JP2719363B2 - Molten carbonate fuel cell - Google Patents
Molten carbonate fuel cellInfo
- Publication number
- JP2719363B2 JP2719363B2 JP63261701A JP26170188A JP2719363B2 JP 2719363 B2 JP2719363 B2 JP 2719363B2 JP 63261701 A JP63261701 A JP 63261701A JP 26170188 A JP26170188 A JP 26170188A JP 2719363 B2 JP2719363 B2 JP 2719363B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- fuel cell
- molten carbonate
- battery
- electrolyte
- 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 - Fee Related
Links
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
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
-
- 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
-
- 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)
Description
【発明の詳細な説明】 （イ） 産業上の利用分野 本発明は溶融炭酸塩燃料電池に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Industrial application field The present invention relates to a molten carbonate fuel cell.
（ロ） 従来の技術 溶融炭酸塩燃料電池の電解質は、多孔質セラミツクス
体に溶融炭酸塩を保持させたもので、その作成に際し、
先づ電解質保持材の微粉末に可塑剤・バインダーを加え
て得たシートを対極間に介在させて電池に組立て、電池
昇温過程で前記シートから可塑剤・バインダーを除去し
て多孔性保持体とした後、これに溶融炭酸塩を含浸させ
る方式は周知である。この方式は電池組立時完成電解質
板を組込む場合に比しソフトなシートを用いるため、締
付圧によつて割れの生ずるおそれなく、また生産性にす
ぐれているという利点がある。(B) Conventional technology The electrolyte of a molten carbonate fuel cell is a porous ceramic body that holds molten carbonate.
First, a sheet obtained by adding a plasticizer / binder to the fine powder of the electrolyte holding material is interposed between the counter electrodes to assemble into a battery, and the plasticizer / binder is removed from the sheet in the process of raising the temperature of the battery, and the porous holding body is removed. Then, a method of impregnating this with a molten carbonate is well known. Since this method uses a softer sheet than when a completed electrolyte plate is incorporated at the time of assembling the battery, it has the advantage that there is no risk of cracking due to the tightening pressure and the productivity is excellent.
しかし可塑剤・バインダーの熱分解生成物もしくはそ
の不完全燃焼物を完全に燃焼するにはガススペースに酸
素を含むガスの供給が必要となるため、アノード極やそ
の背面スペースに保持した改質触媒が強く酸化されて特
性の劣化をともなう。又供給ガスの酸素濃度を低くおさ
えると不完全燃焼となつて熱分解で生成したオレフイン
類などが、炭素としてセル構成材に析出したり、タール
として温度の低い配管部分に付着するなどの問題があつ
た。However, in order to completely burn off the pyrolysis products of plasticizers / binders or their incompletely burned products, it is necessary to supply oxygen-containing gas to the gas space. Is strongly oxidized, resulting in deterioration of characteristics. In addition, if the oxygen concentration of the supply gas is kept low, olefins generated by thermal decomposition due to incomplete combustion will precipitate as carbon on the cell constituent materials, and will adhere as tar to the low temperature piping. Atsuta.
（ハ） 発明が解決しようとする課題 本発明は電解質保持体となるシート中の有機物を、電
極や改質触媒を損うことのない比較的低温低酸素濃度下
で分解燃焼させることにより、前記問題点を解消するも
のである。(C) Problems to be Solved by the Invention The present invention is to decompose and burn an organic substance in a sheet serving as an electrolyte holder at a relatively low temperature and a low oxygen concentration without damaging an electrode or a reforming catalyst. This is to solve the problem.
（ニ） 課題を解決するための手段 本発明は、電解質保持材の微粉末に可塑剤・バインダ
ーなどを加えて得たシートをアノード極・カソード極間
に介在させて電池に組立て、電池昇温過程で前記シート
から添加有機物を除去して溶融電解質が含浸される多孔
性保持体に作成する溶融炭酸塩燃料電池において、前記
各極背面のガススペースのうち、少くともアノード側ス
ペースに、前記可塑剤・バインダーの燃焼促進触媒を保
持したものである。又、アノード側スペースの燃焼促進
触媒は、内部改質型電池の場合改質触媒と分離してもし
くは混合して保持される。(D) Means for Solving the Problems According to the present invention, a sheet obtained by adding a plasticizer, a binder, and the like to fine powder of an electrolyte holding material is interposed between an anode electrode and a cathode electrode to assemble into a battery, and the temperature of the battery is raised. In a molten carbonate fuel cell produced in a porous support impregnated with a molten electrolyte by removing added organic substances from the sheet in the process, at least the anode side space among the gas spaces on the back side of each of the electrodes is provided with the plasticized material. It holds the catalyst for promoting the combustion of the agent / binder. In the case of an internal reforming type battery, the combustion promoting catalyst in the anode side space is held separately from or mixed with the reforming catalyst.
