JPH04104470A - Manufacture of electrode for solid electrolyte fuel cell - Google Patents
Manufacture of electrode for solid electrolyte fuel cellInfo
- Publication number
- JPH04104470A JPH04104470A JP2221776A JP22177690A JPH04104470A JP H04104470 A JPH04104470 A JP H04104470A JP 2221776 A JP2221776 A JP 2221776A JP 22177690 A JP22177690 A JP 22177690A JP H04104470 A JPH04104470 A JP H04104470A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- electrode
- intermediate layer
- fuel cell
- powder
- 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
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000000446 fuel Substances 0.000 title claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000001301 oxygen Substances 0.000 claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 abstract description 21
- 229910002319 LaF3 Inorganic materials 0.000 abstract description 16
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 abstract description 16
- 239000011812 mixed powder Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 238000010285 flame spraying Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 13
- 239000007921 spray Substances 0.000 description 11
- 239000012159 carrier gas Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007750 plasma spraying Methods 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 239000010408 film Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000007751 thermal spraying Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000010409 thin film Substances 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
Landscapes
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
Description
【発明の詳細な説明】
Ａ、産業上の利用分野
本発明は、酸素極と固体電解質層間又は固体電解質層と
水素極間に中間層を設けた固体電解質型燃料電池の製造
方法に関する。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a method for manufacturing a solid oxide fuel cell in which an intermediate layer is provided between an oxygen electrode and a solid electrolyte layer or between a solid electrolyte layer and a hydrogen electrode.
Ｂ３発明の概要
本発明の固体電解質型燃料電池の製造方法は、酸素極、
固体電解質、水素極を積層して成る固体電解質型燃料電
池において、各層間のうち少なくとも一方の層間に、積
層時に相互に接する両相料の混合体から成る中間層を設
け、酸素極と固体電解質間の界面インピーダンスを減少
させると共に、又は、固体電解質と水素極間に温度変化
による剥離が生じないようにしたものである。B3 Summary of the Invention The method for manufacturing a solid oxide fuel cell of the present invention includes an oxygen electrode,
In a solid electrolyte fuel cell consisting of a stack of a solid electrolyte and a hydrogen electrode, an intermediate layer made of a mixture of both phase materials that come into contact with each other during stacking is provided between at least one of the layers, and an oxygen electrode and a solid electrolyte are stacked together. This is to reduce the interfacial impedance between the solid electrolyte and the hydrogen electrode, or to prevent separation due to temperature changes between the solid electrolyte and the hydrogen electrode.
Ｃ９従来の技術
従来、低温固体電解質型燃料電池、特に平板型電池のセ
ルは、第３図に示すように、多孔質基板１上に酸素極２
．電解質４．水素極６を順次積層した構造になっている
。C9 Prior Art Conventionally, a low-temperature solid electrolyte fuel cell, especially a flat plate cell, has an oxygen electrode 2 on a porous substrate 1, as shown in FIG.
．． Electrolyte4. It has a structure in which hydrogen electrodes 6 are sequentially stacked.
この電池の製造方法としてはプラズマスプレー法が知ら
れており、実際にもこの方法でセルが作られている。A plasma spray method is known as a method for manufacturing this battery, and cells are actually manufactured using this method.
多孔質基板１は自立できない薄膜型燃料電池を支えるも
ので、かつカス透過性の良いものである。The porous substrate 1 supports a thin film fuel cell that cannot stand on its own, and has good sludge permeability.
固体電解質がＬａＦ３で膨張係数（］、］７．２Ｘ１０
−６／’Ｃが大ぎいために、膨張係数をマツチングする
ようにステンレス５ＵＳ３１．６Ｌの多孔質板を使用し
ている。The solid electrolyte is LaF3 and has an expansion coefficient (], ]7.2X10
-6/'C is too large, so a porous plate of stainless steel 5US31.6L is used to match the expansion coefficient.
酸素極２は低温での酸素分子の酸素イオン化の触媒能の
高い、膨張係数のマツチングを考えて、ペロブスカイト
化合物Ｌａｏ、ｅＳ ｒｏ ４ｃＯｏ 、８ＮＯ０２０
３又はＬａｏ、ｏＳ ｒｏ４ＭｎＯ，、、Ｌａ０．６Ｓ
ｒ ｏ、、Ｃ’ｒ Ｏ３等を使用している。The oxygen electrode 2 is made of perovskite compounds Lao, eS ro 4cOo, 8NO020, which have high catalytic ability for oxygen ionization of oxygen molecules at low temperatures and matching expansion coefficients.
