JPH0356631A - Production of sintered plate of porous cu alloy for anode electrode of fused carbonate type fuel cell - Google Patents
Production of sintered plate of porous cu alloy for anode electrode of fused carbonate type fuel cellInfo
- Publication number
- JPH0356631A JPH0356631A JP19218889A JP19218889A JPH0356631A JP H0356631 A JPH0356631 A JP H0356631A JP 19218889 A JP19218889 A JP 19218889A JP 19218889 A JP19218889 A JP 19218889A JP H0356631 A JPH0356631 A JP H0356631A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- plate
- porous
- powder
- sintered
- 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
Links
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 49
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 15
- 239000000446 fuel Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000007606 doctor blade method Methods 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000011812 mixed powder Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 229910010092 LiAlO2 Inorganic materials 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000005275 alloying Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000012733 comparative method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、主としてＣｕを還元してＣｕまたはＣｕ合
金素地中に微細なＡｆｉ，Ｚｒ，ＴＩ ．およびＣ『の
うちＩＦｌｉまたは２ＦＩｉ以上からなる酸化物粒子を
均一に分散せしめた組織を有する溶融炭酸塩型燃Ｉ４１
ｔＳ池のアノード電極用多孔質Ｃｕ合金焼結板の製造方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] This invention mainly involves reducing Cu to produce fine Afi, Zr, TI. Molten carbonate type fuel I41 having a structure in which oxide particles consisting of IFli or 2FIi or more are uniformly dispersed
The present invention relates to a method for manufacturing a porous Cu alloy sintered plate for an anode electrode of a tS pond.
溶進炭酸塩型燃料電池のアノード電極として、Ｃｕまた
はＣｕ合金素地中に微細なＡＪ，Ｚｒ，ＴＩ，およびＣ
『のうち１８または２種以上（以下、合金元素という）
の酸化物粒子を均一に分散せしめた組織を有する多孔質
Ｃｕ合金焼結板が提案されている（特開昭Ｈ− １６５
８４号公報参照）。As an anode electrode of a molten carbonate fuel cell, fine AJ, Zr, TI, and C are incorporated into a Cu or Cu alloy matrix.
18 or 2 or more of the following (hereinafter referred to as alloying elements)
A porous Cu alloy sintered plate having a structure in which oxide particles of
(See Publication No. 84).
この多孔ｉｉ Ｃ ｕ合金焼結板の素地中に分散する酸
化物粒子は、多孔質Ｃｕ合金焼結板の硬度およびクリー
プ強度を向上させる作用をする。The oxide particles dispersed in the matrix of the porous Cu alloy sintered plate serve to improve the hardness and creep strength of the porous Cu alloy sintered plate.
上記多孔質Ｃｕ合金焼結板は、上記合金元素を含有する
Ｃｕ合金粉末を成型して成型体とし、上記成型体を酸性
雰囲気中、温度：４００〜９００℃に加熱して酸化焼結
し、ついで、この酸化焼結体を還元雰囲気中、温度二６
００〜９００℃に加熱し、主としてＣｕを還元せしめ、
ＣｕまたはＣｕ合金素地中に微細な合金元素の酸化物粒
子を均一に分散せしめることにより製造される（特開昭
６２ − ２８１０２７号公報および特開昭６３− ７
８８３３号公報参照）。The porous Cu alloy sintered plate is obtained by molding Cu alloy powder containing the alloying element to form a molded body, heating the molded body in an acidic atmosphere at a temperature of 400 to 900°C to oxidize and sinter it, Next, this oxidized sintered body was heated at a temperature of 26°C in a reducing atmosphere.
Heating at 00 to 900°C to mainly reduce Cu,
It is manufactured by uniformly dispersing fine oxide particles of alloying elements in Cu or Cu alloy matrix (Japanese Patent Laid-Open Nos. 62-281027 and 63-7).
(See Publication No. 8833).
