JPS6366855A - Electrode for molten salt fuel cell - Google Patents
Electrode for molten salt fuel cellInfo
- Publication number
- JPS6366855A JPS6366855A JP61210078A JP21007886A JPS6366855A JP S6366855 A JPS6366855 A JP S6366855A JP 61210078 A JP61210078 A JP 61210078A JP 21007886 A JP21007886 A JP 21007886A JP S6366855 A JPS6366855 A JP S6366855A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- molten salt
- fuel cell
- plate
- salt fuel
- 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.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
- H01M4/8621—Porous electrodes containing only metallic or ceramic material, e.g. made by sintering or sputtering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/14—Fuel cells with fused electrolytes
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Inert Electrodes (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、５００〜７００℃程度またはその近辺の温度
で作動する溶融塩燃料電池用の電極、詳しくはニッケル
（Ｎｉ）系多孔質板からなるガス拡散電極にタングステ
ン（Ｗ）を添加して、電極反応の促進効果を発揮させる
ようにした溶融塩燃料電池用の電極に関するものである
。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an electrode for a molten salt fuel cell that operates at a temperature of about 500 to 700°C or around 500°C, specifically an electrode made of a nickel (Ni) based porous plate. The present invention relates to an electrode for a molten salt fuel cell in which tungsten (W) is added to a gas diffusion electrode to exhibit an effect of promoting electrode reactions.
従来、溶融塩燃料電池としては、溶融アルカリ炭酸塩を
用いる系が最も一般的である。すなわち、炭酸リチウム
、炭酸ナトリウム、炭酸カリウムなどのアルカリ金属炭
酸塩またはこれらの混合物を電解質とし、これをリチウ
ムアルミネートなどの耐溶融塩性の粉末とともに板状に
加工し、これを燃料極（アノード）と空気極（カソード
）との間に保持して電池を構成している。Conventionally, the most common molten salt fuel cell is a system using molten alkali carbonate. That is, an alkali metal carbonate such as lithium carbonate, sodium carbonate, potassium carbonate, or a mixture thereof is used as an electrolyte, and this is processed into a plate shape together with a molten salt-resistant powder such as lithium aluminate, which is then used as a fuel electrode (anode). ) and the air electrode (cathode) to form a battery.
上記のアルカリ金属炭酸塩を電解性とする溶融塩燃料電
池の場合、その電気化学的反応は次式（１）、（２）の
ごとく進行し、イオン伝ｍは炭酸イオン（Ｃｆ）３”−
）によって行われる。In the case of a molten salt fuel cell using the above-mentioned alkali metal carbonate as an electrolyte, the electrochemical reaction proceeds as shown in the following equations (1) and (2), and the ion conduction m is carbonate ion (Cf)3''-
).
アノード：Ｈ２＋ＣＯ１ト−４Ｈ２Ｏ＋ＣＱ２ ＋２ｅ
（１１カソード’ ： ’ＡＯｔ ＋ Ｃｏｇ ＋
２ｅ−Ｃ（ｈ”−（２１７ノードにおいては、水素が
電極細孔内を拡散して電解質および電極と三相界面を形
成し、上記式（１）の反応が進行して水（スチーム）、
炭酸ガスおよび電子となる。Anode: H2+CO1-4H2O+CQ2 +2e
(11 cathode': 'AOt + Cog +
2e-C(h”-(217) At the node, hydrogen diffuses within the electrode pores to form a three-phase interface with the electrolyte and the electrode, and the reaction of formula (1) above proceeds to produce water (steam),
becomes carbon dioxide gas and electrons.
一方、カソードにおいては、酸素および炭酸ガスが電極
細孔内を拡散して、上記と同様に電解質および電極と三
相界面を形成し、上記式（２）の反応が進行して炭酸イ
オンとなる。炭酸イオンはカソードからアノードにイオ
ン伝道し、電子は外部回路を通ってアノードからカソー
ドに到達する。On the other hand, at the cathode, oxygen and carbon dioxide gas diffuse within the electrode pores and form a three-phase interface with the electrolyte and electrode in the same way as above, and the reaction of formula (2) above proceeds to form carbonate ions. . Carbonate ions travel from the cathode to the anode, and electrons travel from the anode to the cathode through an external circuit.