3 or Lao, oS ro4MnO, , La0.6S
r o, , C'r O3, etc. are used.
これらのペロブスカイト酸素極２はプラズマスプレー法
により１００μｍの厚さに作製され、その後熱処理を十
分に行いプラスマスプレー時の熱及び機械的ストレスよ
り生じる結晶構造の乱れを回復させである。These perovskite oxygen electrodes 2 are fabricated to a thickness of 100 μm by plasma spraying, and then sufficiently heat treated to recover the disordered crystal structure caused by heat and mechanical stress during plasma spraying.
このように作成したペロブスカイト酸素極２の上にプラ
ズマスプレー法によりＬａＦ３を１００μｍの厚さに積
層して電解質層４とし、この上に水素イオン化能が高く
、かつ価格の安いＮｉを１００μｍの厚さに積層し水素
極６としてセルが作られている。LaF3 is laminated to a thickness of 100 μm using a plasma spray method on the perovskite oxygen electrode 2 created in this way to form an electrolyte layer 4, and Ni, which has high hydrogen ionization ability and is inexpensive, is deposited on top of this to a thickness of 100 μm. A cell is made by stacking the hydrogen electrodes 6 on top of each other.
なお、Ｎｉはプラズマスプレーの際中に一部ＮｉＯに変
化するか、電池運転中Ｈ２ガスによってＮｉに変化する
。Note that Ni partially changes to NiO during plasma spraying or changes to Ni by H2 gas during battery operation.
Ｄ６発明が解決しようとする課題
上記従来セルは、複素インピーダンス測定法により界面
インピーダンスを測定すると、３０〜１００Ω・０ｍ２
（４００°Ｃ）あり、これは主にペロブスカイト酸素極
／ＬａＦ３界面が原因であることがわかった。出力０．
７Ｖ−２００〜３００ｍ Ａ ／ ｃ ｍ ２のＶ−Ｉ
特性を得るためには、セル全体のインピーダンスを０．
ＸΩ・０ｍ２にしなければならないのに、現在界面イン
ピータンスだけで２０〜６０Ω・０ｍ２もあり、大きな
技術的問題となっている。（セル全体のインピーダンス
−固体電解質のバルクインピーダンス＋Ｌ ａ Ｆ ３
／ペロブス力イト界面インピーダンス＋ＬａＦ３／Ｎｉ
電極界面インピーダンス＋それぞれの電極のバルクイン
ピーダンス）
また、水素電極として触媒能の高いＮｉを使用している
が、固体電解質（ＬａＦ３）の膨張係数（１７，２Ｘ１
０−６／°Ｃ）に比べてＮｉ（１１，９×１０−６／°
Ｃ）は非常に小さいので、膨張係数のミスマツチングが
生じており、電池の運転（高温）−電池の運転停止（低
温）の繰り返しによるヒＩ・ザイクルにより固体電解質
（Ｌａ、Ｆ、、）とＮｉ極との間で剥離が生じるという
問題点があった。D6 Problems to be Solved by the Invention When the interface impedance of the above conventional cell is measured using the complex impedance measurement method, it is 30 to 100Ω・0m2.
(400°C), and it was found that this was mainly caused by the perovskite oxygen electrode/LaF3 interface. Output 0.
7V-200~300m A/cm2 V-I
In order to obtain the characteristics, the impedance of the entire cell should be set to 0.
Although it has to be set to XΩ·0m2, currently the interfacial impedance alone is 20 to 60Ω·0m2, which is a big technical problem. (Impedance of the entire cell - Bulk impedance of solid electrolyte + L a F 3
/ Perobus force interface impedance + LaF3/Ni
(electrode interface impedance + bulk impedance of each electrode) In addition, Ni with high catalytic ability is used as the hydrogen electrode, but the expansion coefficient of the solid electrolyte (LaF3) (17,2X1
Ni (11,9×10-6/°C) compared to Ni (11,9×10-6/°C)
Since C) is very small, mismatching of expansion coefficients occurs, and the solid electrolyte (La, F,...) and Ni There was a problem in that peeling occurred between the electrodes.
