JPH0732019B2 - Negative electrode for high temperature fuel cell - Google Patents
Negative electrode for high temperature fuel cellInfo
- Publication number
- JPH0732019B2 JPH0732019B2 JP62328545A JP32854587A JPH0732019B2 JP H0732019 B2 JPH0732019 B2 JP H0732019B2 JP 62328545 A JP62328545 A JP 62328545A JP 32854587 A JP32854587 A JP 32854587A JP H0732019 B2 JPH0732019 B2 JP H0732019B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- fuel cell
- hydrogen
- high temperature
- temperature 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.)
- Expired - Lifetime
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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/14—Fuel cells with fused electrolytes
- H01M8/141—Fuel cells with fused electrolytes the anode and the cathode being gas-permeable electrodes or electrode layers
- H01M8/142—Fuel cells with fused electrolytes the anode and the cathode being gas-permeable electrodes or electrode layers with matrix-supported or semi-solid matrix-reinforced electrolyte
-
- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
-
- 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
- H01M2008/147—Fuel cells with molten carbonates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0048—Molten electrolytes used at high temperature
- H01M2300/0051—Carbonates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Inert Electrodes (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は水素を含むガスを燃料とし、比較的高温で作動
する燃料電池、特に溶融炭酸塩型燃料電池用負極に関す
る。Description: TECHNICAL FIELD The present invention relates to a fuel cell that uses a gas containing hydrogen as a fuel and that operates at a relatively high temperature, and more particularly to a negative electrode for a molten carbonate fuel cell.
従来の技術 水素を含むガスを燃料とし、比較的高温で作動する燃料
電池、特に溶融炭酸塩型燃料電池の負極は、従来、コス
ト、水素の酸化触媒能、電子伝導度、溶融炭酸塩中での
安定性などを考慮して、ニッケルまたはニッケル／クロ
ム合金粉末に、場合によってはセラミクス粉末を混入
し、焼結またはテープキャスティング法により成型する
ことで作られてきた。2. Description of the Related Art A negative electrode of a fuel cell that operates at a relatively high temperature using a gas containing hydrogen as a fuel, particularly a molten carbonate fuel cell, has been conventionally used in cost, hydrogen oxidation catalytic ability, electronic conductivity, and molten carbonate. In consideration of the stability and the like, nickel or nickel / chromium alloy powder is mixed with ceramic powder in some cases, and is formed by sintering or tape casting.
さらに高性能の燃料電池用負極を得るために、負極材料
に金属水素化物を用いる可能性についても、特開昭63−
218163号で考えられている。Regarding the possibility of using a metal hydride as a negative electrode material in order to obtain a higher performance negative electrode for fuel cells, JP-A-63-
Considered in issue 218163.
発明が解決しようとする問題点 溶融炭酸塩型燃料電池の負荷をとった場合の正極と負極
の分極を比較すると、一般に負極の分極の方が大きい。
これは、負極では反応の生成物である炭酸ガスや水が発
生し、燃料の拡散を阻害するためと考えられる。Problems to be Solved by the Invention Comparing the polarizations of the positive electrode and the negative electrode when the molten carbonate fuel cell is loaded, the polarization of the negative electrode is generally larger.
It is considered that this is because carbon dioxide gas and water, which are reaction products, are generated in the negative electrode, and the diffusion of fuel is hindered.
問題点を解決するための手段 しかし、実際に高温燃料電池の負極材料に金属水素化物
を用いた場合、金属水素化物の活性が高いため、高温で
の水素以外の物質、例えば水蒸気や炭酸ガスや溶融炭酸
塩等に対する安定性の問題が考えられる。また常温付近
に水素平衡圧力を有する金属水素化物を用いた場合、高
温では金属水素化物の特性を十分利用できず、負極の活
性を高めることが期待できない等の課題が考えられる。
そこで高温に水素平衡圧力を有する少なくともZrを成分
として含む水素吸蔵合金もしくは水素を吸蔵した金属水
素化物の表面に、高温での水素以外の物質に対する安定
性を向上させるためNi,Cu,Al,Cr,Co,Pd,Ptの内、少なく
ともいずれか１種を含む金属で被覆したものを高温燃料
電池の負極構成材料の少なくとも一部に用いることによ
り、負極の活性を高め電池の高性能化を図った。However, when a metal hydride is actually used as a negative electrode material of a high-temperature fuel cell, the activity of the metal hydride is high, and therefore substances other than hydrogen at high temperature, such as steam and carbon dioxide gas, There may be a problem of stability against molten carbonate and the like. In addition, when a metal hydride having a hydrogen equilibrium pressure near room temperature is used, the characteristics of the metal hydride cannot be fully utilized at high temperatures, and it is expected that the activity of the negative electrode cannot be expected to increase.
