッケル中に
酸化コバルトを固溶状態に分散させたカソードを使用し
て、リチウム−カリウム系溶融炭酸塩と酸化コバルトと
の反応生成物であるリチウムコバルト二酸化物の薄膜で
カソード表面を被覆させる溶融炭酸塩型燃料電池カソー
ドの溶解抑制方法である。また、本発明の上記目的は次
の構成によっても達成される。すなわち、酸化ニッケル
中に酸化コバルトを固溶状態に分散させた溶融炭酸塩型
燃料電池カソード、または、酸化ニッケル中に酸化コバ
ルトを固溶状態に分散させたカソードを使用する溶融炭
酸塩型燃料電池である。The above objects of the present invention can be achieved by the following constitutions. That is, by using a cathode in which cobalt oxide is dispersed in a solid solution state in nickel oxide, the cathode surface is coated with a thin film of lithium cobalt dioxide which is a reaction product of lithium-potassium molten carbonate and cobalt oxide. And a method for suppressing dissolution of a molten carbonate fuel cell cathode. The above object of the present invention can also be achieved by the following configuration. That is, a molten carbonate fuel cell cathode in which cobalt oxide is dispersed in a solid solution state in nickel oxide, or a molten carbonate fuel cell using a cathode in which cobalt oxide is dispersed in a solid solution state in nickel oxide is used. Is.
【０００７】[0007]
【作用】本発明者らは、酸化ニッケルからなるカソード
の溶融炭酸塩への溶解を抑制する手段を探索するため
に、種々の実験研究を重ねた結果、溶融炭酸塩の改良や
電池の運転条件を変更しただけでは酸化ニッケル製のカ
ソードの溶解度を目標値以下にコントロールすることは
困難であり、他になんらかの対策を講じる必要があると
の結論に達した。従来、この課題を解決する目的で種々
の代替材料の開発が試みられてきたが、代替材料の候補
に上がったものは溶融炭酸塩中で化学的に不安定である
もの、電子伝導性が不十分なものなど、酸化ニッケルに
替わり得るものは未だに発見されていない。すなわち、
溶融炭酸塩に接することによって酸化リチウムが０．５
〜３％固溶した状態となった酸化ニッケルは、電子伝導
性が極めて良好なカソード材料になるため、上記の溶解
問題以外には、溶融炭酸塩型燃料電池のカソード材料と
しては極めて優れた材料であり、この材料を凌駕するの
は容易なことでない。The present inventors have conducted various experimental studies in order to find a means for suppressing the dissolution of the nickel oxide cathode in the molten carbonate, and as a result, have improved the molten carbonate and the operating conditions of the battery. It has been concluded that it is difficult to control the solubility of the nickel oxide cathode below the target value simply by changing, and it is necessary to take some other measures. Conventionally, various attempts have been made to develop alternative materials for the purpose of solving this problem, but those which have been selected as alternative materials are those that are chemically unstable in molten carbonate and that they have poor electronic conductivity. No alternative, such as sufficient, that could replace nickel oxide has yet been discovered. That is,
Lithium oxide is reduced to 0.5 by contact with molten carbonate.
Nickel oxide in the form of a solid solution of ˜3% is a cathode material having an extremely good electron conductivity, and thus is a material very excellent as a cathode material for a molten carbonate fuel cell, in addition to the above-mentioned dissolution problem. It is not easy to surpass this material.
【０００８】そこで、本発明者らは種々の思考をめぐら
せた結果、この酸化ニッケルの優れた特徴を残しつつ、
溶融炭酸塩への溶解を抑制することが最善の方策である
との結論に達した。引続き、この考え方に基づいて酸化
ニッケルの表面を溶融炭酸塩に難溶性の物質の薄膜で覆
う方法が有効であろうとの推測のもとに検討をした。こ
の際に、この被覆薄膜の厚みをできるだけ薄くしておく
ことが酸化リチウムが固溶している酸化ニッケルの良好
な電子伝導性を生かす上で重要であるとの認識のもとに
鋭意検討を重ねた。[0008] Therefore, as a result of various thoughts, the present inventors have retained the excellent characteristics of nickel oxide,
It was concluded that suppressing dissolution in molten carbonate is the best strategy. Subsequently, based on this idea, the investigation was conducted based on the assumption that a method of covering the surface of nickel oxide with a thin film of a substance that is hardly soluble in molten carbonate would be effective. At this time, a diligent study was conducted with the recognition that it is important to make the thickness of this coating thin film as thin as possible in order to take advantage of the good electronic conductivity of nickel oxide in which lithium oxide forms a solid solution. Overlaid.