本発明は従来術のこのような問題点に鑑みてなされたも
のであり、その目的とするところは、界面インピーダン
スを減小させることのできる低温固体電解質型燃料電池
用電極の製造法及びヒートザイクルにより電解質と水素
極との間で剥離の生することのない低温固体電解質型燃
料電池用電極の製造法を提供することにある。The present invention has been made in view of the above-mentioned problems of the conventional techniques, and its purpose is to provide a method for manufacturing electrodes for low-temperature solid oxide fuel cells that can reduce interfacial impedance, and a heat cycle. An object of the present invention is to provide a method for manufacturing an electrode for a low-temperature solid electrolyte fuel cell in which peeling does not occur between an electrolyte and a hydrogen electrode.
Ｅ９課題を解決するための手段
上記目的を達成するために、本発明の固体電解質型燃料
電池用電極の製造方法は、
酸素極、固体電解質、水素極を積層して成る固体電解質
型燃料電池において、各層間のうち少なくとも一方の層
間に、積層時に相互に接する両材料の混合体から成る中
間層を設けるものである。E9 Means for Solving the Problems In order to achieve the above object, the method for manufacturing an electrode for a solid oxide fuel cell of the present invention includes the following steps: , an intermediate layer made of a mixture of both materials that contacts each other during lamination is provided between at least one of the layers.
また、ペロブスカイト化合物を製膜した酸素極の上に固
体電解質層を積層し、その上にＮｉを使用した水素極を
積層してなる燃料電池の製造方法において、前記酸素極
の上に該酸素極に使用しているペロブスカイト化合物と
前記固体電解質層に使われている固体電解質との混合体
からなる中間層を設けた後、この中間層上に前記固体電
解質層を設けるものである。Further, in a method for producing a fuel cell in which a solid electrolyte layer is laminated on an oxygen electrode formed of a perovskite compound film, and a hydrogen electrode using Ni is laminated on top of the solid electrolyte layer, the oxygen electrode is laminated on the oxygen electrode. After providing an intermediate layer made of a mixture of the perovskite compound used in the solid electrolyte layer and the solid electrolyte used in the solid electrolyte layer, the solid electrolyte layer is provided on the intermediate layer.
また、ペロブスカイト化合物を製膜した酸素極の上に固
体電解質層を積層し、その上にＮｉを使用した水素極を
積層してなる燃料電池の製造方法において、前記固体電
解質層の上に該固体電解質層に使用している固体電解質
と前記水素極に使用しているＮｉとの混合体からなる中
間層を設けた後、この中間層上に前記水素電極を設ける
ものである。In addition, in a method for manufacturing a fuel cell in which a solid electrolyte layer is laminated on an oxygen electrode formed of a film of a perovskite compound, and a hydrogen electrode using Ni is laminated on top of the solid electrolyte layer, the solid After providing an intermediate layer made of a mixture of the solid electrolyte used in the electrolyte layer and Ni used in the hydrogen electrode, the hydrogen electrode is provided on this intermediate layer.
Ｆ９作用
ペロブスカイト化合物よりなる酸素極と固体電解層との
間に酸素極に使われているペロブスカイト化合物と固体
電解層に使われている固体電解質との混合体からなる中
間層を設けると、界面インピータンスが小さくなる。こ
のため電池の電圧電流特性が向上する。If an intermediate layer made of a mixture of the perovskite compound used in the oxygen electrode and the solid electrolyte used in the solid electrolyte layer is provided between the oxygen electrode made of the F9 action perovskite compound and the solid electrolyte layer, the interfacial impedance will be reduced. The chest of drawers becomes smaller. Therefore, the voltage-current characteristics of the battery are improved.
また、固体電解層とＮｉ水素極との間に固体電解質層に
使われている固体電解質と水素極に使われているＮｉと
の混合体からなる中間層を設けると、隣接層間の膨張係
数の差が小さくなるので、温度変化により固体電解質と
Ｎｉ水素極間に剥離を生ずることがなくなる。Furthermore, if an intermediate layer made of a mixture of the solid electrolyte used in the solid electrolyte layer and the Ni used in the hydrogen electrode is provided between the solid electrolyte layer and the Ni hydrogen electrode, the expansion coefficient between the adjacent layers can be reduced. Since the difference becomes smaller, separation between the solid electrolyte and the Ni hydrogen electrode will not occur due to temperature changes.