アノードとしては、還元性雰囲気中で溶融炭酸塩に耐え
る必要があるところから、多くの導電性材料のうち、ニ
ッケルが最も多く取り上げられ、これに作動時での過焼
結（シンタリング）を抑制する目的でクロム、コバルト
、アルミナなどの添加剤が加えられている。すなわち、
従来はＮｉ Ｃｒ５Ｎｉ−Ｃ０％ Ｎｉ−Ａｌ２Ｏ３
などのＮｉ系多孔質板が用いられている。Among many conductive materials, nickel is the most commonly used material for the anode because it must withstand molten carbonate in a reducing atmosphere, and it also suppresses over-sintering during operation. Additives such as chromium, cobalt, and alumina are added for this purpose. That is,
Conventionally, Ni Cr5Ni-C0% Ni-Al2O3
Ni-based porous plates such as Ni-based porous plates are used.
一方、カソードとしては、酸化性雰囲気中で耐溶融塩性
を必要とするところから、リチウムをドープした酸化ニ
ッケルが最も普通に考えられ試験されてきた。On the other hand, as a cathode, nickel oxide doped with lithium has been most commonly considered and tested because it requires resistance to molten salts in an oxidizing atmosphere.
すなわち、従来、最も一般的な電池構成としては、Ｏニ
ッケル／溶融炭酸アルカリ塩＋リチウムアルミネート／
リチウムドープニッケル酸化物■である。In other words, conventionally, the most common battery configuration is O nickel/molten alkali carbonate + lithium aluminate/
It is a lithium-doped nickel oxide ■.
高い電池出力を得るためには、良好な三相界面を形成し
、かつ安定に維持させることが必要であり、そのために
は電解質保持能力が高く、かつ内部抵抗の低い高強度、
薄板状電解質体と、電気化学反応の触媒作用が優れた広
い電極表面積と良好な電極特性を有し、かつ長期にわた
って安定に電極細孔構造を維持できるアノードおよびカ
ソード電極が不可欠となる。In order to obtain high battery output, it is necessary to form a good three-phase interface and maintain it stably.
It is essential to have a thin plate electrolyte body, an anode and a cathode electrode that have a large electrode surface area with excellent catalytic action for electrochemical reactions, good electrode properties, and can maintain a stable electrode pore structure over a long period of time.
しかしながら、従来の電池構成では、電気化学反応促進
の面で十分満足な結果を得ることができないという問題
点があった。However, the conventional battery configuration has a problem in that it is not possible to obtain sufficiently satisfactory results in terms of promoting electrochemical reactions.
本発明は上記の諸点に鑑みなされたもので、従来の電極
の基板であるＮｉ系多孔質板に、タングステンを添加す
ることにより、従来の電極に比べ、反応速度が速くなり
電極性能が向上した溶融塩燃料電池用の電極の提供を目
的とするものである。The present invention was made in view of the above points, and by adding tungsten to the Ni-based porous plate that is the substrate of the conventional electrode, the reaction speed is faster and the electrode performance is improved compared to the conventional electrode. The object of the present invention is to provide an electrode for a molten salt fuel cell.
〔問題点を解決するための手段および作用〕本発明の溶
融塩燃料電池用の電極は、ニッケル系多孔質板にタング
ステンを添加したことを特敬としている。[Means and effects for solving the problems] The electrode for a molten salt fuel cell of the present invention is characterized by adding tungsten to a nickel-based porous plate.