【０００９】一方、当該検討の過程で被覆層の厚みが薄
くなると被覆薄膜の耐久性が十分でないことも判明し
た。そこで被覆薄膜の耐久性を向上させる対策を模索し
た結果、酸化ニッケルにあらかじめ被覆薄膜を構成する
物質を少量混合しておき、表面の被覆薄膜が破損した際
には酸化ニッケルに混合してある当該物質が新しい被覆
薄膜を形成する方法を考案した。しかし、酸化ニッケル
は溶融炭酸塩と接触すると極めて微細な結晶粒子に変化
する特徴を有しているために酸化ニッケル粒子表面の被
膜用に混合しておいた物質が酸化ニッケルの結晶とは別
個の結晶として遊離されてしまうという大きな技術上の
問題に遭遇した。On the other hand, in the course of the study, it was also found that the durability of the coating thin film was not sufficient when the thickness of the coating layer became thin. Therefore, as a result of searching for a measure for improving the durability of the coating thin film, a small amount of a substance forming the coating thin film is mixed in advance with nickel oxide, and when the surface coating thin film is damaged, it is mixed with nickel oxide. A method was devised in which the material formed a new coated film. However, since nickel oxide has the characteristic that it changes into extremely fine crystal particles when it comes into contact with molten carbonate, the substance mixed for the coating on the surface of the nickel oxide particles is different from the crystals of nickel oxide. I encountered a big technical problem of being released as crystals.
【００１０】本発明者らは当該問題の解決に腐心した結
果、酸化ニッケルに固溶状態で混合することができる物
質を採用する方法に到達した。さらに、種々の組成比率
で酸化ニッケルに容易に固溶する物質として酸化コバル
トが存在することを突止めて検討を進めた結果、幸いに
も酸化コバルトは溶融炭酸塩中では当該炭酸塩に溶解し
にくいリチウムコバルト二酸化物（ＬｉＣｏＯ2）に変
換されることが判明し、酸化ニッケル被覆薄膜を構成す
る物質としてはほぼ理想的なものであることを見い出し
た。本発明は以上の知見からなされたものであって、酸
化コバルトを酸化ニッケル中に固溶状態に分散させる過
程を経由させて酸化ニッケルをＬｉＣｏＯ2の薄膜で被
覆させることによってカソードの溶解現象を抑制するも
のである。As a result of striving to solve the problem, the present inventors have arrived at a method of adopting a substance that can be mixed with nickel oxide in a solid solution state. Furthermore, as a result of further investigations by finding out that cobalt oxide exists as a substance that easily dissolves in nickel oxide in various composition ratios, fortunately, cobalt oxide does not dissolve in the carbonate in molten carbonate. It was found to be converted into a difficult lithium cobalt dioxide (LiCoO 2 ), and it was found that it is an almost ideal material for forming a nickel oxide coating thin film. The present invention has been made based on the above findings, and suppresses the dissolution phenomenon of the cathode by coating nickel oxide with a thin film of LiCoO 2 through a process of dispersing cobalt oxide in a solid solution state in nickel oxide. To do.