Ｇ、実施例
第１図は実施例１〜３により作成される電池のセル断面
を示す。G. Example FIG. 1 shows cell cross sections of batteries prepared according to Examples 1 to 3.
実施例１
（１）ステンレス５ＵＳ３１６Ｌ製焼結フイルター（直
径４４．５ｍｍ、厚さ３．０ ｍｍ、ろ過精度２μｍ）
よりなる多孔質基板１の上に、ペロブスカイト化合物Ｌ
ａｏ、ｅＳ ｒ＋）４ＣＯｏ ９ｇＮｉｏ、ｏ２０３を
プラズマスプレー法で約１００μｍの厚さに製膜し、そ
の後十分に熱処理してペロブスカイト酸素極２を作る。Example 1 (1) Sintered filter made of stainless steel 5US316L (diameter 44.5 mm, thickness 3.0 mm, filtration accuracy 2 μm)
A perovskite compound L is placed on a porous substrate 1 made of
ao, eS r+)4COo 9gNio, o203 is formed into a film with a thickness of about 100 μm by a plasma spray method, and then sufficiently heat-treated to form a perovskite oxygen electrode 2.
（２）この酸素極２の上に同じＬａ（１，ｅＳ ｒｏ
４ＣＯ０，９８Ｎ ｉ Ｏ０２０３（以下ＬＳＣＮと
いう）粉と電解質層に使用する電解質ＬａＦ３粉（どち
らの粉末も１０〜８０μｍに粉径調整）から、ＬＳＣＮ
／ＬａＦ３＝１ ： １ （容積比）の混合粉を作り、
この混合粉を以下のプラズマスプレー条件で溶射し約２
０μｍに積層した中間層３を作る。(2) The same La (1, eS ro
From 4CO0,98N i O0203 (hereinafter referred to as LSCN) powder and electrolyte LaF3 powder used for the electrolyte layer (both powders have a powder diameter adjusted to 10 to 80 μm), LSCN
/LaF3=1:1 (volume ratio) mixed powder was made,
This mixed powder was sprayed under the following plasma spray conditions for approximately 2
An intermediate layer 3 is made by laminating the layers to a thickness of 0 μm.
プラズマガス：Ａｉｒ ２．８Ａ！／ｍｉｎ保護カス
：Ａｒ、］、ＱＡ／ｍｉｎ
溶射距離・１２０ｍｍ
パウダー供給量：６ｇ／ｍｉｎ
キャリアーガス Ａ ｉ ｒ、 １．８Ａ ／ｍ ｉ
ｎパワー＋１４．３Ｖ−１１０Ａ
（３）この中間層３の上に、ＬａＦ３粉を次のプラズマ
スプレー条件で積層し約１００μｍ厚さのＬａＦ３電解
質層４を作る。Plasma gas: Air 2.8A! /min Protective residue: Ar, ], QA/min Thermal spraying distance: 120mm Powder supply amount: 6g/min Carrier gas Air, 1.8A/min
n power +14.3V-110A (3) On this intermediate layer 3, LaF3 powder is laminated under the following plasma spray conditions to form a LaF3 electrolyte layer 4 with a thickness of about 100 μm.
プラズマガス：Ａｒ ２，３Ａ／ｍｉｎ保護ガス：Ａ
ｒ、１．ＯＡ／ｍｉｎ
溶射距離：９０ｍｍ
パウダー供給量：５ｇ／ｍｉｎ
キャリアーガス：Ａｒ ］、８＃／ｍｉｎパワー：
１−３７Ｖ−］、 １０Ａ
（４）ＬａＦ３電解質層上に、溶射用Ｎｉ粉（昭和電工
製Ｍ−８０）１．０〜４４μｍのものを次のプラズマス
プレー条件で約１００μｍ厚さに積層しＮｉ水素極６を
作る。Plasma gas: Ar 2,3A/min Protective gas: A
r, 1. OA/min Spraying distance: 90mm Powder supply amount: 5g/min Carrier gas: Ar], 8#/min Power:
1-37V-], 10A (4) On the LaF3 electrolyte layer, Ni powder for thermal spraying (M-80 manufactured by Showa Denko) with a thickness of 1.0 to 44 μm was laminated to a thickness of about 100 μm under the following plasma spray conditions. Make hydrogen electrode 6.