上述のように、溶融炭酸塩型燃料電池のアノード電極と
して用いられる多孔質のＣｕ合金焼結板は、上記合金元
素を含有するＣｕ合金粉末を戊型して得られた板状成型
体を酸性雰囲気中にて加熱して酸化焼結し、ついで、こ
の板状酸化焼結体を還元雰囲気中にて加熱することによ
り製造されるが、上記酸性雰囲気中加熱に際して大きく
膨脹し、還元雰囲気中加熱に際して大きく収縮するため
に、反りまたは撓みが発生し、変形した多孔質Ｃｕ合金
焼桔板が得られやすい（ただし上記酸性雰囲気中加熱で
の膨脹量と、還元雰囲気中加熱での収縮量とは、互いに
相殺するので寸法誤差は少むい）。As mentioned above, porous Cu alloy sintered plates used as anode electrodes of molten carbonate fuel cells are produced by molding Cu alloy powder containing the above-mentioned alloying elements. It is manufactured by heating in an atmosphere to oxidize and sinter, and then heating this plate-shaped oxidized sintered body in a reducing atmosphere, but it expands greatly when heated in the acidic atmosphere, and is heated in a reducing atmosphere. Due to the large shrinkage during heating, warping or deflection occurs, and a deformed porous Cu alloy sintered plate is likely to be obtained. , the dimensional errors are small because they cancel each other out).
上記反りまたは撓みが発生し変形した多孔質Ｃｕ合金焼
結板をアノード電極とし、このアノード電極を電解質板
と空気チャンネルの間に挟圧した状態で溶融炭酸塩型燃
料電池に組込むと、屯解質板とアノード電極の間に間隙
が生じて起電力が低下したりアノード電極に亀裂が発生
するなどの問題点があった。When the porous Cu alloy sintered plate which has been deformed due to warping or bending is used as an anode electrode, and this anode electrode is inserted into a molten carbonate fuel cell with pressure between the electrolyte plate and the air channel, There were problems such as a gap formed between the quality plate and the anode electrode, resulting in a decrease in electromotive force and cracks in the anode electrode.
そこで、本発明者らは、溶融炭酸塩型燃料電池のアノー
ド電極に用いる上記反りまたは撓みのない多孔質Ｃｕ合
金焼結板を製造すべく研究を行った結果、
Ｃｕ合金粉末に、アルミン酸リチウム（ＬＩＡＮＯ２）
粉末＝１〜５重量％を配合し混合して得られた混合粉末
の成型体を酸性雰囲気中加熱して酸化焼結し、ついで、
この酸化焼結体を還元雰囲気中にて加熱すると、上記酸
性雰囲気中加熱での膨脹が少なく、また還元雰囲気中加
熱での収縮が少ないために、反りまたは撓みの発生が少
’ｔ ＜ 、変形のない多孔質Ｃｕ合金焼結板が得られ
るという知見を得たのである。Therefore, the present inventors conducted research to produce a porous Cu alloy sintered plate that does not warp or bend as described above for use in the anode electrode of a molten carbonate fuel cell, and found that lithium aluminate was added to Cu alloy powder. (LIANO2)
A molded body of mixed powder obtained by blending and mixing powder = 1 to 5% by weight is heated in an acidic atmosphere to oxidize and sinter, and then,
When this oxidized sintered body is heated in a reducing atmosphere, there is little expansion when heated in the acidic atmosphere, and there is little contraction when heated in a reducing atmosphere, so there is little warpage or deformation. They found that it is possible to obtain a porous Cu alloy sintered plate free of porosity.
この発明は、かかる知見にもとづいてなされたものであ
って、
原料粉末からドクターブレード法により板状成型体を成
型し、脱バインダーして固化した後、上記板状成型体を
酸性雰囲気中、温度＝４００〜９００℃に加熱して酸化
焼結し、ついで、この板状酸化焼結体を還元雰囲気中、
温度＝４００〜９００℃に加熱し、主としてＣｕを還元
してＣｕまたはＣｕ合金素地中に微細ｔｉ酸化物粒子を
均一に分散せしめた組織を有する溶融炭酸塩型燃料電池
のアノード電極用多孔ｆｊ Ｃ ｕ合金焼結板を製造す
る方法において、上記原料粉末として、合金元素＝２〜
６ｉＩ！Ｑ％を含有し、残りがＣｕおよび不可避不純物
からなるＣｕ合金１）末に、アルミン酸リチウムわ｝末
：１〜５ｆｆｉ量％を配合し混合して得られた混合わ）
末を用いる溶融炭酸塩型斑料電池のアノード電極用多孔
質Ｃｕ合金焼結板の製造方法に特徴を有するものである
。The present invention was made based on this knowledge, and consists of molding a plate-shaped molded body from raw material powder by a doctor blade method, removing the binder and solidifying the plate-shaped molded body, and then heating the plate-shaped molded body in an acidic atmosphere at temperature. = 400 to 900°C for oxidative sintering, and then this plate-shaped oxidized sintered body was heated in a reducing atmosphere.