（ホ） 作用 本発明は電池昇温過程でシート中に含まれた有機物
は、燃焼促進触媒の存在により熱分解後短時間で完全燃
焼しガスとして排出されるため、電極や改質触媒を汚染
することなく、有機物を完全に除去することができる。(E) Function In the present invention, the organic matter contained in the sheet in the process of raising the temperature of the battery is completely burned in a short time after thermal decomposition due to the presence of the combustion promoting catalyst and is discharged as gas, so that the electrode and the reforming catalyst are contaminated. The organic matter can be completely removed without performing.
（ヘ） 実施例 第１図は本発明電池の要部斜面図、第２図は同上単セ
ルの模式的断面図である。(F) Example FIG. 1 is a perspective view of an essential part of the battery of the present invention, and FIG. 2 is a schematic sectional view of the single cell of the battery.
電解質保持体となるシート（１）は、電解質保持材と
してｒ−リチウムアルミネートの微粉末に、可塑剤（例
えばフタル酸ジオクチル）・バインダー（例えばポリビ
ニルブチラール樹脂）及び溶媒（例えばエタノール）を
加えて充分混合し、得られたスラリーを通常のテープキ
ヤステイング法によりテープ状とし、ホツトプレスして
溶媒を揮散させたものである。このようにして作成され
たシート（１）はアノード極（２）・カソード極（３）
間に介在させ、集電板（４）、波板（５）及びガス分離
板（６）と共に電池に組立てられる。The sheet (1) serving as an electrolyte retainer is prepared by adding a plasticizer (for example, dioctyl phthalate), a binder (for example, polyvinyl butyral resin) and a solvent (for example, ethanol) to fine powder of r-lithium aluminate as an electrolyte retainer. The slurry was sufficiently mixed, and the resulting slurry was formed into a tape by a usual tape casting method, and hot-pressed to evaporate the solvent. The sheet (1) thus prepared is composed of an anode (2) and a cathode (3).
The battery is assembled together with the current collector plate (4), the corrugated plate (5) and the gas separator plate (6).
ニツケルアルミ合金の焼結体よりなるアノード極
（２）及びニツケル焼結体よりなるカソード極（３）に
は、組立前に予め電解質成分が含浸されている。The anode electrode (2) made of a nickel aluminum alloy sintered body and the cathode electrode (3) made of a nickel sintered body are impregnated with an electrolyte component before assembly.
本発明では組立時ガススペースの波板（５）に燃焼促
進触媒（７）が保持される。第１図及び第２図の実施例
では燃焼促進触媒（７）がアノード側ガススペースにの
み設けた場合、又第３図の他実施例ではアノード側・カ
ソード側両スペースに設けた場合を示す。更に第４図・
第５図のもう一つの実施例（内部改質型電池）では、ア
ノードガススペースの燃焼促進触媒（７）が改質触媒
（８）と分離して〔波板（５）により〕及び混合して設
けられた場合を夫々示す。In the present invention, the combustion promoting catalyst (7) is held on the corrugated plate (5) in the gas space during assembly. 1 and 2 show the case where the combustion promoting catalyst (7) is provided only in the anode side gas space, and the other embodiment in FIG. 3 shows the case where it is provided in both the anode side and cathode side spaces. . Fig. 4
In another embodiment (internal reforming type battery) shown in FIG. 5, the combustion promoting catalyst (7) in the anode gas space is separated from the reforming catalyst (8) [by the corrugated plate (5)] and mixed. Each case is shown.
この触媒（７）はアルミナなどのセラミツクス粒子を
担体として夫々ｒ−Mno2、白金、銅系などの触媒を担持
させたものである。The catalyst (7) is a catalyst in which a ceramic particle such as alumina is used as a carrier and a catalyst such as r-Mno 2 , platinum or copper is supported on the carrier.
