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JPH038065B2 - - Google Patents
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JPH038065B2 - - Google Patents

Info

Publication number
JPH038065B2
JPH038065B2 JP59150691A JP15069184A JPH038065B2 JP H038065 B2 JPH038065 B2 JP H038065B2 JP 59150691 A JP59150691 A JP 59150691A JP 15069184 A JP15069184 A JP 15069184A JP H038065 B2 JPH038065 B2 JP H038065B2
Authority
JP
Japan
Prior art keywords
fuel cell
molten carbonate
manifold
corrosion
main body
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
Application number
JP59150691A
Other languages
Japanese (ja)
Other versions
JPS6129074A (en
Inventor
Hakaru Ogawa
Kenji Murata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toshiba Corp
Original Assignee
Tokyo Shibaura Electric Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tokyo Shibaura Electric Co Ltd filed Critical Tokyo Shibaura Electric Co Ltd
Priority to JP59150691A priority Critical patent/JPS6129074A/en
Publication of JPS6129074A publication Critical patent/JPS6129074A/en
Publication of JPH038065B2 publication Critical patent/JPH038065B2/ja
Granted legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/24Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465Details of groupings of fuel cells
    • H01M8/2484Details of groupings of fuel cells characterised by external manifolds
    • H01M8/2485Arrangements for sealing external manifolds; Arrangements for mounting external manifolds around a stack
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/24Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/244Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes with matrix-supported molten electrolyte
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Description

【発明の詳細な説明】 〔発明の技術分野〕 本発明は、経時的な特性劣化を抑制するように
した溶融炭酸塩型燃料電池に関する。
DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a molten carbonate fuel cell that suppresses deterioration of characteristics over time.

〔発明の技術的背景とその問題点〕[Technical background of the invention and its problems]

近年、次世代の燃料電池として溶融炭酸塩型燃
料電池の開発が進められている。溶融炭酸塩型燃
料電池は、炭素塩からなる電解質を高温下で溶融
状態にし、電極反応を生起させるもので、リン酸
型、固体電解質型等の他の燃料電池に比べ、電極
反応が起り易く、発電熱効率が高いうえ、効果な
貴金属触媒を必要としない等の特長を有してい
る。
In recent years, molten carbonate fuel cells have been developed as next-generation fuel cells. Molten carbonate fuel cells melt an electrolyte made of carbonate at high temperatures to cause electrode reactions, and electrode reactions occur more easily than other fuel cells such as phosphoric acid and solid electrolyte fuel cells. It has features such as high heat generation efficiency and no need for an effective precious metal catalyst.

ところで、このような溶融炭酸塩型燃料電池で
高出力の発電プラントを構成するには、複数の単
位電池を直列に積層して燃料電池本体を構成し、
各単位電池の加算出力を得るようにしなければな
らない。このため、この種の燃料電池は、通常、
次のように構成される。
By the way, in order to construct a high-output power generation plant using such a molten carbonate fuel cell, it is necessary to construct a fuel cell main body by stacking a plurality of unit cells in series.
It is necessary to obtain the summed output of each unit battery. For this reason, this type of fuel cell typically
It is composed as follows.

すなわち、各単位電池は、一対の多孔質電極板
と、これらの間に介在させたアルカリ炭酸塩から
なる電解質板とから構成される。これら単位電池
は、セパレータを介して積層される。セパレータ
は、各単位電池間の電気的な接続機能と、各電極
板への反応ガスの通路を形成する機能と兼備えた
ものである。
That is, each unit cell is composed of a pair of porous electrode plates and an electrolyte plate made of an alkali carbonate interposed between them. These unit batteries are stacked with separators in between. The separator has both the function of electrical connection between each unit cell and the function of forming a passage for reaction gas to each electrode plate.

燃料電池本体の4つの側面には、反応ガスの分
配、回収機能を有するマニホールドが当てがわれ
ており、これらマニホールドのうちの一つに酸化
剤ガスを供給するとともに、隣接するマニホール
ドに燃料ガスを供給し、燃料電池本体で両ガスを
反応させて直流出力を得た後、それぞれの対向す
るマニホールドからガスを排出させるようにして
いる。上記各単位電池の周縁部には、これら両ガ
スの燃料電池本体内部における交差混合を防止す
るためのウエツトシール部が形成されている。
Manifolds with reactive gas distribution and recovery functions are placed on the four sides of the fuel cell body, and while supplying oxidizing gas to one of these manifolds, fuel gas is supplied to the adjacent manifold. After the gases are supplied and reacted in the fuel cell body to obtain a DC output, the gases are discharged from the respective manifolds facing each other. A wet seal portion is formed at the periphery of each of the unit cells to prevent cross-mixing of both gases inside the fuel cell main body.