Porous fj C for an anode electrode of a molten carbonate fuel cell having a structure in which fine Ti oxide particles are uniformly dispersed in a Cu or Cu alloy matrix by heating to a temperature of 400 to 900°C and mainly reducing Cu. In the method for manufacturing a u-alloy sintered plate, the raw material powder contains alloying elements = 2 to
6iI! A mixture obtained by blending and mixing 1 to 5 ffi of lithium aluminate powder to Cu alloy 1) containing Q% and the rest consisting of Cu and unavoidable impurities.
The present invention is characterized by a method for manufacturing a porous Cu alloy sintered plate for an anode electrode of a molten carbonate type speckled material battery.
一般に、ｆａ融炭酸塩型燃料電池のアノード電極は、５
０〜８０容量％の気孔率を有することが必要であり、そ
のためには、
平均粒径：２〜２０−のＣｕ合金粉末、平均粒径： ０
．０５〜５ｐのアルミン酸リチウム粉末、
を用いることが必要である。Generally, the anode electrode of a fused carbonate fuel cell is 5
It is necessary to have a porosity of 0 to 80% by volume, and for that purpose, Cu alloy powder with an average particle size of 2 to 20 -, an average particle size of 0
．． It is necessary to use 05-5p lithium aluminate powder.
つぎに、この発明の溶融炭酸壇型世料電池のアノード電
極用多孔質Ｃｕ合金焼結阪の製造方法における限定理由
について説明する。Next, the reason for the limitation in the method for manufacturing the porous Cu alloy sintered plate for the anode electrode of the molten carbonate battery of the present invention will be explained.
（ａ） Ｃｕ合金粉末における合金元素の含有ユＣｕ
合金粉末における合金元素は、Ａｌ、Ｚｒ，ＴＩ，およ
びＣｒのうちＩＦＪまたは２種以上であるが、そのほと
んどが酸化物となって多孔質Ｃｕ合金焼結板の素地中に
分散する。しかし、その含有量が２ｆｆ！ｆｆｉ％未満
では、製造される多孔質Ｃｕ合金焼結板における酸化物
粒子の存在効果が少なく、一方、その含有量が６重量％
を越えると、分散する酸化物粒子の成長が著しく収り、
粗大化して多孔質Ｃｕ合金焼結板に割れが生じる原因に
なる。したがって、上記Ｃｕ合金粉末における合金元素
の含有量は、２〜６重量％に定めた。(a) Content of alloying elements in Cu alloy powder
The alloying elements in the alloy powder are IFJ or two or more of Al, Zr, TI, and Cr, and most of them become oxides and are dispersed in the matrix of the porous Cu alloy sintered plate. However, the content is 2ff! If the content is less than ffi%, the effect of the presence of oxide particles on the produced porous Cu alloy sintered plate will be small; on the other hand, if the content is less than 6% by weight,
When the value exceeds 1, the growth of the dispersed oxide particles significantly slows down.
It becomes coarse and causes cracks to occur in the porous Cu alloy sintered plate. Therefore, the content of alloying elements in the Cu alloy powder was set to 2 to 6% by weight.
（ｂ） アルミン酸リチウム粉末
上記Ｃｕ合金粉末にアルミン酸リチウム粉末を配合し混
合して得られた混合粉末の板状成型体を酸性雰囲気中で
加熱し酸化焼結すると、膨脹工は少なく、ついで、この
板状酸化焼桔体を還元雰囲気中で加熱すると、収縮量は
少ない。しかしながら上記アルミン酸リチウム粉末の配
合量が１重量％未満では、所望の効果が得られず、一方
、５ｆｆｉ量％を越えて含有すると、板状酸化焼結体の
強度が低下し、起電力も弱くなる。(b) Lithium aluminate powder When a plate-shaped molded body of the mixed powder obtained by blending and mixing the above-mentioned Cu alloy powder with lithium aluminate powder is heated in an acidic atmosphere and oxidized and sintered, there is little expansion. When this plate-shaped oxidized sintered body is heated in a reducing atmosphere, the amount of shrinkage is small. However, if the content of the lithium aluminate powder is less than 1% by weight, the desired effect cannot be obtained. On the other hand, if the content exceeds 5ffi, the strength of the plate-shaped oxidized sintered body decreases and the electromotive force also decreases. become weak.