【００１１】[0011]
【実施例】以下に、本発明を比較例および実施例によっ
て詳細に説明する。 （１）試験用カソードの作製 まず、以下のようにして試験用カソードを作製した。水
とメタノールの混合溶剤にメチルセルロースを添加溶解
させておき、以下の各実施例に述べる試験用粉末を加
え、ボールミル内でよく混合して、粘度がおよそ３０，
０００センチポイズの混練物とした。次いで、当該混練
物をドクターブレード法により板状に成型し、乾燥した
後、各実施例に述べる適当な雰囲気ガスが供給された電
気炉中に入れ、逐次温度を上昇させて多孔質焼結体の薄
板に焼結加工した。多孔質焼結薄板の厚みが１ｍｍとな
るようにドクターブレード法の成型装置を調整した。な
お、（ａ）試験用粉末が金属酸化物の場合には電気炉に
供給する雰囲気ガスとしては空気を使用し、（ｂ）試験
用粉末が金属粉末の場合にはアルゴンガスと水素の混合
ガスを使用した。前記（ｂ）の金属粉末を焼結して製作
した多孔質薄板はカソードとして試験に供する前に空気
が供給された電気炉中で加熱して酸化処理をして酸化物
多孔質焼結板に変化させた。The present invention will be described in detail below with reference to comparative examples and examples. (1) Preparation of Test Cathode First, a test cathode was prepared as follows. Methylcellulose was added and dissolved in a mixed solvent of water and methanol, and the test powder described in each of the following examples was added and mixed well in a ball mill to give a viscosity of about 30,
It was a kneaded product of 000 centipoise. Next, the kneaded material is molded into a plate shape by a doctor blade method, dried, and then placed in an electric furnace supplied with an appropriate atmospheric gas described in each example, and the temperature is successively increased to obtain a porous sintered body. Sintered into a thin plate. The doctor blade method molding apparatus was adjusted so that the thickness of the porous sintered thin plate was 1 mm. When (a) the test powder is a metal oxide, air is used as the atmosphere gas to be supplied to the electric furnace, and (b) when the test powder is a metal powder, a mixed gas of argon gas and hydrogen. It was used. The porous thin plate prepared by sintering the metal powder of (b) was heated in an electric furnace supplied with air to be oxidized before being subjected to a test as a cathode to form an oxide porous sintered plate. Changed.
【００１２】（２）試験用材料の試験方法 上記の方法で試験用粉末を焼結して製作した酸化物多孔
質焼結薄板を１.５ｃｍ径の円盤状に切断したものをカ
ソードとして試験に供した。電池を組立てるためのアノ
ードとしては金属ニッケルの粉末を焼結して得た多孔質
薄板をカソードと同様に１．５ｃｍ径の円盤状に切断し
たものを使用した。また、電解質板としてはアルミン酸
リチウム粉末の焼結体をマトリックスとして、これに通
常の方法で生成した炭酸リチウムと炭酸カリウムからな
る溶融炭酸塩を含浸してある厚みが０．８ｍｍの薄板を
３ｃｍ径の円盤状に切断して使用した。電解質板を両電
極で挟んで電池を組立てた後、アノードには水素ガスを
供給し、カソードには炭酸ガス３容量部と空気７容量部
の組成比からなる混合ガスを供給した。電池の発電試験
においては電流が２５０ミリアンペアになるように負荷
装置を調節して電圧を読み取った。およそ１０００時間
の連続運転を続けた後で電池を分解して電解質板を取出
して発光分光分析法で電解質板中のニッケル含量を定量
した。(2) Test method for test material The oxide porous porous sintered thin plate produced by sintering the test powder by the above method was cut into a disc shape with a diameter of 1.5 cm and used as a cathode for the test. I served. As the anode for assembling the battery, a porous thin plate obtained by sintering powder of metallic nickel was cut into a disk shape having a diameter of 1.5 cm like the cathode. Further, as the electrolyte plate, a sintered body of lithium aluminate powder was used as a matrix, and a molten carbonate of lithium carbonate and potassium carbonate produced by a usual method was impregnated into the matrix, and a thin plate having a thickness of 0.8 mm was 3 cm. It was used by cutting it into a disk with a diameter. After the battery was assembled by sandwiching the electrolyte plate between both electrodes, hydrogen gas was supplied to the anode, and a mixed gas having a composition ratio of 3 parts by volume of carbon dioxide gas and 7 parts by volume of air was supplied to the cathode. In the battery power generation test, the load device was adjusted so that the current was 250 mA, and the voltage was read. After continuous operation for about 1000 hours, the battery was disassembled, the electrolyte plate was taken out, and the nickel content in the electrolyte plate was quantified by emission spectroscopy.