Therefore, on the surface of a hydrogen storage alloy containing at least Zr as a component having a hydrogen equilibrium pressure at high temperature or a metal hydride that has stored hydrogen, Ni, Cu, Al, Cr in order to improve the stability against substances other than hydrogen at high temperature. , Co, Pd, Pt coated with a metal containing at least one of them is used as at least a part of the negative electrode constituent material of the high temperature fuel cell to enhance the activity of the negative electrode and improve the performance of the battery. It was
作用 高温に水素平衡圧力を有する少なくともZrを成分とする
水素吸蔵合金もしくは水素を吸蔵した金属水素化物の表
面をNi,Cu,Al,Cr,Co,Pd,Ptの内、少なくともいずれか１
種を含む金属で被覆した負極は、高温燃料電池の作動条
件で水素の吸蔵放出ができ、また高温での水素以外の物
質に対する安定性が高いため、高温燃料電池の負極の性
能向上に寄与する。その上これにNiをふくませると、こ
れらの効果が一層向上する。Action At least one of Ni, Cu, Al, Cr, Co, Pd, and Pt should have a surface of a hydrogen storage alloy containing at least Zr as a component having a hydrogen equilibrium pressure at high temperature or a metal hydride that stores hydrogen.
The negative electrode coated with a metal containing seeds can absorb and release hydrogen under the operating conditions of a high temperature fuel cell, and has high stability to substances other than hydrogen at high temperatures, thus contributing to the performance improvement of the negative electrode of the high temperature fuel cell. . Moreover, if Ni is added to this, these effects are further improved.
実施例 まず、金属水素化物としてZr/Cu系合金を用いた。これ
は約600〜700℃に水素平衡圧力を有する。そこで、この
Zr/Cu系合金を溶融炭酸塩型燃料電池用負極として用い
た。この合金をそのまま負極材料として用いてもよい
が、本実施例では、まず400メッシュ以下の粉末に粉砕
し、つぎに粉末表面に耐食性向上のためニッケルの無電
解メッキをほどこし、さらにカーボニルニッケル粉末と
混合して成型助剤や溶媒を用いて電極状に成型し、この
電極状成型体をそのまま電池に組み込んで、作動温度に
昇温するとともに、成型助剤等を焼散させて負極として
用いた。この際、正極には多孔質リチウムドープ酸化ニ
ッケルを用い、電解質には炭酸リチウム：炭酸カリウム
の比が62:38mol％のものを電解質保持体であるアルミン
酸リチウムとともにテープキャスティング法にて作製し
使用した。また燃料ガスには水素：炭酸ガス：水蒸気の
比が76:19:5の割合のものを、酸化剤として空気：炭酸
ガスの比が70:30の割合のものを適用し、650℃の温度で
試験を行なった。Example First, a Zr / Cu alloy was used as a metal hydride. It has a hydrogen equilibrium pressure at about 600-700 ° C. So this
A Zr / Cu alloy was used as a negative electrode for a molten carbonate fuel cell. Although this alloy may be used as a negative electrode material as it is, in the present example, it is first pulverized into a powder of 400 mesh or less, and then electroless plating of nickel is applied to the surface of the powder to improve the corrosion resistance. The mixture was mixed and molded into an electrode shape using a molding aid or a solvent, and this electrode-shaped molded body was incorporated into a battery as it was, heated to an operating temperature, and the molding aid and the like were burned off and used as a negative electrode. . At this time, porous lithium-doped nickel oxide was used for the positive electrode, and an electrolyte having a lithium carbonate: potassium carbonate ratio of 62:38 mol% was prepared by tape casting together with lithium aluminate, which is the electrolyte holder, and used. did. As the fuel gas, the hydrogen: carbon dioxide: water vapor ratio of 76: 19: 5 is used, and as the oxidant, the air: carbon dioxide gas ratio of 70:30 is applied. The test was conducted at.
つぎに、同様に金属水素化物としてZr/Ni系合金にTiとA
lを添加した合金を用いた。Zr/Ni系合金もZr/Cu系合金
とほぼ同じ温度に水素平衡圧力を有する。そこでまず水
素の吸蔵放出を３回行なわせた後、400メッシュ以下の
粉末に粉砕し、次に粉末表面に耐食性向上のためNi/Cu
合金の無電解メッキをほどこし、さらにその表面にアル
ミナの微粉末を被覆して、溶融炭酸塩型燃料電池用負極
材料とした。本実施例ではこれとカーボニルニッケル粉
末とを混合して成型助剤や溶媒を用いて電極状に成型
し、この電極状成型体をそのまま電池に組み込んで、作
動温度に昇温するとともに、成型助剤等を焼散させて負
極として用いた。その他の電池構成条件は、全てZr/Cu
系の場合と同じとした。Next, in the same manner, Ti and A were added to Zr / Ni alloys as metal hydrides.
