JPH04141957A - Manufacture of oxygen gas electrode of solid electrolyte fuel cell - Google Patents
Manufacture of oxygen gas electrode of solid electrolyte fuel cellInfo
- Publication number
- JPH04141957A JPH04141957A JP2260430A JP26043090A JPH04141957A JP H04141957 A JPH04141957 A JP H04141957A JP 2260430 A JP2260430 A JP 2260430A JP 26043090 A JP26043090 A JP 26043090A JP H04141957 A JPH04141957 A JP H04141957A
- Authority
- JP
- Japan
- Prior art keywords
- platinum
- plating
- ysz
- oxygen gas
- fuel cell
- 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
- 239000000446 fuel Substances 0.000 title claims abstract description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims description 15
- 229910001882 dioxygen Inorganic materials 0.000 title claims description 15
- 239000007784 solid electrolyte Substances 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000007747 plating Methods 0.000 claims abstract description 20
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 19
- 238000005530 etching Methods 0.000 claims abstract description 6
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims abstract description 6
- 238000005238 degreasing Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 abstract description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 abstract description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 abstract 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 abstract 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 abstract 1
- QCDFRRQWKKLIKV-UHFFFAOYSA-M chloroplatinum Chemical compound [Pt]Cl QCDFRRQWKKLIKV-UHFFFAOYSA-M 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 235000011150 stannous chloride Nutrition 0.000 abstract 1
- 239000001119 stannous chloride Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 oxygen ions Chemical class 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- BQENXCOZCUHKRE-UHFFFAOYSA-N [La+3].[La+3].[O-][Mn]([O-])=O.[O-][Mn]([O-])=O.[O-][Mn]([O-])=O Chemical compound [La+3].[La+3].[O-][Mn]([O-])=O.[O-][Mn]([O-])=O.[O-][Mn]([O-])=O BQENXCOZCUHKRE-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
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
- Y02E60/50—Fuel cells
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は固体電解質燃料電池（以下、５ＯＦＣと略畜乙
する）の酸素ガス電極の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing an oxygen gas electrode for a solid electrolyte fuel cell (hereinafter abbreviated as 5OFC).
５ＯＦＣは主としてイツ）ＩＪア安定化ジルコニア（以
下、ＹＳＺと略記する）を固体電解質として用い、その
片側に燃料極としてニッケルをコーティング、もう一方
に白金ペーストあるいはストロンチウムドープのランタ
ンマンガナイト等をコーティングし酸素ガス電極として
おり、これを１０００℃に保持し、燃料極側に水素ガス
、酸素ガス電極側に空気を流すことにより、発電するよ
うな構成にしている。5OFC mainly uses IJ-stabilized zirconia (hereinafter abbreviated as YSZ) as a solid electrolyte, one side of which is coated with nickel as a fuel electrode, and the other side coated with platinum paste or strontium-doped lanthanum manganite. The electrode is an oxygen gas electrode, which is maintained at 1000° C., and is configured to generate electricity by flowing hydrogen gas to the fuel electrode side and flowing air to the oxygen gas electrode side.
この電極の材料およびコーティング方法により、電池と
しての発電効率が大きく変わってくる。The power generation efficiency of the battery varies greatly depending on the electrode material and coating method.
酸素ガス電極では空気中の酸素が多孔質になっている電
極のすき間を通って固体電解質と酸素ガス電極材料とガ
スの３相界面に到達する。In the oxygen gas electrode, oxygen in the air passes through the gaps between the porous electrodes and reaches the three-phase interface between the solid electrolyte, the oxygen gas electrode material, and the gas.
ここに到達した酸素は酸素ガス電極材料を通ってきた電
子をもらって酸素イオンとなり固体電解質中を移動する
。このため、酸素ガス電極材料は電子導伝性が高く、酸
素を酸素イオンとする反応を促進し、さらにガスを通し
やすい構造とする必要がある。しかしながら、これまで
に満足しうる酸素電極はなかった。The oxygen that has arrived here receives electrons that have passed through the oxygen gas electrode material, becomes oxygen ions, and moves through the solid electrolyte. Therefore, the oxygen gas electrode material needs to have a structure that has high electronic conductivity, promotes the reaction of oxygen into oxygen ions, and facilitates gas passage. However, until now there has been no satisfactory oxygen electrode.
本発明は上記技術水準に鑑み、５ＯＦＣの酸素ガス電極
として発生電流が従来よりのものよりも優れ、結果的に
高出力の５ＯＦＣが得られる同電池の酸素ガス電極の製
造方法を提供しようとするも゛のである。In view of the above-mentioned state of the art, the present invention aims to provide a method for producing an oxygen gas electrode for a 5OFC cell, which generates a higher current than conventional ones and which results in a high output 5OFC. It's also true.