【００１３】実施例１ 平均粒径が１マイクロメーターの市販の酸化ニッケル粉
末２重量部と平均粒径が２マイクロメーターの市販の酸
化コバルト粉末１重量部をめのう製の乳鉢内で混合した
後、混合粉末を空気を供給した電気炉中で９００℃で１
５時間加熱した。冷却後にこの粉末をＸ線回折法で分析
したところ、酸化ニッケルと酸化コバルトが完全に固溶
していることが確認できた。引続いて、この粉末を通常
の方法でシート状に成型、乾燥したのち空気雰囲気の電
気炉中で１３００℃にて加熱焼結処理した。得られた酸
化物多孔質焼結板を直径１．５ｃｍの円盤状に切断して
カソードを製作し、発電試験に供した。発電試験の結
果、２５０ミリアンペアの電流で０．７６ボルトの発電
性能が得られた。９９３時間連続運転を続けた後に電池
を分解して電解質板を取出して発光分光分析法で電解質
板に含まれるニッケルの含量を定量した結果、３．８ｍ
ｇのニッケルが含まれていた。Example 1 2 parts by weight of a commercially available nickel oxide powder having an average particle size of 1 micrometer and 1 part by weight of a commercially available cobalt oxide powder having an average particle size of 2 micrometers were mixed in an agate mortar, 1 at 900 ℃ mixed powder in an electric furnace supplied with air
Heated for 5 hours. When this powder was analyzed by X-ray diffractometry after cooling, it could be confirmed that nickel oxide and cobalt oxide were completely dissolved. Subsequently, this powder was molded into a sheet by a usual method, dried, and then heat-sintered at 1300 ° C. in an electric furnace in an air atmosphere. The obtained oxide porous sintered plate was cut into a disk having a diameter of 1.5 cm to prepare a cathode, and the cathode was subjected to a power generation test. As a result of the power generation test, a power generation performance of 0.76 V was obtained at a current of 250 mA. After continuously operating for 993 hours, the battery was disassembled, the electrolyte plate was taken out, and the content of nickel contained in the electrolyte plate was quantified by emission spectroscopy.
g nickel was included.
【００１４】実施例２ ニッケル２重量部、コバルト１重量部からなる組成比で
平均粒径が５マイクロメーターの合金粉末を入手した。
通常の方法でシート状に成型、乾燥した後、アルゴンガ
スと水素の混合ガス（Ａｒ：Ｈ2＝５：１（モル比））
が供給されている電気炉中に入れ１２００℃で３時間加
熱焼結した。このようにして得られた合金の焼結多孔質
板を引続いて空気を供給してある電気炉で１０００℃に
５時間、酸化処理して酸化物焼結多孔質板を得た。Ｘ線
回折法で分析した結果、酸化ニッケルと酸化コバルトの
固溶体であることが確認できた。この焼結多孔質板を
１．５ｃｍ径の円盤に切断したものをカソードに使用し
て発電試験を実施した。発電試験の結果、２５０ミリア
ンペアの電流で０．７４ボルトの発電性能が得られた。
１００９時間連続運転を続けた後に電池を分解して電解
質板を取出して発光分光分析法で電解質板に含まれるニ
ッケルの含量を定量した。その結果、電解質板には４．
２ｍｇのニッケルが含まれていることが判明した。Example 2 An alloy powder having a composition ratio of 2 parts by weight of nickel and 1 part by weight of cobalt and an average particle size of 5 micrometers was obtained.
After being formed into a sheet by a normal method and dried, a mixed gas of argon gas and hydrogen (Ar: H 2 = 5: 1 (molar ratio))
Was placed in an electric furnace which was supplied with and was heated and sintered at 1200 ° C. for 3 hours. The sintered porous plate of the alloy thus obtained was subsequently subjected to oxidation treatment at 1000 ° C. for 5 hours in an electric furnace supplied with air to obtain an oxide sintered porous plate. As a result of an X-ray diffraction analysis, it was confirmed to be a solid solution of nickel oxide and cobalt oxide. A power generation test was carried out by using this sintered porous plate cut into a disk having a diameter of 1.5 cm as a cathode. As a result of the power generation test, a power generation performance of 0.74 V was obtained at a current of 250 mA.
After continuous operation for 1009 hours, the battery was disassembled, the electrolyte plate was taken out, and the content of nickel contained in the electrolyte plate was quantified by an emission spectroscopic analysis method. As a result, 4.