ところで、このような構造の燃料電池には、次
のような問題があつた。
By the way, the fuel cell having such a structure has the following problems.

すなわち、上記マニホールドの燃料電池本体側
面との接触部や、セパレータの周縁部は、ウエツ
トシールを形成するため溶融炭酸塩と接触状態に
ある。ところが、炭酸塩は、作動温度で溶融する
と腐蝕性を有するため、これら接触部位の耐食性
が問題となる。そこで、従来は、セパレータやマ
ニホールドの上記部位にアルミナ、ジルコニアな
どの酸化物セラミツク粉未をプラズマ溶射して耐
食層を形成していた。
That is, the contact portion of the manifold with the side surface of the fuel cell main body and the peripheral edge of the separator are in contact with the molten carbonate to form a wet seal. However, since carbonates are corrosive when melted at operating temperatures, the corrosion resistance of these contact areas becomes a problem. Therefore, conventionally, a corrosion-resistant layer was formed by plasma spraying oxide ceramic powder such as alumina or zirconia on the above-mentioned portions of the separator or manifold.

しかしながら、上記の方法で形成された耐食層
には、微細な孔が多数存在し、この微細孔に溶融
炭酸塩が浸透して母材を腐蝕させてしまうという
問題があつた。このように母材が腐蝕すると、耐
食層が母材から剥離し、微小隙間を介して炭酸塩
が移動逸散してしまうことになる。したがつて、
従来の溶融炭酸塩型燃料電池は、経時的な劣化を
免れ得ないという問題があつた。
However, the corrosion-resistant layer formed by the above method has a problem in that there are many fine pores, and molten carbonate penetrates into these fine pores and corrodes the base material. When the base material corrodes in this way, the corrosion-resistant layer peels off from the base material, and carbonate moves and escapes through minute gaps. Therefore,
Conventional molten carbonate fuel cells have had the problem of being subject to deterioration over time.

〔発明の目的〕[Purpose of the invention]

本発明は、上述した問題点に鑑みなされたもの
であり、その目的とするところは、マニホールド
またはセパレータのウエツトシールを形成する面
の耐食性向上を図り、もつて経時的劣化の少ない
溶融炭酸塩型燃料電池を提供することにある。
The present invention has been made in view of the above-mentioned problems, and its purpose is to improve the corrosion resistance of the surface forming the wet seal of the manifold or separator, and to provide a molten carbonate fuel with less deterioration over time. The goal is to provide batteries.

〔発明の概要〕[Summary of the invention]

本発明は、セパレータおよびマニホールドのウ
エツトシール部を形成する面に、酸化物セラミツ
クと酸化クロムとからなる耐食層を設けたことを
特徴としている。
The present invention is characterized in that a corrosion-resistant layer made of oxide ceramic and chromium oxide is provided on the surfaces of the separator and the manifold that form the wet seal portion.

耐食層は、たとえば母材表面に酸化物セラミツ
クをプラズマ溶射した後、酸化クロム溶液を塗布
または噴霧して、しかる後熱処理を施して形成す
るようにしている。
The corrosion-resistant layer is formed by, for example, plasma-spraying oxide ceramic onto the surface of the base material, applying or spraying a chromium oxide solution, and then subjecting it to heat treatment.

〔発明の効果〕〔Effect of the invention〕

本発明によれば、耐食性のある酸化クロムで、
酸化物セラミツク層の微細孔を塞ぐことができる
ため、従来のように溶融炭酸塩が微細孔に浸透す
るのを有効に防止することができる。したがつ
て、マニホールドまたはセパレータの耐食性を向
上させることができ、経時的特性の向上化を図る
ことができる。
According to the present invention, corrosion-resistant chromium oxide,
Since the fine pores of the oxide ceramic layer can be closed, it is possible to effectively prevent molten carbonate from penetrating into the fine pores as in the prior art. Therefore, the corrosion resistance of the manifold or separator can be improved, and the characteristics over time can be improved.