プラズマガス：Ａｒ、 ２．３１／ｍｉｎ保護ガス：
Ａｒ、１．Ｏｎ／ｍｉｎ
溶射距離＋１４０ｍｍ
パウダー供給量：９．Ｏｇ／ｍｉｎ
キャリアーガス： Ａ ｒ 、 ２ Ｉ／ ｍ ｉ
ｎパワー１４５Ｖ−１１０Ａ
（比較例１）
実施例１において、（２）の工程によるＬＳＣＮ／Ｌａ
Ｆ３混合物の中間層３がないもの、他は全て同じ。Plasma gas: Ar, 2.31/min Protective gas:
Ar, 1. On/min Spraying distance +140mm Powder supply amount: 9. Og/min Carrier gas: A r , 2 I/mi
n power 145V-110A (Comparative example 1) In Example 1, LSCN/La by step (2)
The one without intermediate layer 3 of the F3 mixture, all else being the same.
実施例２
実施例１のペロブスカイト混合物をＬａｏ、６Ｓ ｒ
ｏ、、Ｍｎ Ｏ３（以下ＬＳＭＯという）に変え、他は
実施例１と同様に作った。Example 2 The perovskite mixture of Example 1 was mixed with Lao, 6S r
o,,MnO3 (hereinafter referred to as LSMO) was used, and the other conditions were the same as in Example 1.
（比較例２）
実施例２において（２）の工程によるＬＳＭＯ／ＬａＦ
３の混合物の中間層がないもの。(Comparative Example 2) LSMO/LaF obtained by step (2) in Example 2
A mixture of 3 without an intermediate layer.
実施例３ 実施例１のペロブスカイト混合物をＬ ａ ｏ、。Example 3 The perovskite mixture of Example 1 is L ao.
Ｓ ｒ（、，４ＣｒＯｓ （以下ＬＳＣｒ○という）に
変え、他は実施例１と同様に作った。It was made in the same manner as in Example 1 except that Sr(,,4CrOs (hereinafter referred to as LSCr○)) was used.
（比較例３）
実施例３において（２）の工程による
Ｌ Ｓ Ｃｒ Ｏ／ Ｌ ａ Ｆ ３の混合物の中間層
がないもの。(Comparative Example 3) Example 3 without the intermediate layer of the L S Cr O/La F 3 mixture obtained in step (2).
表１に、実施例１．．２．３及び比較例１，２３により
作成したセルの界面インピーダンスを複素インピーダン
ス法で測定した結果を示す。Table 1 shows Example 1. ．． 2.3 and Comparative Examples 1 and 23, the interfacial impedances of the cells prepared according to Comparative Examples 1 and 23 were measured using the complex impedance method.
表１
単位・Ω・０ｍ２
表１の結果より明らかなように、実施例１〜３によれば
、酸素極２と電解質層４との間にペロブスカイト化合物
／ Ｌ ａ Ｆ ３の中間層３を設けたことにより界面
インピータンスを大幅に減少させることができた。Table 1 Unit・Ω・0m2 As is clear from the results in Table 1, according to Examples 1 to 3, the intermediate layer 3 of perovskite compound/L a F 3 was provided between the oxygen electrode 2 and the electrolyte layer 4. This made it possible to significantly reduce the interfacial impedance.
なお、固体電解質とペロブスカイト化合物の混合割合１
：１が望ましいが、１：９９〜９９：１（容積比）とす
ることができる。In addition, the mixing ratio of solid electrolyte and perovskite compound is 1
:1 is desirable, but it can be 1:99 to 99:1 (volume ratio).
酸素極及び中間層に使用されるペロブスカイＩ・化合物
は、次の３種である。The following three types of Perovsky I compounds are used for the oxygen electrode and the intermediate layer.
■Ｌａ１−ｘＳｒ、Ｃｏ１−ｙＮｉＶＯ３Ｘ、０〜０．
９．ｙ：０〜０．５望ましくはＸＯ，４，ｙ＝０．０２
■Ｌ ａ １−ｘＳ ｒ、Ｍｎ ０３
Ｘ、０〜０．９望ましくはｘ＝０．４
■Ｌａ１−．５ｒｘＣｒ○３
Ｘ＝Ｏ〜０．９望ましくはｘ＝０．４
固体電解質としては、ＬａＦ３．ＬａｏＦ、Ｌａ１−ｘ
ＭｘＦ３−ｘ （Ｍ： Ｓ ｒ、Ｓａ、Ｃａ等）Ｌａ
１− ｘ Ｍ Ｘ Ｏｐ ＋ −ｘを使用する。■La1-xSr, Co1-yNiVO3X, 0-0.