An alloy added with 1 was used. The Zr / Ni alloy also has a hydrogen equilibrium pressure at about the same temperature as the Zr / Cu alloy. Therefore, hydrogen is first occluded and released three times, then pulverized into powder of 400 mesh or less, and then Ni / Cu for improving corrosion resistance on the powder surface.
The alloy was subjected to electroless plating, and its surface was coated with fine alumina powder to obtain a negative electrode material for a molten carbonate fuel cell. In this example, this and carbonyl nickel powder were mixed and molded into an electrode using a molding aid or a solvent, and this electrode-shaped molded body was directly incorporated into a battery to raise the operating temperature and The agent was burned off and used as a negative electrode. All other battery configuration conditions are Zr / Cu
Same as the case of the system.
これらの電池の負極の特性を調べるため、電解質体部分
に参照電極を設け、負極の性能を分離して、通常のニッ
ケル多孔体を用いた同条件の溶融炭酸塩型燃料電池の負
極の特性と比較し、図に示した。明らかに金属水素化物
を負極に用いた場合に性能の向上が見られた。In order to investigate the characteristics of the negative electrode of these cells, a reference electrode is provided in the electrolyte part, the performance of the negative electrode is separated, and the characteristics of the negative electrode of a molten carbonate fuel cell under the same conditions using a normal nickel porous body are The results are compared and shown in the figure. Apparently, the performance was improved when the metal hydride was used for the negative electrode.
本実施例では、特に溶融炭酸塩型燃料電池の負極に少な
くともZrを成分とする水素吸蔵合金もしくは水素を吸蔵
した金属水素化物の表面をNi,Cu,Al,Cr,Co,Pd,Ptの内、
少なくともいずれか１種を含む金属で被覆したものを用
いた例について示したが、その他の高温燃料電池、例え
ば高温固体電解質燃料電池の負極として用いても、もち
ろん良い。また、本実施例に示したように、少なくとも
Zrを成分とする水素吸蔵合金もしくは水素を吸蔵した金
属水素化物の表面Ni,Cu,Al,Cr,Co,Pd,Ptの内、少なくと
もいずれか１種を含む金属で被覆した負極の表面をアル
ミナなどのセラミクスで被服して用いてももちろん良
い。In this example, the surface of a hydrogen storage alloy containing at least Zr or a metal hydride storing hydrogen is used as the Ni, Cu, Al, Cr, Co, Pd, and Pt in the negative electrode of the molten carbonate fuel cell. ,
Although the example of using the one coated with a metal containing at least one kind is shown, it may be used as a negative electrode of other high temperature fuel cells, for example, high temperature solid electrolyte fuel cells. Further, as shown in this embodiment, at least
The surface of a negative electrode coated with a metal containing at least one of Ni, Cu, Al, Cr, Co, Pd, and Pt of the surface of a hydrogen storage alloy containing Zr or a metal hydride that has stored hydrogen is alumina. Of course, it is also possible to use it with clothes such as ceramics.
発明の効果 以上のことから本発明は、高温燃料電池の負極材料に少
なくともZrを成分とする水素吸蔵合金もしくは水素を吸
蔵した金属水素化物の表面をNi,Cu,Al,Cr,Co,Pd,Ptの
内、少なくともいずれか１種を含む金属で被覆したもの
を用いることにより、さらにはNiを成分として含むこと
により電池の性能を向上させるものであることが判明し
た。Effects of the Invention From the above, the present invention, the negative electrode material of the high-temperature fuel cell, the surface of at least a hydrogen storage alloy containing Zr as a component or a hydrogen storage metal hydride Ni, Cu, Al, Cr, Co, Pd, It was found that the performance of the battery is improved by using a Pt coated with a metal containing at least one of Pt and further by including Ni as a component.