本発明はイツトリア安定化ジルコニアを脱脂、エツチン
グ、触媒化処理後、化学メッキによって白金をメッキす
ることを特徴とする固体電解質燃料電池の酸素ガス電極
の製造方法である。The present invention is a method for producing an oxygen gas electrode for a solid electrolyte fuel cell, which comprises degreasing, etching, and catalyzing yttria-stabilized zirconia and then plating it with platinum by chemical plating.
更に、本発明を具体的に云うと、ＹＳＺをアセトンのよ
うな溶媒で脱脂し、フッ化水素などの強酸でエツチング
し、塩化スズ及び塩化パラジウムなどにより触媒化処理
を施した後、これを例えば塩化白金酸溶液と塩化ヒドラ
ジン溶液からなるメッキ溶液に浸漬して白金を化学メッ
キする方法である。Furthermore, to describe the present invention specifically, YSZ is degreased with a solvent such as acetone, etched with a strong acid such as hydrogen fluoride, and catalyzed with tin chloride, palladium chloride, etc., and then, for example, This is a method of chemically plating platinum by immersing it in a plating solution consisting of a chloroplatinic acid solution and a chlorinated hydrazine solution.
Ｓ’ＯＦＣに用いるセルは１０００℃の条件下において
も耐える必要がある。この時ＹＳｚの酸素ガス電極側に
薄膜の白金メッキを施すと発電性能が向上することが発
明者らの研究によって分っているが、その時の白金メッ
キ処理は通常の白金メッキ処理が脱脂後、メッキ処理を
するだけで充分であるのに対し、ＹＳｚの如きセラミッ
クスには本処理のみでは不十分であるのでエツチング処
理も必要とする。また本発明で用いるＹＳＺは１０００
℃という条件で用いられるものであり、この条件下で発
電・停止を繰り返していると白金メッキは剥離しやすい
。このことから更に白金メッキ処理に先立って触媒化処
理を行うものである。Cells used in S'OFC need to withstand conditions of 1000°C. At this time, the inventors' research has shown that power generation performance is improved by applying a thin layer of platinum plating to the oxygen gas electrode side of the YSz. While plating alone is sufficient, this treatment alone is not sufficient for ceramics such as YSz, so etching is also required. Moreover, YSZ used in the present invention is 1000
It is used under conditions of ℃, and if power generation and shutdown are repeated under these conditions, the platinum plating is likely to peel off. For this reason, catalytic treatment is further performed prior to platinum plating treatment.
白金は金属であり電子導電性が高く、また１０００℃の
酸素中でも酸化されない。白金メッキとしたために０，
５μｍの厚さと薄くすることができ、酸素ガスが３相界
面まで到達しやすい。また、白金メッキには酸素分子が
通過できる微細な気孔や粒界があり、酸素の３相界面ま
での到達をさまたげない。そしてメッキであるた給に固
体電解質に微細構造をもって密着しており、３相界面の
真の面積が大きく、酸素を酸素イオンにする反応が容易
に進行する。Platinum is a metal, has high electronic conductivity, and is not oxidized even in oxygen at 1000°C. 0, due to platinum plating
It can be made as thin as 5 μm, and oxygen gas can easily reach the three-phase interface. Furthermore, platinum plating has fine pores and grain boundaries through which oxygen molecules can pass, and does not prevent oxygen from reaching the three-phase interface. In addition to being plated, it adheres to the solid electrolyte with a fine structure, and the true area of the three-phase interface is large, so that the reaction that converts oxygen to oxygen ions progresses easily.
更に、また白金メッキであるために高価な白金を多量に
使用する必要がなく、５ＯＦＣのコスト低減が可能であ
る。Furthermore, since it is platinum plated, there is no need to use a large amount of expensive platinum, and the cost of 5OFC can be reduced.
以下、本発明の固体電解質燃料電池の酸素ガス電極の製
造方法の一実施例をあげ、本発明の効果を立証する。Hereinafter, an example of the method for manufacturing an oxygen gas electrode for a solid electrolyte fuel cell according to the present invention will be given to demonstrate the effects of the present invention.
５０〜５００μｍのＹＳＺ（８ｍｏ１％Ｙ２０゜安定化
ＺｒＤ□）を下記の工程順で処理して白金メッキを行っ
て酸素ガス電極を形成させた。YSZ (8 mo1% Y20° stabilized ZrD□) having a thickness of 50 to 500 μm was treated in the following process order and plated with platinum to form an oxygen gas electrode.
