JPH038264A - Solid electrolyte fuel cell - Google Patents
Solid electrolyte fuel cellInfo
- Publication number
- JPH038264A JPH038264A JP1142816A JP14281689A JPH038264A JP H038264 A JPH038264 A JP H038264A JP 1142816 A JP1142816 A JP 1142816A JP 14281689 A JP14281689 A JP 14281689A JP H038264 A JPH038264 A JP H038264A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- cathode
- solid electrolyte
- cell
- gas passage
- 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 description 13
- 239000000446 fuel Substances 0.000 title claims description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract 3
- 239000002184 metal Substances 0.000 claims abstract 3
- 239000011247 coating layer Substances 0.000 claims description 8
- 239000010410 layer Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 25
- 230000001590 oxidative effect Effects 0.000 abstract description 9
- 239000002737 fuel gas Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 abstract description 3
- 238000007733 ion plating Methods 0.000 abstract description 2
- 229910002262 LaCrO3 Inorganic materials 0.000 abstract 2
- 239000010408 film Substances 0.000 abstract 2
- 229910002254 LaCoO3 Inorganic materials 0.000 abstract 1
- 229910002328 LaMnO3 Inorganic materials 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910001026 inconel Inorganic materials 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
Classifications
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
- H01M8/0208—Alloys
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0215—Glass; Ceramic materials
- H01M8/0217—Complex oxides, optionally doped, of the type AMO3, A being an alkaline earth metal or rare earth metal and M being a metal, e.g. perovskites
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0215—Glass; Ceramic materials
- H01M8/0217—Complex oxides, optionally doped, of the type AMO3, A being an alkaline earth metal or rare earth metal and M being a metal, e.g. perovskites
- H01M8/0219—Chromium complex oxides
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- 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
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
-
- 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】 （イ）産業上の利用分野 本発明は高温固体電解質燃料電池に関するものである。[Detailed description of the invention] (b) Industrial application field The present invention relates to high temperature solid electrolyte fuel cells.
（ロ）従来の技術
高温固体電解質燃料電池（以下５ＯＦＣと記す）は、固
体電解質内での酸素イオン導電性を利用し、燃料ガスと
酸化剤ガスを反応させるものである。固体電解質及び対
向極を平板状に重ねたセルでは、各極背面に反応ガスの
供給及び集電のためガス通路板を設ける必要があり、こ
のガス通路板として、耐熱性に優れたニッケルークロム
合金（商品名インコネル）が検討されている。(B) Conventional Technology A high temperature solid electrolyte fuel cell (hereinafter referred to as 5OFC) utilizes oxygen ion conductivity within a solid electrolyte to cause fuel gas and oxidant gas to react. In a cell in which a solid electrolyte and a counter electrode are layered in a flat plate, it is necessary to provide a gas passage plate on the back of each electrode for supplying reactive gas and collecting current, and this gas passage plate is made of nickel-chromium, which has excellent heat resistance. An alloy (trade name: Inconel) is being considered.
しかし１０００℃の高温下で酸化雰囲気にさらされるカ
ソード側ガス通路板は、表面に酸化皮膜を形成して酸化
の進行を防ぐが、長期に亘る使用により酸化膜が成長し
、特にＣｒｔ Ｏ１層の成長はｔ気導電性の低下をもた
らし、カソード極との接触抵抗を増大させるという問題
があった。However, the cathode side gas passage plate, which is exposed to an oxidizing atmosphere at a high temperature of 1000°C, forms an oxide film on the surface to prevent the progress of oxidation. There was a problem that the growth caused a decrease in electrical conductivity and increased contact resistance with the cathode.
（ハ）発明が解決しようとする課題
本発明は長期に亘ってガス通路板とカソード極間の電気
的接触状態を安定化するものである。(c) Problems to be Solved by the Invention The present invention is intended to stabilize the state of electrical contact between the gas passage plate and the cathode electrode over a long period of time.