本発明の電極は、Ｎｉｓ Ｎｉ Ｃｒ、 Ｎｉ Ｃ
ｏ、 Ｎ１−Ａｈ（ｈなどのＮｉ系多孔質板に、ＫｔＷ
Ｏａ 、 Ｌｊ２１ＩＩＯｎ、Ｎａ！１ｌ１０４などを
添加したＫＣＩ −ＬｉＣ１電析浴からタングステンを
電析させて製造される。なおＫＣＩ −ＬｉＣｌ電析浴
電析りにＫＦ −ＬｉＦ電析電析使用することも可能で
ある。The electrode of the present invention includes Nis Ni Cr, Ni C
o, N1-Ah (h, etc.), KtW
Oa, Lj21IIOn, Na! It is produced by electrodepositing tungsten from a KCI-LiC1 electrodeposition bath to which 1l104 and the like are added. Note that it is also possible to use KF-LiF electrodeposition for the KCI-LiCl electrodeposition bath electrodeposition.
また他の製造方法として、Ｗを含む合金粉末を焼結する
方法、Ｎｉ系多孔質板にＣＶＤ（ｃｈｅｍｉｃａｌ ｖ
ａｐｏｒｄｅｐｏｓｉｔｉｏｎ） 、ＰＶＤ（ｐｈｙｓ
ｉｃａｌ ｖａｐｏｒ ｄｅｐｏｓｉｔｉｏｎ）などに
よりＷを蒸着させる方法、Ｗをプラズマ状態で溶射して
蒸着させる方法などを用いることができる。Other manufacturing methods include a method of sintering alloy powder containing W, and a method of applying CVD (chemical vapor deposition) to a Ni-based porous plate.
apordeposition), PVD (phys
A method of vapor depositing W by ical vapor deposition, etc., a method of vapor depositing W by thermal spraying in a plasma state, etc. can be used.
しかしながら、上記の種々の製造方法のうち、電析が反
応の制御、析出量の制御を容易に行えるので、最も適し
ている。However, among the above-mentioned various manufacturing methods, electrodeposition is the most suitable because the reaction and the amount of deposition can be easily controlled.
Ｗの含有量は、Ｎｉに対して０．１〜１５ｗｔ％、好ま
しくは１〜１０ｗｔ％である。Ｗ７！ｌ（１５ｗｔ％を
超える場合は、多孔質板に目詰りが生じるので好ましく
ない、一方、Ｗが０．１ｗｔ％未満の場合は、電極反応
の促進効果が発揮されない。The content of W is 0.1 to 15 wt%, preferably 1 to 10 wt% based on Ni. W7! If W exceeds 15 wt%, the porous plate will become clogged, which is undesirable. On the other hand, if W is less than 0.1 wt%, the effect of promoting the electrode reaction will not be exhibited.
以下、本発明の好適な実施例を説明する。ただし、これ
らの実施例は、本発明の範囲をそれらのみに限定する趣
旨のものではなく、鼠なる一例にすぎない。Hereinafter, preferred embodiments of the present invention will be described. However, these Examples are not intended to limit the scope of the present invention to them, and are merely examples.
実施例１
下記のＮｉ多孔質板３種類にＷを電析させたものにつき
、分極特性測定を行った。Example 1 Polarization characteristics were measured on the following three types of Ni porous plates on which W was electrodeposited.
＋１１ Ｎｉ粉末焼結板（気孔径８μ、気孔率６０％
）＋２） Ｎｉ繊維焼結板（気孔径１３μ、気孔率７
０％）（３）（気孔径１３μ、気孔率８０％）電析条件
はつぎの通りであった。+11 Ni powder sintered plate (pore diameter 8μ, porosity 60%
)+2) Ni fiber sintered board (pore diameter 13μ, porosity 7)
0%) (3) (pore diameter 13μ, porosity 80%) The electrodeposition conditions were as follows.
