JPH0343963A - Treatment method for molten carbonate fuel cell - Google Patents

Treatment method for molten carbonate fuel cell

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Publication number
JPH0343963A
JPH0343963A JP1175641A JP17564189A JPH0343963A JP H0343963 A JPH0343963 A JP H0343963A JP 1175641 A JP1175641 A JP 1175641A JP 17564189 A JP17564189 A JP 17564189A JP H0343963 A JPH0343963 A JP H0343963A
Authority
JP
Japan
Prior art keywords
electrolyte
fuel cell
organic binder
temperature
pressure
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
Application number
JP1175641A
Other languages
Japanese (ja)
Other versions
JPH07123049B2 (en
Inventor
Isamu Sone
曽根　勇
Yasuyuki Tsutsumi
泰行 堤
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.)
Hitachi Ltd
Original Assignee
Hitachi 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 Hitachi Ltd filed Critical Hitachi Ltd
Priority to JP1175641A priority Critical patent/JPH07123049B2/en
Publication of JPH0343963A publication Critical patent/JPH0343963A/en
Publication of JPH07123049B2 publication Critical patent/JPH07123049B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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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

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  • Fuel Cell (AREA)

Abstract

PURPOSE:To effectively conduct decomposition and scattering of an organic binder by gasifying the organic binder in an electrolyte plate by directly contacting pressured and heated air to the electrolyte plate. CONSTITUTION:A fuel cell 1 comprising a cathode 1a, an anode 1b, and an electrolyte plate 1c is accommodated into a pressure vessel 2. An oxidizing gas is supplied to the cathode 1a through a flow rate control valve 3 and a flow meter 6, and a fuel gas is supplied to the anode 1b through a flow rate control valve 4 and a flow meter 7. The fuel cell 1 generates power in the pressure vessel under a specified pressure and at a specified temperature. When the temperature of the fuel cell is 400 deg.C or lower, pressured air is supplied to the cathode 1a, the anode 1b, and the pressure vessel 2, and the organic binder in a green sheet is effectively decomposed and scattered. Decomposition and scattering of the organic binder is effectively conducted.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、溶融炭酸塩型燃料電池の処理方法にに関する
。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing molten carbonate fuel cells.

〔従来の技術〕[Conventional technology]

イオン導電性材料である燃料電池の電解質は、内部抵抗
が低くてイオン導電性が高いことが重要な特性である。The important characteristics of the electrolyte of a fuel cell, which is an ion-conductive material, are low internal resistance and high ion-conductivity.

溶融炭酸塩型燃料電池では、電解質としてＬｉ、　Ｎａ
、　Ｋの混合炭酸塩を使用し、電解質の保持材料（マト
リックス材）としてリチウムアルミネートＬｉへ１０□
、アル旦す繊維へＩ２Ｏ３なと゛の無機材料を使用して
いる。通常は、室温での取扱いが容易になるように、有
機バインダーを加えてマトリックス材をシート状に形成
している。このシート状態のマトリックス材を、グリー
ンシート、生テープ、などと呼称している。In molten carbonate fuel cells, Li and Na are used as electrolytes.
, using a mixed carbonate of K, 10□ to lithium aluminate Li as a holding material (matrix material) for the electrolyte.
Inorganic materials such as I2O3 are used in the aluminum fibers. Usually, the matrix material is formed into a sheet by adding an organic binder so that it can be easily handled at room temperature. This matrix material in sheet form is called green sheet, raw tape, etc.

燃料電池の内部で電解質として機能する時には電解質が
マトリックス利の全気孔容積に対して１００ｖｏ１％含
浸して、その結果、内部抵抗が低くてイオン導電性が高
い特性を示すことが理想的である。グリーンシートの状
態で加えていた有機バインダーが電池作動時にも残留す
ると、電解質のマトリックス材への含浸を阻害して内部
抵抗を増加させる要因となり、電池性能が低下する。When functioning as an electrolyte inside a fuel cell, it is ideal that the electrolyte impregnates the total pore volume of the matrix at 100 vol %, resulting in low internal resistance and high ionic conductivity. If the organic binder added in the form of a green sheet remains during battery operation, it will inhibit the impregnation of the electrolyte into the matrix material and increase internal resistance, resulting in a decrease in battery performance.