（ニ）課題を解決するための手段
本発明はアノード極、固体電解質、カソード極からなる
平板状セルの各極背面にニッケルークロム合金などの耐
熱性ガス通路板を配置した５ＯＦＣにおいて、前記ガス
通路板のカソード極と接触する部分に耐酸化性、良導電
性のペロブスカイト型酸化物の被覆層を形成したもので
ある。(d) Means for Solving the Problems The present invention provides a 5OFC in which a heat-resistant gas passage plate made of nickel-chromium alloy or the like is arranged on the back surface of each electrode of a flat cell consisting of an anode, a solid electrolyte, and a cathode. A coating layer of perovskite-type oxide, which is oxidation-resistant and has good conductivity, is formed on the portion of the path plate that contacts the cathode electrode.
（ホ）作 用
本発明では耐酸化性に優れた導電被覆層がガス通路板の
カソード極と接触する部分に形成されているので、長期
に亘って接触部の酸化を抑制し、電池特性の低下を防止
する。(E) Function In the present invention, since a conductive coating layer with excellent oxidation resistance is formed on the part of the gas passage plate that contacts the cathode electrode, oxidation of the contact part is suppressed over a long period of time, and the battery characteristics are improved. Prevent decline.
（へ）実施例
第１図は本発明平板状単セルの断面図、第２図は同上の
要部拡大断面図を示す。(f) Example FIG. 1 is a sectional view of a flat unit cell of the present invention, and FIG. 2 is an enlarged sectional view of the same essential parts.
平板状セル（１）は、８％イツトリアで安定化したジル
コニアの焼成体からなる電解質層（２）と、Ｎｉ Ｚ
ｒ０ｍサーメットからなるアノード極（３）と、Ｌａｏ
、 ＊ Ｓ ｒｅ、 ＋ＭｎＯｒペロブスカイト型酸化
物からなるカソード極（４）とで構成され、これら各ｐ
ｉ（３）（４）はｔ極構成材粉末を含むスラリーを電解
質層（２）の各面に夫々０，２閣厚で塗布して後焼成し
た。The flat cell (1) has an electrolyte layer (2) consisting of a fired body of zirconia stabilized with 8% ittria, and a NiZ
An anode pole (3) made of r0m cermet and Lao
, *S re, + cathode electrode (4) made of MnOr perovskite type oxide, and each of these p
For i(3) and (4), a slurry containing the t-electrode constituent material powder was applied to each surface of the electrolyte layer (2) at a thickness of 0.2 mm and then post-baked.
このセル（１）を挟持する一対のガス通路板（５）（６
）はニッケルクロム合金（商品名インコネル６００．６
０１）などの耐熱性金属からなり、カソード極（４）に
酸化剤ガスを供給するガス溝（５゛）及びアノード極（
３）に燃料ガスを供給するガス溝（６′）を夫々有する
。A pair of gas passage plates (5) (6) sandwiching this cell (1).
) is a nickel-chromium alloy (trade name Inconel 600.6
A gas groove (5゛) that supplies oxidant gas to the cathode electrode (4) and an anode electrode (
3) respectively have gas grooves (6') for supplying fuel gas.
このカソード側ガス通路板（５）には、カソード極（４
）と接する部分に予めＬａＣｒＯｓをイオンブレーティ
ング法により厚み５μｍの薄′層（７）として被覆する
。被覆材としてＬａＣｒ０．の他ＬａＭｎＱ ｊ＋
Ｌ ａＣｏＯ、あるいはその置換体（Ｌａ、−ｘＭｘＣ
ｒｙｓ ここでＭ＝Ｍｇ、Ｃａ、Ｓｒなどのアルカ
リ土類金属）なとの高温酸化雰囲気において安定で導電
性（導電率１０１〜１０″ｓ／ｃｍ）を示すものであれ
ば使用できる。以上列記した被覆材はカソード極（４）
に用いたと同様のペロブスカイト型酸化物である。This cathode side gas passage plate (5) has a cathode electrode (4
) is coated in advance with LaCrOs as a thin layer (7) with a thickness of 5 μm by ion blasting. LaCr0. Other LaMnQ j+
L aCoO or its substituted product (La, -xMxC
rys (where M=alkaline earth metals such as Mg, Ca, and Sr) can be used as long as it is stable and has conductivity (conductivity 101 to 10"s/cm) in a high-temperature oxidizing atmosphere. Listed above. The covered material is the cathode electrode (4)
It is a perovskite-type oxide similar to that used in .