したがって、Ｃｕ合金粉末に配合されるアルミン酸リチ
ウム粉末は、１〜５重量％に定めた。Therefore, the amount of lithium aluminate powder added to the Cu alloy powder was determined to be 1 to 5% by weight.
つぎに、この発明を、実施例にもとづいて具体的に説明
する。Next, the present invention will be specifically explained based on examples.
原料粉末として、第１表に示される成分組成を有し、平
均粒径： １０ｍのＣｕ合金粉末、および平均粒径：０
．５−のアルミン酸リチウム粉末を用意し、これら粉末
を第１表に示される配合組成となるように混合して混合
粉末とし、これとは別途用意した有機バインダーとして
のポリビニルブチラール（ＰＶＢ） 、溶剤としてのト
ルエンとエタノールの重量比で１＝１の混合液、可塑剤
としてのポリエチレングリコール、および解膠剤として
のオレイン酸メチルを、ｆｆｌ量比で、
混合粉末：有機バインダー二溶剤二可塑剤：ｆｉＩＩ膠
剤−２００： ５ ：９０： ２ ： ３の割合いで配
合し、撹拌混合してスラリー状とし、このスラリーをド
クターブレード法によりキャリャーテープ上に塗布し、
縦： ｇｏａｍ、横＝４０■、厚さ：Ｉ．Ｏｗ＋Ｃ７）
塗布層を形成し、この塗布層を赤外線乾燥器にて溶剤を
揮発させて板状成型体とし、ついでこれら板状成型体を
空気中で、温度＝４５０℃に３０分間加熱保持し、脱バ
インダーして固化した後、同じく空気中で、第１表に示
される条件で酸化燐結し、引続いてこの結果得られた酸
化焼結板を水素気流中で第１表に示される条件で、主と
してＣｕを還元し上記合金元素の酸化物粒子は還元せず
に素地中に分散残存せしめることにより、本発明法１〜
１５、比較法１〜２および従来法をそれぞれ実施し、多
孔質Ｃｕ合金焼結板を製造した。The raw material powder was Cu alloy powder having the component composition shown in Table 1, average particle size: 10 m, and average particle size: 0.
．． 5- Lithium aluminate powder was prepared, and these powders were mixed to have the composition shown in Table 1 to form a mixed powder, and in addition to this, polyvinyl butyral (PVB) as an organic binder and a solvent prepared separately. A mixture of toluene and ethanol in a weight ratio of 1=1 as a plasticizer, polyethylene glycol as a plasticizer, and methyl oleate as a deflocculant in an ffl weight ratio: Mixed powder: Organic binder, two solvents, and two plasticizers: fiII glue-200: 5: 90: 2: 3 ratio was mixed and stirred to form a slurry, and this slurry was applied onto a carrier tape using a doctor blade method.
Length: goam, width = 40cm, thickness: I. Ow+C7)
A coating layer is formed, and the solvent is evaporated from this coating layer using an infrared dryer to form a plate-shaped molded body.The plate-shaped molded body is then heated and held in air at a temperature of 450°C for 30 minutes to remove the binder. After solidification, oxidation phosphorization was carried out under the conditions shown in Table 1, also in air, and the resulting oxidized sintered plate was then oxidized and sintered in a hydrogen stream under the conditions shown in Table 1. By mainly reducing Cu and leaving the oxide particles of the alloying elements dispersed in the matrix without reducing them, methods 1 to 1 of the present invention can be carried out.
15. Comparative Methods 1 and 2 and the conventional method were each carried out to produce porous Cu alloy sintered plates.
ｔｌお、比較法１〜２は、いずれもＣｕ合金粉末の合金
元素の含有量またはアルミン酸リチウムの配合量がこの
発明の範囲から外れたものであり、第１表において、こ
の発明の範囲から外れた値に※印を付して示した。tl Oh, in Comparative Methods 1 and 2, the content of alloying elements in the Cu alloy powder or the blending amount of lithium aluminate is outside the scope of this invention, and in Table 1, Outlier values are marked with *.
また、アルミン酸リチウムを全く含まないＣｕ合金粉末
から多孔賀Ｃｕ合金焼結板を製造し、従来法として第１
表に示した。In addition, we have manufactured Pooka Cu alloy sintered plates from Cu alloy powder that does not contain any lithium aluminate, and have achieved the first conventional method.
Shown in the table.