9. y: 0 to 0.5, preferably XO, 4, y=0.02 ■La 1-xS r, Mn 03 X, 0 to 0.9, preferably x=0.4 ■La1-. 5rxCr○3 X=O~0.9 Preferably x=0.4 As the solid electrolyte, LaF3. LaoF, La1-x
MxF3-x (M: S r, Sa, Ca, etc.) La
1- x M X Op + -x is used.
酸素極上に設ける中間層の厚さは、１０〜２０μｍとす
るのがよい。The thickness of the intermediate layer provided on the oxygen electrode is preferably 10 to 20 μm.
ペロブスカイト酸素極、Ｎｉ水素極はプラズマスプレー
以外にガス溶射でもよい。The perovskite oxygen electrode and the Ni hydrogen electrode may be formed by gas spraying instead of plasma spraying.
第２図は実施例４及び５により作成される電池のセル断
面を示す。FIG. 2 shows cell cross sections of batteries produced according to Examples 4 and 5.
実施例４
（１）ステンレスＳＵＳ ３０４製の焼結フィルター（
直径４４．５ｍｍ、厚さ３．０ｍｍ、ろ過精度２μｍ）
よりなる多孔質基板１の上に、ペロブスカイト化合物Ｌ
ａｏ、６Ｓ ｒＱ ４ＣＯｏ ９８ＮｊＯ，１）２０３
をプラズマスプレー法で約１００μｍの厚さに積層し酸
素極２を作り、この」−にＬ ａ Ｆ ３をプラズマス
プレー法で１００μｍの厚さに積層して電解質層４を作
る。Example 4 (1) Sintered filter made of stainless steel SUS 304 (
Diameter 44.5mm, thickness 3.0mm, filtration accuracy 2μm)
A perovskite compound L is placed on a porous substrate 1 made of
ao, 6S rQ 4COo 98NjO, 1) 203
was laminated to a thickness of about 100 μm using a plasma spray method to form an oxygen electrode 2, and L a F 3 was laminated to a thickness of about 100 μm to a thickness of 100 μm to this layer by a plasma spray method to form an electrolyte layer 4.
（２）この電解質層４の上に、溶射用Ｎｉ粉（昭和電工
製Ｍ ８０）１０〜４４ μｍ ＋ ＬａＦ、、粉（
造粒して１０〜８０μｍに調整したもの）−１１（容積
比）に混合した混合粉を作り、この混合粉を以下の条件
でプラズマスプレーで約２０μｍの厚さに積層し中間層
５を作る。(2) On top of this electrolyte layer 4, Ni powder for thermal spraying (M80 manufactured by Showa Denko) 10 to 44 μm + LaF powder (
(granulated and adjusted to 10 to 80 μm) - 11 (volume ratio) mixed powder is made, and this mixed powder is laminated to a thickness of about 20 μm using plasma spray under the following conditions to form the intermediate layer 5. .
プラズマガス：Ａｒ、２．８Ａ／ｍｉｎ保護ガス：Ａｒ
、１．０Ａ／ｍｉｎ
溶則距離：１４０ｍｍ
粉供給量：６ｇ／ｍｉｎ
キャリアーガス” ｒ 、 １ 、８ （！ ／ ｍ
ｉ ｎパワー １３７Ｖ−１，１ＯＡ
（３）この中間層５ （７）−、ｈｌ： Ｎ ｉ粉（Ｍ
−８０）のみを使ってこのＮｉ粉を以下の条件でプラズ
マスプレーにより約１００μｍの厚さに積層し水素極６
を作った。Plasma gas: Ar, 2.8A/min Protective gas: Ar
, 1.0A/min Melting distance: 140mm Powder supply amount: 6g/min Carrier gas "r, 1, 8 (! / m
i n power 137V-1,1OA (3) This intermediate layer 5 (7)-, hl: Ni powder (M
-80), this Ni powder was laminated to a thickness of about 100 μm by plasma spraying under the following conditions.
made.