又被覆法としてイオンプレーテングの他スパッタリング
法各種溶射法（プラズマ溶射、アーク溶射）及び化学蒸
着（ＣＶＤ）法なども使用できる。被覆層として密着性
が良く緻密であることが要求されるので、減圧下で被覆
することが好ましい。又厚みについてはできるだけ小さ
いことが望ましいが、１μｍ以下では長期使用に耐えら
れず、密着性を考慮して２〜１０μｍ程度とする。In addition to ion plating, sputtering, various thermal spraying methods (plasma spraying, arc spraying), and chemical vapor deposition (CVD) can also be used as coating methods. Since the coating layer is required to have good adhesion and be dense, it is preferable to coat under reduced pressure. Further, it is desirable that the thickness be as small as possible, but if it is less than 1 .mu.m, it will not be able to withstand long-term use, so the thickness should be about 2 to 10 .mu.m in consideration of adhesion.
尚第１図実施例で一方のガス通路板（６）と一体に他方
のガス通路板（５）の外周をとっかこむ溜部（８）を形
成し、この溜部に、パイレックスガラスのような非導電
性高粘度融体（９）を満たすことによりシール部を構成
した場合を例示した。In the embodiment shown in FIG. 1, one gas passage plate (6) is integrally formed with a reservoir (8) that encloses the outer periphery of the other gas passage plate (5), and this reservoir is made of a material such as Pyrex glass. The case where the seal portion is constructed by filling the non-conductive high viscosity melt (9) is illustrated.
上記単セルを所定の条件で１０００℃まで昇温し、燃料
ガスにＨｌ、酸化剤ガスにＯ８を用い、５００ｍＡハか
にて長期運転した場合の電池特性を第３図に示す。又比
較のため被覆層を有しない同様の単セルの特性を点線で
示した。比較電池では８００時間経過後除々に特性の低
下が見られるに対し本発明電池では安定した特性を示す
ことがわかる。FIG. 3 shows the cell characteristics when the above single cell was heated to 1000° C. under predetermined conditions and operated for a long period at 500 mA using H1 as the fuel gas and O8 as the oxidant gas. For comparison, the characteristics of a similar single cell without a coating layer are shown by dotted lines. It can be seen that the characteristics of the comparative battery gradually deteriorated after 800 hours, whereas the battery of the present invention exhibited stable characteristics.
（ト）発明の効果
本発明によればガス通路板のカソード極と接触する部分
に耐酸化性・導電性に優れた被覆層が形成されているの
で、電池作動時の高温酸化雰囲気下で接触部分の酸化を
長期間に亘って抑制し、電池特性の安定化を図ることが
できる。(G) Effects of the Invention According to the present invention, a coating layer with excellent oxidation resistance and conductivity is formed on the part of the gas passage plate that comes into contact with the cathode electrode, so that contact may occur under a high-temperature oxidizing atmosphere during battery operation. It is possible to suppress the oxidation of the portion over a long period of time, thereby stabilizing the battery characteristics.
第１図は本発明固体電解質燃料電池の平板状単セル断面
図、第２図は同上の要部拡大断面図、第３図は電池特性
比較図である。
（２）・・・固体電解質層、（３）・・・アノード極、
（４）・・・カソード極、（５）（６）・・・ガス通路
板、（５’）（６゛）・・・ガス溝、（７）・・・被覆
層、（８）・・・溜部、（９）・・・シール用融体。FIG. 1 is a sectional view of a flat single cell of the solid electrolyte fuel cell of the present invention, FIG. 2 is an enlarged sectional view of the same main part, and FIG. 3 is a comparison diagram of cell characteristics. (2)...Solid electrolyte layer, (3)...Anode electrode,
(4)...Cathode electrode, (5)(6)...Gas passage plate, (5')(6゛)...Gas groove, (7)...Coating layer, (8)... - Reservoir, (9)...melt for sealing.