〔発明の実施例〕[Embodiments of the invention]

以下、本発明の実施例について説明する。 Examples of the present invention will be described below.

実施例 1 幅2cm、長さ5cm、厚さ5mmのステンレス板
(SUS316)にアルミナをプラズマ溶射して、厚
さ0.2mmのアルミナ層を形成した。この上から
CrO3の水溶液を塗布し、550℃で熱処理した。上
記CrO3水溶液の塗布と熱処理とを、上記水溶液
がアルミナ層に浸透しなくなるまで繰返し、厚さ
0.1mmの耐食層を形成した。
Example 1 Alumina was plasma sprayed onto a stainless steel plate (SUS316) with a width of 2 cm, a length of 5 cm, and a thickness of 5 mm to form an alumina layer with a thickness of 0.2 mm. from above this
An aqueous solution of CrO 3 was applied and heat treated at 550°C. The application of the above CrO 3 aqueous solution and the heat treatment are repeated until the above aqueous solution no longer penetrates into the alumina layer.
A corrosion-resistant layer of 0.1 mm was formed.

実施例 2 幅2cm、長さ5cm、厚さ5mmのステンレス板
(SUS316)にジルコニアをプラズマ照射して、
厚さ0.2mmのジルコニア層を形成した。この上か
らCrO3の水溶液を噴霧後、550℃で熱処理した。
上記CrO3水溶液の塗布と熱処理とを、上記水溶
液がジルコニア層に浸透しなくなるまで繰返し、
厚さ0.12mmの耐食層を形成した。
Example 2 A stainless steel plate (SUS316) with a width of 2 cm, a length of 5 cm, and a thickness of 5 mm was irradiated with zirconia using plasma.
A zirconia layer with a thickness of 0.2 mm was formed. After spraying an aqueous solution of CrO 3 on this, it was heat-treated at 550°C.
Repeating the application of the CrO 3 aqueous solution and heat treatment until the aqueous solution no longer penetrates into the zirconia layer,
A corrosion-resistant layer with a thickness of 0.12 mm was formed.

従来例 幅2cm、長さ5cm、厚さ5mmのステンレス板
(SUS316)にアルミナをプズマ照射して、厚さ
0.2mmのアルミナ耐食層を形成した。
Conventional example: A stainless steel plate (SUS316) with a width of 2 cm, a length of 5 cm, and a thickness of 5 mm is irradiated with alumina using PSMA.
A 0.2 mm alumina corrosion-resistant layer was formed.

上記実施例1、2および従来例の耐食層を
SEM観察したところ、従来例では、無数の微細
孔が観測されたが、実施例1および実施例2では
空孔が観測されなかつた。また、水銀圧入法で各
耐食層の空孔率を測定したとところ、従来例では
空孔率が20であつたのに対し、実施例1および実
施例2では測定不可能であり、微細孔が少なくと
も0.01μm以下であることが確認された。ちなみ
に、この程度の微細孔であれば、溶融炭酸塩型の
表面張力によつて、炭酸塩が耐食層に浸透するこ
とはない。
The corrosion-resistant layers of Examples 1 and 2 and the conventional example
As a result of SEM observation, countless micropores were observed in the conventional example, but no pores were observed in Examples 1 and 2. In addition, when the porosity of each corrosion-resistant layer was measured by mercury intrusion method, the porosity was 20 in the conventional example, but it was impossible to measure in Examples 1 and 2, and the microporosity was 20. was confirmed to be at least 0.01 μm or less. Incidentally, if the pores are of this size, the carbonate will not penetrate into the corrosion-resistant layer due to the surface tension of the molten carbonate.

また、各サンプルの耐食層に、Li2CO3
K2CO3=62 38(モル比)の混合炭素塩粉末を1
gずつ乗せ、Air/CO2=70/30(モル比)、650℃
の雰囲気下で100時間保持したところ、従来例で
は下地表面(母材)が腐蝕して、耐食層が剥離し
たのに対し、実施例1および実施例2では、耐食
層の剥離は無かつた。
In addition, Li 2 CO 3 /
K 2 CO 3 = 62 38 (mole ratio) mixed carbon salt powder 1
Load each g, Air/CO 2 = 70/30 (molar ratio), 650℃
When held for 100 hours in an atmosphere of .