プラズマガス：Ａｒ ２．８／／ｍｉｎ保護ガス：Ａ
ｒ、１．Ｏ１／ｍｉｎ
溶射距離：１４０ｍｍ
パウダー供給量：９ｇ／ｍｉｎ
キャリアーガス：２４／ｍｉｎ
パワー： １４５Ｖ−１１ＯＡ
実施例５
実施例４の水素極をＮｉ粉を次のガス溶射条件で溶射し
たものに変え、他は実施例４と同様にして作った。Plasma gas: Ar 2.8//min Protective gas: A
r, 1. O1/min Spraying distance: 140mm Powder supply amount: 9g/min Carrier gas: 24/min Power: 145V-11OA Example 5 The hydrogen electrode in Example 4 was replaced with one in which Ni powder was sprayed under the following gas spraying conditions. The rest was made in the same manner as in Example 4.
カス組成：Ｃ２Ｈ２１０２
溶射距離＋２００ｍｍ
パウダー供給量：２５ｇ／ｍｉｎ
キャリアーガス： Ｎ２． ４ｆｆｌ ７ｍ ｉ ｎ実
施例４及び５により作製した固体電解質型燃料電池を室
温→５００°Ｃの温度昇降を昇降速度１００°Ｃ／ｈで
１００回繰り返したところ電解質４と水素極６との間で
の剥離は何ら現れなかった。Residue composition: C2H2102 Spraying distance +200mm Powder supply amount: 25g/min Carrier gas: N2. 4ffl 7min When the temperature of the solid electrolyte fuel cell prepared according to Examples 4 and 5 was raised and lowered from room temperature to 500°C 100 times at a raising/lowering rate of 100°C/h, the temperature between the electrolyte 4 and the hydrogen electrode 6 was No peeling appeared.
また、室温→５００℃で昇降を速度２００°Ｃ／ｈで１
００回繰り返しても剥離は何ら現れなかった。Also, from room temperature to 500°C, lift and lower at a speed of 200°C/h.
Even after repeating the test 00 times, no peeling appeared.
なお、固体電解質とＮｉとの混合割分は、望ましくは１
：１であるが、■＝９９〜９９・１ （容積比）とする
ことかできる。Note that the mixing ratio of the solid electrolyte and Ni is preferably 1
:1, but ■=99 to 99·1 (volume ratio) can be used.
固体電解質としては、ＬａＦ３．Ｌａ０Ｆ。As the solid electrolyte, LaF3. La0F.
Ｌａ１−、ＭｘＦ３−ｘ （Ｍ： Ｓ ｒ ：Ｂａ）、
ＬａＭ ｘ ＯＦｌ−Ｘが使用できる。La1-, MxF3-x (M: S r :Ba),
LaM x OFl-X can be used.
固体電解質上の中間層、及びＮｉ水素極の製膜法はプラ
ズマスプレー法、ガス溶射法に限定されるものではない
。The method for forming the intermediate layer on the solid electrolyte and the Ni hydrogen electrode is not limited to the plasma spray method or the gas spray method.
Ｈ１発明の効果
本発明は、上述のとおり構成されているので、次に記載
する効果を奏する。H1 Effects of the Invention Since the present invention is configured as described above, it produces the following effects.
（１）酸素極と固体電解質問に中間層を設けることによ
り、固体電解質との間の界面インピーダンスが小さい酸
素電極が得られる。これにより電圧電流特性のより燃料
電池を得ることができる。(1) By providing an intermediate layer between the oxygen electrode and the solid electrolyte, an oxygen electrode with low interfacial impedance with the solid electrolyte can be obtained. This makes it possible to obtain a fuel cell with better voltage-current characteristics.
（２）固体電解質と水素極間に中間層を設けることによ
り、温度変化により固体電解質層から剥離することのな
い水素電極が得られる。これにより燃料電池の寿命が向
上する。(2) By providing an intermediate layer between the solid electrolyte and the hydrogen electrode, a hydrogen electrode that does not peel off from the solid electrolyte layer due to temperature changes can be obtained. This improves the lifespan of the fuel cell.