電析量： ＬｉＣ１（５８，５ａ＋ｏ１％） −ＸＣＨ
４１，５ｍｏ１％）添加剤： ＫｚＷＯｎ ０．１
ｍｏ１％温度ニア００℃
電析方法：＋０．１〜＋〇、 ３ Ｖ （Ｌ、ｉ／Ｌｉ
”に対して）で定電位電解
理論電析量＝０．８〜１０−ｔ％
上記のようにして得られた電極板のうち（３）のＮｉ繊
維焼結板にＮｉに対して４ｗｔ％のＷを添加した電極板
をアノードに用い、１鶴φの金線をカソードに用い、リ
チウムおよびカリウムの炭酸塩の混合物（モル比６２
： ３８、重量比４６．７ ： ５３．３）を電解質に
用い、参照電極として酸素電極を用い、６５０℃でアノ
ードの分極特性を測定した。燃料は水素を８０ ｖｏ１
％、ＣＯ！を２０ ｖｏ１％含存するガスを用い、酸化
剤は酸素を３３．３ ｖｏ１％、Ｃｏ、を６６．７ ｖ
ｏ１％含有するガスを用いた。結果は第１図に示す如く
であった。なお比較例として、（］）のＮｉ粉末焼結板
の値をプロットしている。Amount of electrodeposition: LiC1 (58,5a+o1%) -XCH
41.5mo1%) Additive: KzWOn 0.1
Mo1% temperature near 00℃ Electrodeposition method: +0.1~+〇, 3 V (L, i/Li
Theoretical amount of electrolyte deposited using constant potential = 0.8 to 10-t% (with respect to ``10-t%'') Among the electrode plates obtained as described above, the Ni fiber sintered plate (3) has 4 wt% of Ni to Ni. An electrode plate added with W of
: 38, weight ratio 46.7 : 53.3) as an electrolyte, and an oxygen electrode as a reference electrode, the polarization characteristics of the anode were measured at 650°C. Fuel is hydrogen at 80 vol.
%, CO! A gas containing 20 vol.
A gas containing 1% o was used. The results were as shown in FIG. As a comparative example, the values of the Ni powder sintered plate ( ) are plotted.
実施例２
（１１のＮｉ粉末焼結板にＮｉに対してＷを０．８ｗｔ
％、４ｗｔ％添加した電極板について、実施例１と同様
の実験を行った。結果は第２図に示す如くであった。参
考のため実施例１におけるＮｉ繊維焼結板にＷを４ｗｔ
％添加した場合の結果も示した。Example 2 (0.8wt of W relative to Ni on the Ni powder sintered plate of 11)
The same experiment as in Example 1 was conducted on the electrode plate to which 4 wt % of the oxide was added. The results were as shown in FIG. For reference, 4wt of W was applied to the Ni fiber sintered plate in Example 1.
% addition is also shown.
実施例３
実施例１．２で用いた電極板をアノードに用い、（３）
のＮｉ繊維焼結板（３６Ｈφ×厚さ０．８龍）をカソー
ドに用い、リチウムアルミネートを不活性支持物質（マ
トリックス材）として、リチウムおよびカリウムの炭酸
塩の混合物（モル比６２ ： ３８、重量比４６．７
： ５３．３＞を６’Ｏｗｔ％含有してなる５０鶴φ×
厚さ２ｆｉの電解質板を上記アノードおよびカソード間
に配設し、燃料室および酸化剤室をそれぞれ備える集電
端を兼ねたハウジングで、上記電極板および電解質板を
両側から押さえる構造の単セルを構成し、６５０℃にお
ける初期電池性能および１００時間後の電池性能を測定
した。また比較例として、（１１のＮｉ粉末焼結板（３
６ｆｌφ×厚さ０．８鶴）をアノードに用いた単セルの
６５０℃における初期電池性能、および１００時間後の
電池性能を測定した。その結果を第１表に示す、なお燃
料は水素を８０ｖｏ１％、ＣＯ□を２０ｖｏ１％含有す
るガスを用い、酸化剤は空気を７０ｖｏ１％、ＣＯ，を
３Ｑｖｏ１％含有するガスを用いた。Example 3 Using the electrode plate used in Example 1.2 as an anode, (3)
A Ni fiber sintered plate (36Hφ x 0.8×thickness) was used as the cathode, lithium aluminate was used as the inert support material (matrix material), and a mixture of lithium and potassium carbonates (molar ratio 62:38, Weight ratio 46.7
: 50 cranes φ containing 6'Owt% of 53.3>
A single cell having a structure in which an electrolyte plate with a thickness of 2fi is arranged between the anode and the cathode, and a housing that also serves as a current collecting end and has a fuel chamber and an oxidizer chamber, holds the electrode plate and the electrolyte plate from both sides. The initial battery performance at 650°C and the battery performance after 100 hours were measured. In addition, as a comparative example, (11 Ni powder sintered plates (3