前記の如く組立てられた電池は、常温から電池作動温
度の約650℃まで除々に昇温される。この昇温過程にお
いて両ガススペース共にN2で希釈された空気を供給する
が、約200〜230℃でシート（１）中の可塑剤やバインダ
ーが熱分解をはじめる。しかしこの時の温度が低いため
熱分解生成物は完全燃焼されることなく電極や改質触媒
に炭素として析出付着したり、タール状の排出物となつ
て配管に付着するおそれがあり、又供給されるガスの酸
素分圧を上げても完全燃焼は望めず、むしろ電極が強く
酸化されアノード極では後の還元工程でも復元しない。The battery assembled as described above is gradually heated from room temperature to a battery operating temperature of about 650 ° C. In this heating process, air diluted with N 2 is supplied to both gas spaces. At about 200 to 230 ° C., the plasticizer and the binder in the sheet (1) start to thermally decompose. However, since the temperature at this time is low, the pyrolysis products may not be completely burned and may deposit and adhere to the electrodes and reforming catalyst as carbon, or may become tar-like emissions and adhere to the pipes. Even if the oxygen partial pressure of the gas used is increased, complete combustion cannot be expected. Rather, the electrode is strongly oxidized and the anode electrode is not restored even in the subsequent reduction step.
所が、本発明ではこのような熱分解生成物やその不完
全燃焼物は燃焼促進触媒（７）により比較的低温度低酸
素分圧下次の反応式で表わせるような反応で、ガス体と
して除去される。However, in the present invention, such a pyrolysis product or an incompletely combusted product is converted into a gaseous substance by a reaction which can be represented by the following reaction formula under a relatively low temperature and low oxygen partial pressure by the combustion promoting catalyst (7). Removed.
従つてシート（１）中の可塑剤やバインダーは昇温温
度約370℃までの比較的短期間で除去されるので、供給
ガスの酸素分圧を早い時期に低減ないしは零にすること
が可能で、アノード極（２）や改質触媒（８）が強く酸
化されるのを防止する。尚有機物の分解除去時に発生す
るガスは、電解質を保持する電極（２）（３）の孔部
（残留多孔度15〜17％）を通つてガススペースから送り
出される。 Therefore, since the plasticizer and binder in the sheet (1) are removed in a relatively short period of time up to a temperature rise of about 370 ° C., the oxygen partial pressure of the supplied gas can be reduced or eliminated at an early stage. In addition, the anode (2) and the reforming catalyst (8) are prevented from being strongly oxidized. The gas generated at the time of decomposing and removing the organic matter is sent out of the gas space through the holes (residual porosity of 15 to 17%) of the electrodes (2) and (3) holding the electrolyte.
その後アノードガススペースには、H2・CO2を含むN2
ガスを、カソードガススペースには、CO2を含むN2で希
釈された空気を夫々供給する。やがて500℃程度で電極
（２）（３）中の炭酸塩が溶融し、前記の如くシートか
ら可塑剤・バインダーが除去された多孔質保持体に含浸
されて電解質板を構成する。尚炭酸塩が溶融しはじめる
と各ガススペースに供給されるガス中のCO2濃度を除々
にあげて行く。Subsequent anode gas space, including H 2 · CO 2 N 2
The gas is supplied to the cathode gas space with air diluted with N 2 containing CO 2 . Eventually, the carbonate in the electrodes (2) and (3) is melted at about 500 ° C. and impregnated in the porous holder from which the plasticizer / binder has been removed from the sheet as described above to form an electrolyte plate. When the carbonate begins to melt, the CO 2 concentration in the gas supplied to each gas space is gradually increased.
やがて電池が作動温度（650℃）に近づくと、各極ガ
ススペースに規定のガスを供給して電池反応を開始す
る。即ち、アノードガススペースに改質触媒が保持され
ている内部改質型の場合は、天然ガスとスチームの混合
原料ガスを供給するが、外部改質型の場合改質された燃
料ガスを供給する。又カソードガススペースには、空気
にCO2を混合した酸化剤ガスを供給する。Eventually, when the battery approaches the operating temperature (650 ° C), the specified gas is supplied to each gas space to start the battery reaction. That is, in the case of the internal reforming type in which the reforming catalyst is held in the anode gas space, a mixed raw material gas of natural gas and steam is supplied, whereas in the case of the external reforming type, the reformed fuel gas is supplied. . An oxidizing gas in which CO 2 is mixed with air is supplied to the cathode gas space.
電池の運転時燃焼促進触媒（７）は電池反応に支障を
きたすことなく、そのままガススペースに保持されてい
る。During the operation of the battery, the combustion promoting catalyst (7) is held in the gas space as it is without any hindrance to the battery reaction.