Claims (2)
平板状セルの前記各極背面に、耐熱性金属からなるガス
通路板を配置した固体電解質燃料電池において、前記ガ
ス通路板の前記カソード極と接触する部分に耐酸化性、
良導電性の被覆層を形成したことを特徴とする固体電解
質燃料電池。(1) In a solid electrolyte fuel cell in which a gas passage plate made of a heat-resistant metal is arranged on the back surface of each electrode of a flat cell consisting of an anode electrode, a solid electrolyte layer, and a cathode electrode, the cathode electrode of the gas passage plate Oxidation resistance on contact parts,
A solid electrolyte fuel cell characterized by forming a coating layer with good conductivity.
ＬａＣｏＯ＿３あるいはその置換体（Ｌａ＿１＿−＿ｘ
Ｍ＿ｘＣｒＯ＿３Ｍ＝Ｍｇ、Ｃａ、Ｓｒ）から選ばれた
ペロブスカイト型酸化物であることを特徴とする請求項
１の固体電解質燃料電池。(2) The coating layer is LaCrO_3, LaMnO_3,
LaCoO_3 or its substituted product (La_1_-_x
2. The solid electrolyte fuel cell according to claim 1, wherein the solid electrolyte fuel cell is a perovskite oxide selected from M_xCrO_3M=Mg, Ca, Sr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1142816A JPH038264A (en) | 1989-06-05 | 1989-06-05 | Solid electrolyte fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1142816A JPH038264A (en) | 1989-06-05 | 1989-06-05 | Solid electrolyte fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH038264A true JPH038264A (en) | 1991-01-16 |
Family
ID=15324296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1142816A Pending JPH038264A (en) | 1989-06-05 | 1989-06-05 | Solid electrolyte fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH038264A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399442A (en) * | 1993-02-08 | 1995-03-21 | Fuji Electric Co., Ltd. | Solid electrolyte fuel cell |
| EP0714147A1 (en) * | 1994-11-23 | 1996-05-29 | Sulzer Innotec Ag | High-temperature fuel cell with chromium-containing connecting elements between the electrochemical active plates |
| WO1998036464A1 (en) * | 1997-02-15 | 1998-08-20 | Forschungszentrum Jülich GmbH | Interconnector for sofc fuel cell piles |
| WO1998040921A1 (en) * | 1997-03-13 | 1998-09-17 | Forschungszentrum Jülich GmbH | Material for electric contact layers between a high-temperature fuel cell electrode and an interconnector |
| EP1825553A1 (en) * | 2004-11-16 | 2007-08-29 | Versa Power Systems, Ltd. | Electrically conductive fuel cell contact materials |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01100866A (en) * | 1987-10-14 | 1989-04-19 | Toa Nenryo Kogyo Kk | Heat-resisting component |
-
1989
- 1989-06-05 JP JP1142816A patent/JPH038264A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01100866A (en) * | 1987-10-14 | 1989-04-19 | Toa Nenryo Kogyo Kk | Heat-resisting component |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399442A (en) * | 1993-02-08 | 1995-03-21 | Fuji Electric Co., Ltd. | Solid electrolyte fuel cell |
| EP0714147A1 (en) * | 1994-11-23 | 1996-05-29 | Sulzer Innotec Ag | High-temperature fuel cell with chromium-containing connecting elements between the electrochemical active plates |
| WO1998036464A1 (en) * | 1997-02-15 | 1998-08-20 | Forschungszentrum Jülich GmbH | Interconnector for sofc fuel cell piles |
| WO1998040921A1 (en) * | 1997-03-13 | 1998-09-17 | Forschungszentrum Jülich GmbH | Material for electric contact layers between a high-temperature fuel cell electrode and an interconnector |
| EP1825553A1 (en) * | 2004-11-16 | 2007-08-29 | Versa Power Systems, Ltd. | Electrically conductive fuel cell contact materials |
| EP1825553A4 (en) * | 2004-11-16 | 2012-01-11 | Versa Power Systems Ltd | Electrically conductive fuel cell contact materials |
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