JPH0215573A - Molten carbonate type fuel cell - Google Patents
Molten carbonate type fuel cellInfo
- Publication number
- JPH0215573A JPH0215573A JP63165620A JP16562088A JPH0215573A JP H0215573 A JPH0215573 A JP H0215573A JP 63165620 A JP63165620 A JP 63165620A JP 16562088 A JP16562088 A JP 16562088A JP H0215573 A JPH0215573 A JP H0215573A
- Authority
- JP
- Japan
- Prior art keywords
- molten carbonate
- electrolyte
- electrode
- fuel cell
- cathode
- 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.)
- Granted
Links
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 18
- 239000000446 fuel Substances 0.000 title claims description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- 239000011159 matrix material Substances 0.000 claims abstract description 15
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 9
- 230000000717 retained effect Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910010092 LiAlO2 Inorganic materials 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- -1 was assembled Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M8/14—Fuel cells with fused electrolytes
- H01M8/141—Fuel cells with fused electrolytes the anode and the cathode being gas-permeable electrodes or electrode layers
- H01M8/142—Fuel cells with fused electrolytes the anode and the cathode being gas-permeable electrodes or electrode layers with matrix-supported or semi-solid matrix-reinforced electrolyte
-
- 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
- H01M8/14—Fuel cells with fused electrolytes
- H01M2008/147—Fuel cells with molten carbonates
-
- 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
- H01M2300/0048—Molten electrolytes used at high temperature
- H01M2300/0051—Carbonates
-
- 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
- H01M8/14—Fuel cells with fused electrolytes
- H01M8/148—Measures, other than selecting a specific electrode material, to reduce electrode dissolution
-
- 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
- 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)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野）
この発明は、改良された溶融炭酸塩型燃料電池に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field] This invention relates to an improved molten carbonate fuel cell.
［従来の技術ｊ
図面は、例えば刊行物（三菱電機枝根Ｖｏ１．５８・Ｎ
Ｏ１９・１９８４ 、Ｐ５１〜５２）に示された一般的
な溶融炭酸塩型燃料電池の単電池を示す断面図である。[Prior art j The drawings are, for example, published in the publication (Mitsubishi Electric Branch Vol. 1.58/N
019/1984, pages 51-52) is a cross-sectional view showing a unit cell of a general molten carbonate fuel cell.
（１）はＮ１電極でＮ１多孔質板によるアノード、（２
）はＮｉ０ｔ極でＮｉＯ多孔質板によるカソード、（３
）は例えばＬｉ ＡｌＯ２で形成された電解質マトリク
スである。電解質には通常溶融炭酸塩として ６２ ｍ
ｏｌＪ Ｌｉ ２ ＣＯ３−３８ｍｏ１４に２ｃＯ３の
共融混合物を用いている。（４） （５）はそれぞれ燃
料酸化剤ガスの出入口のパイプであり、（６）（７）は
それぞれのガスの流路、（８） （９）はセル枠である
。(1) is the N1 electrode, an anode made of N1 porous plate, (2
) is a Ni0t electrode with a cathode made of a NiO porous plate, (3
) is an electrolyte matrix formed of, for example, LiAlO2. The electrolyte usually contains 62 m as molten carbonate.
A eutectic mixture of 2cO3 in olJ Li2CO3-38mol4 is used. (4) and (5) are the inlet and outlet pipes for the fuel oxidizing gas, (6) and (7) are the flow paths for the respective gases, and (8) and (9) are the cell frames.
次にこの種の溶融炭酸塩型燃料電池の動作について説明
する。燃料電池は、水素などの燃料ガスと、空気などの
酸化剤ガスのもつ化学エネルギーを電気化学的な反応に
よって、直接電気エネルギーに変換し、電力を得る装置
である。このｔ気化学反応を効率良く行わせるために、
一般的には、多孔質な！極が用いられる。７ノードおよ
びカソードにおける反応は次の通夛である。Next, the operation of this type of molten carbonate fuel cell will be explained. A fuel cell is a device that directly converts the chemical energy of a fuel gas such as hydrogen and an oxidant gas such as air into electrical energy through an electrochemical reaction to obtain electric power. In order to carry out this gas chemical reaction efficiently,
In general, porous! poles are used. The reactions at the 7 nodes and cathode are as follows.