第１図及び第２図は、夫々本発明の異なる実施例により
作られる燃料電池のセル断面構成図、第３図は従来燃料
電池のセル断面構成図を示す。
■・・多孔質基板、２・・酸素極、３，５・・中間層、
４・・・固体電解質層、６・・・水素極。
外１名1 and 2 are cross-sectional configuration diagrams of fuel cells manufactured according to different embodiments of the present invention, and FIG. 3 is a cross-sectional configuration diagram of a conventional fuel cell. ■... Porous substrate, 2... Oxygen electrode, 3, 5... Intermediate layer,
4... Solid electrolyte layer, 6... Hydrogen electrode. 1 other person
Claims (3)
電解質型燃料電池において、各層間のうち少なくとも一
方の層間に、積層時に相互に接する両材料の混合体から
成る中間層を設けることを特徴とする固体電解質型燃料
電池用電極の製造方法。(1) In a solid oxide fuel cell formed by stacking an oxygen electrode, a solid electrolyte, and a hydrogen electrode, an intermediate layer made of a mixture of the two materials that contacts each other during stacking is provided between at least one of the layers. A method for producing an electrode for a solid electrolyte fuel cell, characterized by:
体電解質層を積層し、その上にＮｉを使用した水素極を
積層してなる燃料電池の製造方法において、 前記酸素極の上に該酸素極に使用しているペロブスカイ
ト化合物と前記固体電解質層に使われている固体電解質
との混合体からなる中間層を設けた後、この中間層上に
前記固体電解質層を設けたことを特徴とする固体電解質
型燃料電池用電極の製造方法。(2) A method for producing a fuel cell in which a solid electrolyte layer is laminated on an oxygen electrode formed of a film of a perovskite compound, and a hydrogen electrode using Ni is laminated on top of the solid electrolyte layer, in which the oxygen After providing an intermediate layer made of a mixture of the perovskite compound used in the electrode and the solid electrolyte used in the solid electrolyte layer, the solid electrolyte layer is provided on this intermediate layer. A method for manufacturing an electrode for a solid electrolyte fuel cell.
体電解質層を積層し、その上にＮｉを使用した水素極を
積層してなる燃料電池の製造方法において、 前記固体電解質層の上に該固体電解質層に使用している
固体電解質と前記水素極に使用しているＮｉとの混合体
からなる中間層を設けた後、この中間層上に前記水素電
極を設けたことを特徴とする固体電解質型燃料電池の製
造方法。(3) A method for manufacturing a fuel cell in which a solid electrolyte layer is laminated on an oxygen electrode made of a perovskite compound, and a hydrogen electrode made of Ni is laminated on top of the solid electrolyte layer, wherein A solid state characterized in that an intermediate layer made of a mixture of the solid electrolyte used in the solid electrolyte layer and Ni used in the hydrogen electrode is provided, and then the hydrogen electrode is provided on this intermediate layer. A method for manufacturing an electrolyte fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2221776A JPH04104470A (en) | 1990-08-23 | 1990-08-23 | Manufacture of electrode for solid electrolyte fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2221776A JPH04104470A (en) | 1990-08-23 | 1990-08-23 | Manufacture of electrode for solid electrolyte fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04104470A true JPH04104470A (en) | 1992-04-06 |
Family
ID=16772021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2221776A Pending JPH04104470A (en) | 1990-08-23 | 1990-08-23 | Manufacture of electrode for solid electrolyte fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04104470A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003059523A (en) * | 2001-08-14 | 2003-02-28 | Nissan Motor Co Ltd | Solid electrolyte fuel cell |
| WO2022137691A1 (en) * | 2020-12-23 | 2022-06-30 | 三井金属鉱業株式会社 | Nickel powder, method for producing same, conductive composition, and conductive film |
| WO2024000742A1 (en) * | 2022-06-30 | 2024-01-04 | 苏州大学 | Perovskite oxide-transition metal phosphide heterostructure composite electrode material, preparation method therefor, and use thereof |
-
1990
- 1990-08-23 JP JP2221776A patent/JPH04104470A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003059523A (en) * | 2001-08-14 | 2003-02-28 | Nissan Motor Co Ltd | Solid electrolyte fuel cell |
| WO2022137691A1 (en) * | 2020-12-23 | 2022-06-30 | 三井金属鉱業株式会社 | Nickel powder, method for producing same, conductive composition, and conductive film |
| WO2024000742A1 (en) * | 2022-06-30 | 2024-01-04 | 苏州大学 | Perovskite oxide-transition metal phosphide heterostructure composite electrode material, preparation method therefor, and use thereof |
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