It was found to contain 2 mg of nickel.
【００１５】実施例３ 酸化ニッケルと酸化コバルトの固溶体の組成をニッケ
ル：コバルト＝１：１（重量比）とした以外は実施例１
と同じ条件で酸化物焼結多孔質板を得て、実施例１と同
じ条件で発電試験を実施した。その結果、２５０ミリア
ンペアの電流で０．７３ボルトの性能が得られた。９６
４時間の発電試験終了後の分析では電解質板中のニッケ
ル含量は３．２ｍｇであった。Example 3 Example 1 except that the composition of the solid solution of nickel oxide and cobalt oxide was nickel: cobalt = 1: 1 (weight ratio).
An oxide sintered porous plate was obtained under the same conditions as above, and a power generation test was performed under the same conditions as in Example 1. As a result, a performance of 0.73 V was obtained at a current of 250 mA. 96
The analysis after the completion of the power generation test for 4 hours revealed that the nickel content in the electrolyte plate was 3.2 mg.
【００１６】比較例１ 平均粒径が７マイクロメーターの金属ニッケル粉末を通
常の方法でシート状に成型してこれを乾燥した後、アル
ゴンガスと水素の混合ガスを供給した電気炉中で１２０
０℃で３時間焼結処理を実施した。得られた金属ニッケ
ル多孔質焼結板を空気雰囲気の電気炉中で１０００℃で
５時間酸化処理した。得られた酸化物多孔質焼結板をＸ
線回折法で分析したところ、完全に酸化ニッケルに変換
していることが確認できた。この酸化ニッケル多孔質焼
結板を１．５ｃｍ径の円盤状に切断してカソード電極に
供した。アノードおよび電解質板は実施例１と同様なも
のを使用した。発電試験の結果、電流を２５０ミリアン
ペアとしたときに０．７８ボルトの性能が得られた。９
８８時間の連続運転の後に、電池を分解して電解質板を
取り出し、発光分光分析法でニッケルの定量分析を実施
した結果、電解質板中には１７．７ｍｇのニッケルが含
まれていることが判明した。Comparative Example 1 Metallic nickel powder having an average particle size of 7 micrometers was molded into a sheet by a usual method, dried, and then 120 in an electric furnace supplied with a mixed gas of argon gas and hydrogen.
Sintering was carried out at 0 ° C. for 3 hours. The obtained metallic nickel porous sintered plate was subjected to oxidation treatment at 1000 ° C. for 5 hours in an electric furnace in an air atmosphere. The obtained oxide porous sintered plate is X
An analysis by a line diffraction method confirmed that the nickel oxide was completely converted. This nickel oxide porous sintered plate was cut into a disk having a diameter of 1.5 cm and used as a cathode electrode. The same anode and electrolyte plate as in Example 1 were used. As a result of a power generation test, a performance of 0.78 V was obtained when the current was 250 mA. 9
After 88 hours of continuous operation, the battery was disassembled, the electrolyte plate was taken out, and a quantitative analysis of nickel was carried out by an emission spectroscopy analysis. As a result, it was found that the electrolyte plate contained 17.7 mg of nickel. did.
【００１７】[0017]
【発明の効果】上記のように、酸化ニッケル中に酸化コ
バルトを固溶状態に分散させたカソードを使用して、リ
チウム−カリウム系溶融炭酸塩と酸化コバルトとの反応
生成物であるリチウムコバルト二酸化物の薄膜でカソー
ド表面を被覆する本発明の方法により、溶融炭酸塩型燃
料電池用カソードの溶融炭酸塩への溶解を大いに抑制す
ることができ、同燃料電池の耐用年数を著しく伸ばすこ
とができた。As described above, using a cathode in which cobalt oxide is dispersed in a solid solution state in nickel oxide, lithium cobalt dioxide which is a reaction product of lithium-potassium molten carbonate and cobalt oxide is used. By the method of the present invention for coating the cathode surface with a thin film of a substance, the dissolution of the molten carbonate fuel cell cathode in the molten carbonate can be greatly suppressed, and the service life of the fuel cell can be remarkably extended. It was
───────────────────────────────────────────────────── フロントページの続き (72)発明者 副島 圭治 東京都調布市西つつじケ丘二丁目４番１号 東京電力株式会社技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Keiji Soejima 2-4-1, Nishi-Atsujigaoka, Chofu-shi, Tokyo Inside TEPCO Technical Research Institute
Claims (3)
態に分散させたカソードを使用して、リチウム−カリウ
ム系溶融炭酸塩と酸化コバルトとの反応生成物であるリ
チウムコバルト二酸化物の薄膜でカソード表面を被覆さ
せることを特徴とする溶融炭酸塩型燃料電池カソードの
溶解抑制方法。1. A cathode in which a thin film of lithium cobalt dioxide, which is a reaction product of lithium-potassium molten carbonate and cobalt oxide, is used by using a cathode in which cobalt oxide is dispersed in a solid solution state in nickel oxide. A method for suppressing dissolution of a molten carbonate fuel cell cathode, which comprises coating the surface.