７ノード Ｎ２＋ＣＯ３−４Ｈ２０＋ｃｏ２＋２ｅ−
・・・（１）カソード ＣＯ２”／２０２＋２ａ−Ｃ
Ｏｉ−・＝（２）アノードでは式（１）に示される様に
燃料のＮ２は電解質中のＣ０＝−と反応し、水とＣＯ２
と′電子を生成する。この電子は、アノードを通して外
部負荷に送られた後、カソードに流れ込ひ。カソードで
は、この電子と００２および酸化剤の０２からＣＯ２３
−を生成し、電解質中に溶解することによって電池反応
が進行する。7 nodes N2+CO3-4H20+co2+2e-
...(1) Cathode CO2"/202+2a-C
Oi-・=(2) At the anode, as shown in equation (1), N2 in the fuel reacts with C0=- in the electrolyte, forming water and CO2.
and ′ generate electrons. The electrons are sent to an external load through the anode and then flow into the cathode. At the cathode, CO23 from this electron and 002 and the oxidizing agent 02
The battery reaction progresses by producing - and dissolving it in the electrolyte.
〔発明が解決しようとする課題］
従来の溶融炭酸塩型燃料電池は以上のように構成されて
いるが、電池運転中に、カソード（Ｎｉｐ）が電解質中
に式（３）の反応で溶解する。[Problem to be solved by the invention] A conventional molten carbonate fuel cell is configured as described above, but during cell operation, the cathode (Nip) dissolves in the electrolyte by the reaction of formula (3). .
ＮｉＯ＋ Ｃｏ ２− Ｎｉ” ＋ Ｃｏ七
−（３）この現象によって、カソードの定電反応
面積が減少したシ、カソードと電解質マトリクス層との
間の接触が悲くなシ、電池特性に息影響を及ぼすという
問題点があった。また、溶解したＮｉ２＋はマトリクス
中に拡散し、７ノード側から拡散してくるＮ２によって
還元さ７Ｌ％金＠Ｎｉとしてマトリクス中に析出するの
で、電池の電気的短絡を生じるという問題点があった。NiO+ Co 2- Ni” + Co7
(3) This phenomenon causes problems such as a decrease in the electrostatic reaction area of the cathode, poor contact between the cathode and the electrolyte matrix layer, and adversely affecting battery characteristics. In addition, dissolved Ni2+ diffuses into the matrix, is reduced by N2 diffusing from the 7 node side, and precipitates in the matrix as 7L% gold@Ni, which causes an electrical short circuit in the battery. .
この発明は、上記のような課題を解消するためになされ
たもので、長期間安定な電池特性を維持する溶融炭酸塩
型燃料電池を得ることを目的とする。This invention was made to solve the above-mentioned problems, and aims to obtain a molten carbonate fuel cell that maintains stable cell characteristics for a long period of time.
〔課題を解決するための手段Ｊ
この発明の溶融炭酸塩型燃料電池は、Ｎｉ電極とＮｉＯ
電極で挟持され、電解質マトリックスに保持される溶融
炭酸塩がマグネシウムイオンを５０〜２００Ｑｐｐｔｎ
含有するものである。[Means for Solving the Problems J The molten carbonate fuel cell of this invention has a Ni electrode and a NiO
The molten carbonate sandwiched between the electrodes and retained in the electrolyte matrix carries magnesium ions at 50-200Qpptn.
It contains.