図は負極材料に金属水素化物を含んだ場合と含まない場
合の負極特性を比較したものである。 １……Zr/Cu系合金を含んだ負極、２……Zr/Ni系合金を
含んだ負極、３……Ni負極。The figure compares the characteristics of the negative electrode with and without the metal hydride contained in the negative electrode material. 1 ... Negative electrode containing Zr / Cu alloy, 2 ... Negative electrode containing Zr / Ni alloy, 3 ... Ni negative electrode.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 蒲生 孝治 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 森脇 良夫 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 岩城 勉 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koji Gamo 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Yoshio Moriwaki, 1006 Kadoma, Kadoma City Osaka Prefecture Matsushita Electric Industrial Co., Ltd. 72) Inventor Tsutomu Iwaki 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (3)
を吸蔵した金属水素化物の表面をNi,Cu,Al,Cr,Co,Pd,Pt
の内、少なくともいずれか１種を含む金属で被覆したこ
とを特徴とする高温燃料電池用負極。1. A surface of a hydrogen storage alloy containing Zr as a component or a metal hydride storing hydrogen is coated with Ni, Cu, Al, Cr, Co, Pd, Pt.
Among these, a negative electrode for a high temperature fuel cell, which is coated with a metal containing at least one of the above.
水素化物は、さらにNiを成分として含むことを特徴とす
る特許請求の範囲第１項記載の高温燃料電池用負極。2. The negative electrode for a high temperature fuel cell according to claim 1, wherein the hydrogen storage alloy or the metal hydride that has stored hydrogen further contains Ni as a component.
水素化物は、さらにTi,V,Cr,Mn,Fe,Co,Cu,Nb,Mo,W,Al,M
g,Ca,Srより選ばれた少なくとも１種以上の元素を含む
ことを特徴とする特許請求の範囲第１項または第２項記
載の高温燃料電池用負極。3. A hydrogen-absorbing alloy or a metal hydride that has absorbed hydrogen further comprises Ti, V, Cr, Mn, Fe, Co, Cu, Nb, Mo, W, Al, M.
The negative electrode for a high temperature fuel cell according to claim 1 or 2, which contains at least one element selected from g, Ca, and Sr.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62328545A JPH0732019B2 (en) | 1987-12-24 | 1987-12-24 | Negative electrode for high temperature fuel cell |
| US07/290,189 US4997729A (en) | 1987-12-24 | 1988-12-27 | Anode for high temperature fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62328545A JPH0732019B2 (en) | 1987-12-24 | 1987-12-24 | Negative electrode for high temperature fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01167957A JPH01167957A (en) | 1989-07-03 |
| JPH0732019B2 true JPH0732019B2 (en) | 1995-04-10 |
Family
ID=18211477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62328545A Expired - Lifetime JPH0732019B2 (en) | 1987-12-24 | 1987-12-24 | Negative electrode for high temperature fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0732019B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100429826B1 (en) * | 1997-02-17 | 2004-07-16 | 삼성전자주식회사 | Electrode catalyst layer composition for proton exchange fuel cell(PEMFC), electrode catalyst layer formed therefrom and PEMFC having the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63218163A (en) * | 1987-03-05 | 1988-09-12 | Agency Of Ind Science & Technol | Anode for molten carbonate type fuel cell |
-
1987
- 1987-12-24 JP JP62328545A patent/JPH0732019B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01167957A (en) | 1989-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bittner et al. | Electrochemical utilization of metal hydrides | |
| US5071720A (en) | Electrochemical cell | |
| EP0251385B1 (en) | Electrochemical cell | |
| JPH07211316A (en) | Storage battery | |
| Li et al. | Effects of cobalt content and preparation on electrochemical capacity of AB5-type hydrogen storage alloys at different temperature | |
| JPS5944748B2 (en) | Chikudenchi | |
| JPS62249358A (en) | Hydrogen storage electrode | |
| JPS61185863A (en) | Hydrogen occlusion alloy electrode | |
| JPH0765833A (en) | Hydrogen storage alloy electrode | |
| JPH01167957A (en) | Negative electrode for high temperature fuel cell | |
| EP0550153B1 (en) | Hydrogen-absorbing alloy electrode and its manufacturing method | |
| US3458358A (en) | Fuel cell electrode | |
| JPS63218163A (en) | Anode for molten carbonate type fuel cell | |
| JP2642144B2 (en) | Method for producing hydrogen storage electrode | |
| JPS62264557A (en) | Metal oxide-hydrogen battery | |
| JP2558624B2 (en) | Nickel-hydrogen alkaline storage battery | |
| JP2968360B2 (en) | Method for producing hydride secondary battery | |
| JPH0690922B2 (en) | Sealed alkaline storage battery | |
| JP2730074B2 (en) | Anode for fuel cell | |
| JPH0797497B2 (en) | Hydrogen storage electrode | |
| JPS60175367A (en) | Manufacturing method of negative electrode for sealed storage batteries | |
| JPS5931834B2 (en) | Hydrogen storage electrode | |
| JP3342699B2 (en) | Hydride battery and method for charging negative electrode thereof | |
| JPH0520864B2 (en) | ||
| JPH0815076B2 (en) | Sealed alkaline storage battery |