実施例 3 図に示すような燃料電池本体1を構成した。こ
の燃料電池本体は、エンドプレート2a,2bの
間に、複数の単位電池3をセパレータ4を介して
積層したものである。単位電池は、一対の多孔質
電極板5a,5bの間に電解質板を介挿して構成
されている。電解質板は、Li2CO3/K2CO3
62/38(モル比)の混合炭酸塩粉末と、γ−リチ
ウムアルミネートの保持材とをホツトプレスして
得た。セパレータには、その両面に互いに直交す
る方向に延びる複数のガス通流溝6a,6bを形
成した。
Example 3 A fuel cell main body 1 as shown in the figure was constructed. This fuel cell main body has a plurality of unit cells 3 stacked together with a separator 4 interposed between end plates 2a and 2b. The unit battery is constructed by interposing an electrolyte plate between a pair of porous electrode plates 5a and 5b. The electrolyte plate is Li 2 CO 3 /K 2 CO 3 =
A mixed carbonate powder having a molar ratio of 62/38 and a holding material of γ-lithium aluminate were hot pressed. A plurality of gas flow grooves 6a and 6b extending in directions perpendicular to each other were formed on both surfaces of the separator.

このように構成された燃料電池本体1の各側面
に、それぞれ角型環状のジルコニアフエルト7
a,7b,7c,7dを介してマニホールド8
a,8b,8c,8dを重合させた。ジルコニア
フエルト7a〜7dは、溶融炭酸塩を浸透させて
マニホールド8a〜8dとの間でウエツトシール
を構成する機能を有する。マニホールド8a〜8
dの上記ジルコニアフエルト7a〜7dとの接触
部には、前記実施例1と同様の方法によつて得ら
れた耐食層を形成した。そして、これらマニホー
ルド8a〜8dを図示しない手段で締付けて、燃
料電池を構成した。
A square annular zirconia felt 7 is placed on each side of the fuel cell main body 1 constructed in this way.
Manifold 8 via a, 7b, 7c, 7d
a, 8b, 8c, and 8d were polymerized. The zirconia felts 7a to 7d have the function of permeating molten carbonate and forming a wet seal between them and the manifolds 8a to 8d. Manifold 8a~8
A corrosion-resistant layer obtained by the same method as in Example 1 was formed on the contact portion with the zirconia felts 7a to 7d of d. These manifolds 8a to 8d were then tightened by means not shown to construct a fuel cell.

なお、比較のため、上記従来例と同様の方法で
耐食層を形成したマニホールド9a〜9d(図示
せず)を用いて、上記と同様の燃料電池を構成し
た。
For comparison, a fuel cell similar to that described above was constructed using manifolds 9a to 9d (not shown) in which corrosion-resistant layers were formed in the same manner as in the conventional example.

これら燃料電池を650℃に昇温させ、マニホー
ルド8a,9a側からマニホールド8a,9c側
へ酸化剤ガスPを通流させるとともに、マニホー
ルド8b,9b側からマニホールド8d,9d側
へ燃料ガスQを通流させ、200時間運転した。そ
の後、各マニホールド8a〜8d,9a〜9dを
分解してジルコニアフエルトとの接触部を調べた
ところ、後者のマニホールドには、耐食層の剥離
が生じていたのに対し、前者のマニホールド8a
〜8dには剥離が生じていなかつた。
These fuel cells are heated to 650°C, and oxidizing gas P is passed from the manifolds 8a and 9a to the manifolds 8a and 9c, and fuel gas Q is passed from the manifolds 8b and 9b to the manifolds 8d and 9d. I let it flow and drove it for 200 hours. After that, each manifold 8a to 8d and 9a to 9d was disassembled and the contact parts with the zirconia felt were examined.The latter manifold had peeling of the corrosion-resistant layer, while the former manifold 8a
No peeling occurred between 8d and 8d.

上述した各実施例から明らかな如く、本発明に
よれば、長期に亙つて溶融炭酸塩の移動逸散を防
止でき、経時的劣化の少ない溶融炭酸塩型燃料電
池を提供することができる。
As is clear from the embodiments described above, according to the present invention, it is possible to prevent the movement and escape of molten carbonate over a long period of time, and to provide a molten carbonate fuel cell with little deterioration over time.