［作用」
この発明におけるマグネシウムイオンヲ含む電解質の使
用によシ、運転中のＮｉＯカソードの電解質への溶解量
を減少させ、カソードの損傷と電極の短絡を防止するこ
とができる。[Function] By using the electrolyte containing magnesium ions in the present invention, the amount of NiO cathode dissolved in the electrolyte during operation can be reduced, and damage to the cathode and short circuit of the electrodes can be prevented.
〔実施例］ 以下、この発明の一実施例を説明する。〔Example] An embodiment of this invention will be described below.
例えば従来の電解質（６２ｍｏ１４Ｌｉ２ ＣＯａ −
３８ｍｏ１％に２ＣＯ３）に１ ｍｏｌ Ｎの塩基性炭
酸マグネシウム（３Ｍｇｃｏ３・Ｍｇ（ＯＨ）ｚ・３Ｈ
２０）を混合し、６５０℃で融解させた。冷却後、との
電解質中のＭ２Ｒ度を測定したところ約２０００重量ｐ
ｐｍであった。この電解質を使用して、Ｎ１７ノード、
ＮｉＯカソード、ＬｉＡｌＯ２電解質マトリクスから構
成される図面に示すような有効電極面積２５ｅｓＩの単
電池を組み立て、６５０℃で、燃料ガス８０４Ｈｚ−２
０％ｃｏ２ 、酸化剤ガス７０％Ａｉｒ −３０＊ＣＯ
ｚを用いて運転を行った。電池特性は燃料、酸化剤ガス
利用率ともに４０’Ｊ６ 、１５０ｍＡ／ｃｄで０．８
５Ｖで、従来の電解質を用いた場合と同等であった約１
０００時間運転した後、電池を分解し、電解質マトリク
スに含まれるＮ１の屋を分析した結果、従来、 ｌ
の電解質を用いた場合とくらへて釘程度に減少していた
。また、マトリクス断面の＊＊＊ａ察からも、マトリク
ス中に析出しているＮ１が、従来の電解質を用いた場合
より、はるかに少ないことが確認された。For example, conventional electrolyte (62mo14Li2 COa −
1 mol N of basic magnesium carbonate (3Mgco3・Mg(OH)z・3H
20) were mixed and melted at 650°C. After cooling, the M2R degree in the electrolyte was measured and was approximately 2000 p
It was pm. Using this electrolyte, the N17 node,
A unit cell with an effective electrode area of 25 esI as shown in the drawing, consisting of a NiO cathode and a LiAlO2 electrolyte matrix, was assembled, and a fuel gas of 804 Hz-2 was heated at 650°C.
0% CO2, Oxidizing gas 70% Air -30*CO
Driving was performed using z. The cell characteristics are 0.8 at 40'J6 and 150mA/cd for both fuel and oxidizing gas utilization rates.
At 5V, approximately 1
After 1,000 hours of operation, the battery was disassembled and the amount of N1 contained in the electrolyte matrix was analyzed. As a result, it was found that the amount of N1 contained in the electrolyte matrix was reduced to the level of a nail, much less than when using a conventional electrolyte of 1,000 hours. Furthermore, it was confirmed from ***a observation of the cross section of the matrix that the amount of N1 precipitated in the matrix was much less than when a conventional electrolyte was used.
なお、この発明に係わるマグネシウムイオンは５０〜２
０００ｐｐｍ含まれる。 ５０ｐｐｍ以下ではＮｉＯカ
ソードの溶解量低減の効果が少なく、２０００ｐｐｍ以
上含ませても溶解量低減の効果の増大が見られなヘス、
マグネシウムイオンを含む化合物として、塩基性炭酸マ
グネシウム（３ＭｇＣＯｘ−Ｍｇ（ＯＨ）２”３ＨｚＯ
）を用いたが、これに限らず、ＭｇＣＯ５・３１１２Ｑ
、 ＭｇＯ。In addition, the magnesium ion related to this invention is 50 to 2
Contains 000ppm. If the content is less than 50 ppm, the effect of reducing the amount of dissolved NiO cathode is small, and even if it is contained more than 2000 ppm, no increase in the effect of reducing the amount of dissolved NiO is observed.