このようにして製造した多孔質Ｃυ合金焼結板を第１図
に示されるように平板１上にａｔし、多孔質Ｃｕ合金焼
結板２の反り量３を川定し、その結果を第１表に示した
。The porous Cυ alloy sintered plate thus produced was placed on a flat plate 1 as shown in FIG. 1, the amount of warpage 3 of the porous Cu alloy sintered plate 2 was determined, and the results were It is shown in Table 1.
さらに上記各種多孔質Ｃｕ合金焼結板をアノード電極と
して用い、これを、
バイポーラ集電板：カソード側−ＳｔｌＳ３１ＢＢ穴空
き板、アノード側−Ｎ１ネット、
カソード電￥ｉ：多孔質ＮｉＯ焼結板、電解質板： Ｌ
ｉ Ａｌｌ ０２ ２５）末：４０％、Ｌ ｉ２ Ｃ
Ｏ ３粉末二２８％、Ｋ２ＣＯ３粉末：３２％からな
るホットプレス板（以上、重量％）
とともに単セルの溶融炭酸垣型燃料電池に組込み、電池
温度＝６５０℃でバイボーラ集電板のアノード側にＨ２
：８０％、ＣＯ２：２０％の混合ガスを流し、カソード
側に空気：７０％、Ｃ０２：３０％の混合ガスを流し、
ｌ００時間後の電池開回路電圧および電流密度：１５０
ｍＡ−ｃｒｒｒ−２なる負荷時の電池電圧をＭ１定して
その結果を第１表に示した。Furthermore, the above-mentioned various porous Cu alloy sintered plates are used as anode electrodes, and the bipolar current collector plate: cathode side - StlS31BB hole plate, anode side - N1 net, cathode electrode: porous NiO sintered plate, Electrolyte plate: L
i All 02 25) End: 40%, L i2 C
A hot-pressed plate consisting of 28% O3 powder and 32% K2CO3 powder (by weight) was incorporated into a single cell molten carbon dioxide wall type fuel cell, and placed on the anode side of the bibolar current collector plate at a cell temperature of 650°C. H2
A mixed gas of :80% and CO2:20% is flowed, and a mixed gas of air:70% and CO2:30% is flowed to the cathode side.
Battery open circuit voltage and current density after 100 hours: 150
The battery voltage at a load of mA-crrr-2 was fixed at M1, and the results are shown in Table 1.
第１表の結果から、本発明法１〜ｌ５によって製造され
た多孔ｉｉｉ Ｃ ｕ合金焼結板は、いずれも反り量が
少むく、その多孔質Ｃｕ合金焼結板で製造されたアノー
ド電極を組込んだ単セルの溶融炭酸墳型燃料電池の電池
電圧は、優れた値を示しているのに対し、比較法１およ
び従来法で製造された多孔＠ Ｃ ｕ合金焼結板の反り
量は大きく、また、比較法２にみられるようにアルミン
酸リチウム粉末の配合量が多すぎると電池電圧は低下す
ることがわかる。From the results in Table 1, the porous III Cu alloy sintered plates manufactured by methods 1 to 15 of the present invention all have a small amount of warpage, and the anode electrode manufactured with the porous Cu alloy sintered plates is The cell voltage of the integrated single-cell molten carbonate mound type fuel cell shows an excellent value, whereas the amount of warpage of the porous @ Cu alloy sintered plates manufactured by Comparative Method 1 and the conventional method is Furthermore, as seen in Comparative Method 2, if the amount of lithium aluminate powder blended is too large, the battery voltage will decrease.
この発明によれば、反りまたは撓みの無い溶融炭酸塩型
燃料電池のアノード電極を歩留り良く製造することがで
きるので、溶融炭酸塩型燃料電池の実用化に大いに貢献
できるものである。According to the present invention, an anode electrode for a molten carbonate fuel cell without warping or bending can be manufactured with good yield, and therefore it can greatly contribute to the practical application of molten carbonate fuel cells.