The initial battery performance at 650° C. and the battery performance after 100 hours of a single cell using a single cell (6flφ×0.8 cranes in thickness) as an anode were measured. The results are shown in Table 1. The fuel used was a gas containing 80 vol% hydrogen and 20 vol% CO□, and the oxidizing agent used was a gas containing 70 vol% air and 3Q vol% CO.
第 １ 表
〔発明の効果〕
以上説明したように、本発明の溶融塩燃料電池用の電極
は、高温（５００〜７００℃前後）において優れた電極
触媒作用を有し、かつ長期にわたって高性能を維持でき
るので、高い電池出力を長期間維持することができると
いう効果を有している。Table 1 [Effects of the Invention] As explained above, the electrode for molten salt fuel cells of the present invention has excellent electrocatalytic action at high temperatures (around 500 to 700°C) and maintains high performance over a long period of time. This has the effect that high battery output can be maintained for a long period of time.
【図面の簡単な説明】
第１図は実施例１における本発明の溶融塩燃料電池用の
電極の電流密度と電位との関係を示すグラフ、第２図は
実施例２における本発明の電極の電流密度と電位との関
係を示すグラフである。
第１図
酸３々バヒ＆（工Ａ／。す[Brief Description of the Drawings] Figure 1 is a graph showing the relationship between current density and potential of the electrode for a molten salt fuel cell of the present invention in Example 1, and Figure 2 is a graph showing the relationship between the current density and potential of the electrode for a molten salt fuel cell of the present invention in Example 2. It is a graph showing the relationship between current density and potential. Figure 1 Acid 3-bahi & (Engineering A/.su)
Claims (1)
を特徴とする溶融塩燃料電池用の電極。1. An electrode for a molten salt fuel cell characterized by adding tungsten to a nickel-based porous plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61210078A JPS6366855A (en) | 1986-09-05 | 1986-09-05 | Electrode for molten salt fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61210078A JPS6366855A (en) | 1986-09-05 | 1986-09-05 | Electrode for molten salt fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6366855A true JPS6366855A (en) | 1988-03-25 |
| JPH0440832B2 JPH0440832B2 (en) | 1992-07-06 |
Family
ID=16583451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61210078A Granted JPS6366855A (en) | 1986-09-05 | 1986-09-05 | Electrode for molten salt fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6366855A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0513087A (en) * | 1991-06-20 | 1993-01-22 | Hitachi Ltd | Fuel cell electrode manufacturing method and fuel cell |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62154576A (en) * | 1985-12-27 | 1987-07-09 | Fuji Electric Corp Res & Dev Ltd | Manufacture of molten carbonate fuel cell |
-
1986
- 1986-09-05 JP JP61210078A patent/JPS6366855A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62154576A (en) * | 1985-12-27 | 1987-07-09 | Fuji Electric Corp Res & Dev Ltd | Manufacture of molten carbonate fuel cell |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0513087A (en) * | 1991-06-20 | 1993-01-22 | Hitachi Ltd | Fuel cell electrode manufacturing method and fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0440832B2 (en) | 1992-07-06 |
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