態に分散させた溶融炭酸塩型燃料電池用カソード。2. A cathode for a molten carbonate fuel cell in which cobalt oxide is dispersed in a solid solution state in nickel oxide.
態に分散させたカソードを使用することを特徴とする溶
融炭酸塩型燃料電池。3. A molten carbonate fuel cell characterized by using a cathode in which cobalt oxide is dispersed in a solid solution state in nickel oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17835093A JP3228377B2 (en) | 1993-07-19 | 1993-07-19 | Molten carbonate fuel cell cathode and method for suppressing its dissolution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17835093A JP3228377B2 (en) | 1993-07-19 | 1993-07-19 | Molten carbonate fuel cell cathode and method for suppressing its dissolution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0737591A true JPH0737591A (en) | 1995-02-07 |
| JP3228377B2 JP3228377B2 (en) | 2001-11-12 |
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| Application Number | Title | Priority Date | Filing Date |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100303609B1 (en) * | 1998-04-24 | 2001-11-02 | 박호군 | Methods for Preparing LiCoO2-Coated NiO Cathodes for Molten Carbonate Fuel Cell |
| CN106711424A (en) * | 2017-01-12 | 2017-05-24 | 青岛大学 | Cobaltous oxide based nano complex electrode material and preparation method thereof |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6728851B1 (en) | 1995-07-31 | 2004-04-27 | Lexar Media, Inc. | Increasing the memory performance of flash memory devices by writing sectors simultaneously to multiple flash memory devices |
| US5845313A (en) | 1995-07-31 | 1998-12-01 | Lexar | Direct logical block addressing flash memory mass storage architecture |
| US6978342B1 (en) | 1995-07-31 | 2005-12-20 | Lexar Media, Inc. | Moving sectors within a block of information in a flash memory mass storage architecture |
| GB0123416D0 (en) | 2001-09-28 | 2001-11-21 | Memquest Ltd | Non-volatile memory control |
| GB0123415D0 (en) | 2001-09-28 | 2001-11-21 | Memquest Ltd | Method of writing data to non-volatile memory |
| GB0123421D0 (en) | 2001-09-28 | 2001-11-21 | Memquest Ltd | Power management system |
| GB0123410D0 (en) | 2001-09-28 | 2001-11-21 | Memquest Ltd | Memory system for data storage and retrieval |
| US7725628B1 (en) | 2004-04-20 | 2010-05-25 | Lexar Media, Inc. | Direct secondary device interface by a host |
| US7370166B1 (en) | 2004-04-30 | 2008-05-06 | Lexar Media, Inc. | Secure portable storage device |
| US7594063B1 (en) | 2004-08-27 | 2009-09-22 | Lexar Media, Inc. | Storage capacity status |
| US7464306B1 (en) | 2004-08-27 | 2008-12-09 | Lexar Media, Inc. | Status of overall health of nonvolatile memory |
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1993
- 1993-07-19 JP JP17835093A patent/JP3228377B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100303609B1 (en) * | 1998-04-24 | 2001-11-02 | 박호군 | Methods for Preparing LiCoO2-Coated NiO Cathodes for Molten Carbonate Fuel Cell |
| CN106711424A (en) * | 2017-01-12 | 2017-05-24 | 青岛大学 | Cobaltous oxide based nano complex electrode material and preparation method thereof |
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|---|---|
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