第１図は、多孔質Ｃｕ合金焼結板の反りの測定法を示す
立面図である。
１二平 板 ２：多孔質Ｃｕ合金焼桔板３：反り
量FIG. 1 is an elevational view showing a method for measuring warpage of a porous Cu alloy sintered plate. 12 flat plate 2: Porous Cu alloy sintered plate 3: Amount of warpage
Claims (1)
体を成型し、脱バインダーして固化した後、上記板状成
型体を酸性雰囲気中、温度＝４００〜９００℃に加熱し
て酸化焼結し、この結果得られた板状酸化焼結体を還元
雰囲気中、温度＝４００〜９００℃に加熱し、主として
Ｃｕを還元してＣｕまたはＣｕ合金素地中に微細な酸化
物粒子を均一に分散せしめた組織を有する溶融炭酸塩型
燃料電池のアノード電極用多孔質Ｃｕ合金焼結板の製造
方法において、 上記原料粉末として、Ａｌ、Ｚｒ、Ｔｉ、およびＣｒの
うち１種または２種以上：２〜６重量％を含有し、残り
がＣｕおよび不可避不純物からなるＣｕ合金粉末に、ア
ルミン酸リチウム粉末：１〜５重量％を配合し混合して
得られた混合粉末を用いることを特徴とする溶融炭酸塩
型燃料電池のアノード電極用多孔質Ｃｕ合金焼結板の製
造方法。(1) A plate-shaped molded body is molded from the raw material powder by the doctor blade method, the binder is removed and the plate-shaped molded body is solidified, and then the plate-shaped molded body is heated to a temperature of 400 to 900°C in an acidic atmosphere and oxidized and sintered. The resulting plate-shaped oxidized sintered body is heated to a temperature of 400 to 900°C in a reducing atmosphere to mainly reduce Cu and uniformly disperse fine oxide particles in the Cu or Cu alloy matrix. In the method for producing a porous Cu alloy sintered plate for an anode electrode of a molten carbonate fuel cell having a structure, the raw material powder includes one or more of Al, Zr, Ti, and Cr: 2 to 2. Molten carbonic acid characterized by using a mixed powder obtained by blending 1 to 5% by weight of lithium aluminate powder to a Cu alloy powder containing 6% by weight and the remainder consisting of Cu and unavoidable impurities. A method for manufacturing a porous Cu alloy sintered plate for an anode electrode of a salt-type fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19218889A JPH0356631A (en) | 1989-07-25 | 1989-07-25 | Production of sintered plate of porous cu alloy for anode electrode of fused carbonate type fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19218889A JPH0356631A (en) | 1989-07-25 | 1989-07-25 | Production of sintered plate of porous cu alloy for anode electrode of fused carbonate type fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0356631A true JPH0356631A (en) | 1991-03-12 |
Family
ID=16287143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19218889A Pending JPH0356631A (en) | 1989-07-25 | 1989-07-25 | Production of sintered plate of porous cu alloy for anode electrode of fused carbonate type fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0356631A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993005190A1 (en) * | 1991-09-04 | 1993-03-18 | Nihon Millipore Kogyo Kabushiki Kaisha | Process for producing porous metallic body |
| US5487771A (en) * | 1993-06-04 | 1996-01-30 | Millipore Corporation | High-efficiency metal membrane element, filter, and process for making |
| US7678470B2 (en) * | 2005-03-14 | 2010-03-16 | Korea Institute Of Science And Technology | Reinforced matrix for molten carbonate fuel cell using porous aluminum support and method for preparing the molten carbonate fuel cell comprising the reinforced matrix |
| CN112048635A (en) * | 2020-08-25 | 2020-12-08 | 西安理工大学 | Micro-nano graded porous copper and preparation method thereof |
-
1989
- 1989-07-25 JP JP19218889A patent/JPH0356631A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993005190A1 (en) * | 1991-09-04 | 1993-03-18 | Nihon Millipore Kogyo Kabushiki Kaisha | Process for producing porous metallic body |
| US5417917A (en) * | 1991-09-04 | 1995-05-23 | Nihon Millipore Kabushiki Kaisha | Metallic porous membrane and method of manufacture |
| US5487771A (en) * | 1993-06-04 | 1996-01-30 | Millipore Corporation | High-efficiency metal membrane element, filter, and process for making |
| USRE36249E (en) * | 1993-06-04 | 1999-07-13 | Millipore Investment Holdings, Inc. | High-efficiency metal membrane element, filter, and process for making |
| US7678470B2 (en) * | 2005-03-14 | 2010-03-16 | Korea Institute Of Science And Technology | Reinforced matrix for molten carbonate fuel cell using porous aluminum support and method for preparing the molten carbonate fuel cell comprising the reinforced matrix |
| CN112048635A (en) * | 2020-08-25 | 2020-12-08 | 西安理工大学 | Micro-nano graded porous copper and preparation method thereof |
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