（ト） 発明の効果 本発明によれば、電解質保持材を含むシートを電池に
組込み電池昇温過程でシート中の有機物を分解除去して
多孔質保持体を形成する電池において、電池組立時電極
背面のガススペースに、有機物の燃焼促進触媒を設けた
ので、有機物は比較的低温度・低酸素濃度下短時間で完
全燃焼しガス体として排出されるため、熱分解生成物や
その不完全燃焼物により電極や配管の汚染特にアノード
極や改質触媒の汚染劣化するおそれがなくなり、電池特
性と寿命を大巾に改善する効果がある。(G) Effects of the Invention According to the present invention, in a battery in which a sheet containing an electrolyte holding material is incorporated into a battery to decompose and remove organic substances in the sheet during a battery heating process to form a porous holding body, a battery assembling electrode is provided. Since a combustion promotion catalyst for organic matter is provided in the gas space on the back side, organic matter is completely burned in a short time under a relatively low temperature and low oxygen concentration and is discharged as a gaseous substance. There is no danger of contamination of the electrodes and pipes, particularly of the anode electrode and the reforming catalyst, by the material, and the effect of greatly improving the battery characteristics and life is obtained.
第１図は本発明電池の要部斜面図、第２図は同上単セル
の模式的断面図、第３図は他実施例を示す拡大断面図、
第４図及び第５図は内部改質型電池に本発明を適用した
異る実施例を示す拡大断面図及び要部拡大断面図であ
る。 1:電解質保持材を含むシート、2:アノード極、3:カソー
ド極、5:波板、6:ガス分離板、7:燃焼促進触媒、8:改質
触媒。1 is a perspective view of a main part of the battery of the present invention, FIG. 2 is a schematic cross-sectional view of the single cell, and FIG. 3 is an enlarged cross-sectional view showing another embodiment.
4 and 5 are an enlarged cross-sectional view and a main part enlarged cross-sectional view showing a different embodiment in which the present invention is applied to an internal reforming type battery. 1: sheet containing an electrolyte retainer, 2: anode, 3: cathode, 5: corrugated plate, 6: gas separation plate, 7: combustion promoting catalyst, 8: reforming catalyst.
Claims (4)
ーを加えて得たシートをアノード極・カソード極間に介
在させて電池に組立て、電池昇温過程で前記シートから
可塑剤・バインダーを除去して多孔性保持体とした後溶
融電解質を含浸せしめる溶融炭酸塩燃料電池において、
前記各極背面のガススペースのうち少くともアノード側
スペースに、前記可塑剤・バインダーの燃焼促進触媒を
保持していることを特徴とする溶融炭酸塩燃料電池。1. A sheet obtained by adding a plasticizer / binder to fine powder of an electrolyte-holding material is interposed between an anode and a cathode to assemble into a battery, and the plasticizer / binder is removed from the sheet during the battery heating process. In a molten carbonate fuel cell which is impregnated with a molten electrolyte after being removed to form a porous support,
A molten carbonate fuel cell, wherein the combustion promoting catalyst for the plasticizer / binder is held in at least the anode side space among the gas spaces on the back surfaces of the poles.
触媒と分離してもしくは混合して改質触媒が設けられて
いることを特徴とする請求項１の溶融炭酸塩燃料電池。2. The molten carbonate fuel cell according to claim 1, wherein a reforming catalyst is provided in the anode side space separately or mixed with the combustion promoting catalyst.
は一方に、前記多孔性保持体に移行含浸される電解質が
組立時予め保持されていることを特徴とする請求項１の
溶融炭酸塩燃料電池。3. A molten carbonate fuel cell according to claim 1, wherein an electrolyte which is transferred and impregnated into said porous holder is held in advance in one or both of said anode electrode and cathode electrode during assembly. .
触媒もしくは銅系触媒を、担体としてアルミナなどのセ
ラミツク粒子に担持されたものであることを特徴とする
請求項１の溶融炭酸塩燃料電池。4. The molten carbonate according to claim 1, wherein the combustion-promoting catalyst comprises an r-Mno 2 catalyst, a platinum catalyst or a copper catalyst supported on ceramic particles such as alumina as a carrier. Salt fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63261701A JP2719363B2 (en) | 1988-10-18 | 1988-10-18 | Molten carbonate fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63261701A JP2719363B2 (en) | 1988-10-18 | 1988-10-18 | Molten carbonate fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02109270A JPH02109270A (en) | 1990-04-20 |
| JP2719363B2 true JP2719363B2 (en) | 1998-02-25 |
Family
ID=17365512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63261701A Expired - Fee Related JP2719363B2 (en) | 1988-10-18 | 1988-10-18 | Molten carbonate fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2719363B2 (en) |
-
1988
- 1988-10-18 JP JP63261701A patent/JP2719363B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02109270A (en) | 1990-04-20 |
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