■ 脱脂：アセトンで５分間浸漬洗浄
■ エッチング：フッ化水素酸に１０分間浸漬■ 触媒
化処理： ＳｎＣ］ａ水溶液中に２分間浸漬、ＰｄＣｌ
２水溶液中に２分間浸漬
■ メッキ処理： Ｈ２Ｐｔｃ１ｇ・６Ｈ２０水溶液十
Ｎ、）Ｉ。■ Degreasing: immersion cleaning in acetone for 5 minutes ■ Etching: immersion in hydrofluoric acid for 10 minutes ■ Catalytic treatment: immersion in SnC]a aqueous solution for 2 minutes, PdCl
2 Immersion in aqueous solution for 2 minutes■ Plating treatment: 1 g of H2Ptc, 10N of 6H20 aqueous solution, )I.
・２ＨＣ１水溶液に浸漬
上記工程■、■における各水溶液濃度は数％の濃度であ
ればよく、白金メッキの厚さが０．５〜５μｍとなった
ところで引上げる。- Immersion in 2HC1 aqueous solution The concentration of each aqueous solution in the above steps (1) and (2) may be several percent, and the plate is pulled up when the thickness of the platinum plating reaches 0.5 to 5 μm.
一方、燃料電極を上記ＹＳｚの他面に、Ｎｉ０６０％と
同じＹＳＺ ４０％の粉末の混合物に、シンナー、ア
ルコール類の溶剤などを添加し、粘度１０００〜１０，
０００ポイズ（最適値６０００ポイズ程度）に調整した
スラリーを塗布して焼成することによって形成させた。On the other hand, a fuel electrode was placed on the other side of the above-mentioned YSZ by adding thinner, alcohol solvent, etc. to a powder mixture of 60% Ni and 40% YSZ to obtain a powder with a viscosity of 1000 to 10.
It was formed by applying a slurry adjusted to 000 poise (optimal value of about 6000 poise) and firing.
このようにして製作した５ＯＦＣによると、単位面積当
りの発生電流が飛躍的に向上し、０、７５ Ｖ、 ５
００ ｍＡ７ｃｍ”の出力が得られた。According to the 5OFC manufactured in this way, the generated current per unit area improved dramatically, and the current generated per unit area was 0.75 V.
An output of 00 mA7cm" was obtained.
これに対し、従来方法、すなわち上記の工程の■脱脂、
■メッキ処理の工程のみで、■エツチング、■触媒化処
理工程を施こさない方法、によって製作した５ＯＦＣで
は単位面積当り０．７５Ｖ、２００ｍ＾／ｃｍ”程度の
出力が得られたに過ぎなかった。In contrast, the conventional method, i.e., the above steps:
The 5OFC manufactured using only the plating process without the etching and catalytic processes was able to obtain an output of only 0.75V per unit area and approximately 200m^/cm''. .
〔発明の効果〕
本発明により、単位面積当りの発生電流が飛躍的に向上
した５ＯＦＣが提供され、その工業的効果は極めて著し
いものである。[Effects of the Invention] The present invention provides a 5OFC in which the generated current per unit area is dramatically improved, and its industrial effects are extremely remarkable.
Claims (1)
化処理後、化学メッキによって白金をメッキすることを
特徴とする固体電解質燃料電池の酸素ガス電極の製造方
法。A method for producing an oxygen gas electrode for a solid electrolyte fuel cell, which comprises degreasing, etching, and catalyzing yttria-stabilized zirconia and then plating it with platinum by chemical plating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2260430A JPH04141957A (en) | 1990-10-01 | 1990-10-01 | Manufacture of oxygen gas electrode of solid electrolyte fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2260430A JPH04141957A (en) | 1990-10-01 | 1990-10-01 | Manufacture of oxygen gas electrode of solid electrolyte fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04141957A true JPH04141957A (en) | 1992-05-15 |
Family
ID=17347826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2260430A Pending JPH04141957A (en) | 1990-10-01 | 1990-10-01 | Manufacture of oxygen gas electrode of solid electrolyte fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04141957A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110621806A (en) * | 2017-05-18 | 2019-12-27 | 日本高纯度化学株式会社 | Electroless platinum plating solution and platinum coating film obtained using same |
-
1990
- 1990-10-01 JP JP2260430A patent/JPH04141957A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110621806A (en) * | 2017-05-18 | 2019-12-27 | 日本高纯度化学株式会社 | Electroless platinum plating solution and platinum coating film obtained using same |
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