【図面の簡単な説明】[Brief explanation of the drawing]

図は本発明の一実施例に係る溶融炭酸塩型燃料
電池の主要部の構成を示す図である。 1……燃料電池本体、2a,2b……エンドプ
レート、3……単位電池、4……セパレータ、5
a,5b……多孔質電極板、6a,6b……ガス
通流溝、7a〜7d……ジルコニアフエルト、8
a〜8d……マニホールド、P……酸化剤ガス、
Q……燃料ガス。
The figure is a diagram showing the configuration of main parts of a molten carbonate fuel cell according to an embodiment of the present invention. 1...Fuel cell main body, 2a, 2b...End plate, 3...Unit cell, 4...Separator, 5
a, 5b... Porous electrode plate, 6a, 6b... Gas flow groove, 7a to 7d... Zirconia felt, 8
a to 8d...manifold, P...oxidizing gas,
Q...Fuel gas.

Claims (1)

【特許請求の範囲】 1 単位電池をセパレータを介して複数積層して
なる燃料電池本体と、この燃料電池本体の各側面
に当てがわれ前記各単位電池のガス通路に反応ガ
スを通流させるマニホールドとを備えた溶融炭酸
塩型燃料電池において、前記セパレータの表面で
かつ前記単位電池を構成する電解質層との間でウ
エツトシール部を形成する面および前記マニホー
ルドの表面でかつ前記燃料電池本体の側面との間
でウエツトシール部を形成する面のうちの少なく
とも一方に、酸化物セラミツクと酸化クロムとか
らなる耐食層を形成してなることを特徴とする溶
融炭酸塩型燃料電池。 2 前記耐食層は、前記セパレータまたはマニホ
ールドの母材表面に前記酸化物セラミツクをプラ
ズマ溶射した後、酸化クロム溶液を塗布または噴
霧して、しかる後熱処理を施して形成されたもの
であることを特徴とする特許請求の範囲第1項記
載の溶融炭酸塩型燃料電池。 3 前記酸化物セラミツクは、アルミナであるこ
とを特徴とする特許請求の範囲第1項または第2
項記載の溶融炭酸塩型燃料電池。 4 前記酸化物セラミツクは、ジルコニアである
ことを特徴とする特許請求の範囲第1項または第
2項記載の溶融炭酸塩型燃料電池。
[Scope of Claims] 1. A fuel cell main body formed by stacking a plurality of unit cells with separators interposed therebetween, and a manifold that is applied to each side of the fuel cell main body and allows reaction gas to flow through the gas passages of each of the unit cells. In a molten carbonate fuel cell comprising: a surface of the separator and a surface forming a wet seal portion with an electrolyte layer constituting the unit cell; and a surface of the manifold and a side surface of the fuel cell main body. A molten carbonate fuel cell characterized in that a corrosion-resistant layer made of oxide ceramic and chromium oxide is formed on at least one of the surfaces forming a wet seal portion between the two. 2. The corrosion-resistant layer is formed by plasma spraying the oxide ceramic on the surface of the base material of the separator or manifold, then applying or spraying a chromium oxide solution, and then subjecting it to heat treatment. A molten carbonate fuel cell according to claim 1. 3. Claim 1 or 2, wherein the oxide ceramic is alumina.
The molten carbonate fuel cell described in . 4. The molten carbonate fuel cell according to claim 1 or 2, wherein the oxide ceramic is zirconia.
JP59150691A 1984-07-20 1984-07-20 Fused carbonate type fuel cell Granted JPS6129074A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP59150691A JPS6129074A (en) 1984-07-20 1984-07-20 Fused carbonate type fuel cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59150691A JPS6129074A (en) 1984-07-20 1984-07-20 Fused carbonate type fuel cell

Publications (2)

Publication Number Publication Date
JPS6129074A JPS6129074A (en) 1986-02-08
JPH038065B2 true JPH038065B2 (en) 1991-02-05

Family

ID=15502342

Family Applications (1)

Application Number Title Priority Date Filing Date
JP59150691A Granted JPS6129074A (en) 1984-07-20 1984-07-20 Fused carbonate type fuel cell

Country Status (1)

Country Link
JP (1) JPS6129074A (en)

Also Published As

Publication number Publication date
JPS6129074A (en) 1986-02-08

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