As a compound containing magnesium ions, basic magnesium carbonate (3MgCOx-Mg(OH)2”3HzO
) was used, but is not limited to this, MgCO5・3112Q
, MgO.
Ｍｇ（ｏ１２などでも同様の効果を示す。Similar effects are also shown with Mg(o12, etc.).
又、ＲＩ融炭酸塩の種類も上記実施例に限定されない。Furthermore, the type of RI molten carbonate is not limited to the above examples.
さらｇ、Ｎｉｏカソードの電解質中への溶解量を低減さ
せるのに、効果のあるものとして、マグネシウムと同じ
アルカリ土類金属の例えばカルシウムイオン、バリウム
イオンおよびストロンチウムイオンがある。Additionally, alkaline earth metals like magnesium, such as calcium ions, barium ions, and strontium ions, are effective in reducing the amount of Nio cathode dissolved in the electrolyte.
［発明の効果］
以上説明し九とおシ、この発明はＮｉ電極とＮ１Ｑｔ極
で挟持され、電解質マトリックスに保持される溶融炭酸
塩がマグネシウムイオンを５０〜２０００ｐｐｍ含有す
るものを用いることによ）、長期間安定な電池特性を維
持する溶融炭酸塩型燃料電池を得ることができる。[Effects of the Invention] As explained above, this invention uses a molten carbonate sandwiched between a Ni electrode and a N1Qt electrode and held in an electrolyte matrix containing 50 to 2000 ppm of magnesium ions), A molten carbonate fuel cell that maintains stable cell characteristics for a long period of time can be obtained.
図面は一般的な溶融炭酸塩型燃料電池の断面図である。
図において、（１）はＮ１電極、Ｃ２）はＮｉＯ電極、
（３）は電解質マトリックスである。The drawing is a cross-sectional view of a typical molten carbonate fuel cell. In the figure, (1) is the N1 electrode, C2) is the NiO electrode,
(3) is an electrolyte matrix.
Claims (1)
に保持される溶融炭酸塩がマグネシウムイオンを５０〜
２０００ｐｐｍ含有する溶融炭酸塩型燃料電池。The molten carbonate sandwiched between Ni and NiO electrodes and held in the electrolyte matrix absorbs magnesium ions from 50 to
Molten carbonate fuel cell containing 2000 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63165620A JP2658207B2 (en) | 1988-06-30 | 1988-06-30 | Molten carbonate fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63165620A JP2658207B2 (en) | 1988-06-30 | 1988-06-30 | Molten carbonate fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0215573A true JPH0215573A (en) | 1990-01-19 |
| JP2658207B2 JP2658207B2 (en) | 1997-09-30 |
Family
ID=15815823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63165620A Expired - Lifetime JP2658207B2 (en) | 1988-06-30 | 1988-06-30 | Molten carbonate fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2658207B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5110226A (en) * | 1990-10-19 | 1992-05-05 | Norand Corporation | Battery operated data entry terminal device and printer attachment |
| JP2007238075A (en) * | 2006-02-09 | 2007-09-20 | Nsk Ltd | Electric steering device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6056375A (en) * | 1983-09-07 | 1985-04-01 | Agency Of Ind Science & Technol | Molten-carbonate-type fuel cell |
-
1988
- 1988-06-30 JP JP63165620A patent/JP2658207B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6056375A (en) * | 1983-09-07 | 1985-04-01 | Agency Of Ind Science & Technol | Molten-carbonate-type fuel cell |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5110226A (en) * | 1990-10-19 | 1992-05-05 | Norand Corporation | Battery operated data entry terminal device and printer attachment |
| JP2007238075A (en) * | 2006-02-09 | 2007-09-20 | Nsk Ltd | Electric steering device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2658207B2 (en) | 1997-09-30 |
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