燃料電池の電解質を作成する実用的な方法は、主に、外
部焼成−外部含浸方法と内部焼成−内部含浸方法の２つ
である。前者は、電池組込前に（電池の外部で）グリー
ンシートを焼成して有機バインダーを除去しく脱脂と呼
称する場合もある）、かつ、電池外部で電解質をマトリ
ックス材の内部に含浸する方法である。製作条件の制御
が比較的容易なので、含浸率の高い、高性能な電解質板
（タイルと呼称する場合もある）を製作可能である。し
かし、製作した電解質板はセラミック質の薄板となり、
破損し易いので取扱いが困難になり、電池組込作業など
には細心の注意を要する。また、電解質板の面積が大き
くなると電解質板を製作することも困難になる。後者は
、グリーンシートの状態のマトリックス材と電解質を電
池内部に組込んで電池全体を昇温しで、有機バインダー
を除去し、かつ電解質、をマトリックス内部に含浸する
方法である。取扱いが容易で、かつ電解質の面積が大き
くなっても適用できる方法なので、溶融炭酸塩型燃料電
池では内部焼成−内部含浸方法が主流となりつつある。There are two main practical methods for making fuel cell electrolytes: external firing-external impregnation method and internal firing-internal impregnation method. The former method involves firing the green sheet (outside the battery) to remove the organic binder (sometimes called degreasing), and impregnating the inside of the matrix material with electrolyte outside the battery. be. Since it is relatively easy to control manufacturing conditions, it is possible to manufacture high-performance electrolyte plates (sometimes called tiles) with a high impregnation rate. However, the electrolyte plate produced was a thin ceramic plate,
It is difficult to handle because it is easily damaged, and great care must be taken when assembling the battery. Furthermore, if the area of the electrolyte plate increases, it becomes difficult to manufacture the electrolyte plate. The latter is a method in which a matrix material in the form of a green sheet and an electrolyte are incorporated into the battery, the temperature of the entire battery is raised, the organic binder is removed, and the electrolyte is impregnated into the matrix. The internal firing-internal impregnation method is becoming mainstream in molten carbonate fuel cells because it is easy to handle and can be applied even when the area of the electrolyte becomes large.

しかし、有機バインダーを完全に除去し、電解質をマト
リックス材内部に十分に含浸する方法が、電池性能を左
右する重要な電池製作技術となる。However, the method of completely removing the organic binder and sufficiently impregnating the electrolyte inside the matrix material is an important battery manufacturing technology that influences battery performance.

従来は、例えば特開昭６２−１１５６６９のように、電
池に通気するガスの種類と電池の昇温条件を制御してい
た。Conventionally, as in Japanese Patent Application Laid-Open No. 62-115669, for example, the type of gas vented to the battery and the conditions for raising the temperature of the battery have been controlled.

〔発明が解決しようとする課題〕[Problem to be solved by the invention]

上記従来技術は、有機バインダーの除去が十分でなく、
アノードの酸化を防止する方策が検討されてなく、ガス
化した有機バインダー及びマトリックス材内部の通気ガ
スを除去する方策が検討されてなく、電解質板の特性と
して不十分であった。The above conventional technology does not remove the organic binder sufficiently,
No measures were taken to prevent oxidation of the anode, no measures were taken to remove the gasified organic binder and ventilation gas inside the matrix material, and the properties of the electrolyte plate were insufficient.

本発明は、上記従来技術の問題点を解消し得−る溶融炭
酸塩型燃料電池の処理方法を提供することにある。An object of the present invention is to provide a method for treating a molten carbonate fuel cell that can solve the problems of the prior art described above.

〔課題を解決するための手段〕[Means to solve the problem]

上記の目的を達成するために、本発明の溶融炭酸塩型燃
料電池の処理方法は、内部焼成−内部含浸方法において
、下記の手段を採用するものである。In order to achieve the above object, the method for treating a molten carbonate fuel cell of the present invention employs the following means in the internal firing-internal impregnation method.

まず、有機バインダーの炭化残留を防止して、かつ、ア
ノードを酸化させないために電解質板に、その溶融温度
以下で前記有機バインダーをガス化するに足る温度に加
熱した空気乃至酸素を大気圧以上に加圧して通気する。First, in order to prevent the organic binder from remaining carbonized and to prevent the anode from oxidizing, air or oxygen heated to a temperature sufficient to gasify the organic binder below its melting temperature is applied to the electrolyte plate at a pressure above atmospheric pressure. Pressurize and vent.

なお、この際好ましくはアノードに不活性ガスを通気す
る。また、ガス化した有機バインダーおよび通気した空
気乃至酸素を除去するために、電解質板のガス雰囲気を
炭酸塩電解質の溶融温度以下で大気圧以下に減圧する。At this time, preferably, an inert gas is passed through the anode. Further, in order to remove the gasified organic binder and the aerated air or oxygen, the gas atmosphere in the electrolyte plate is reduced in pressure to below the melting temperature of the carbonate electrolyte and below atmospheric pressure.

さらに、マトリックス材の内部への電解質含浸が容易に
なるように、電解質が溶融する温度以上で、不活性ガス
、好ましくは二酸化炭素で復圧する。Further, to facilitate electrolyte impregnation into the interior of the matrix material, pressure is restored with an inert gas, preferably carbon dioxide, at a temperature above the melting temperature of the electrolyte.

〔作　用］ グリーンシートの有機バインダーを除去するために、通
常は、加熱空気を通気して高い温度で長時間加熱してい
た。しかし、燃料電池に組み込んだ状態では、同時にア
ノードの酸化を進行させて電極を劣化させる可能性があ
る。したがって、所定温度以上の加熱空気は通気しない
ようにして、かつ有機バインダーの分解飛散を助成する
ために、加熱空気を大気圧以上に加圧して通気する。ア
ノードには不活性ガス（二酸化炭素、窒素など）を通気
して、カソードには空気を通気する方法、空気の代わり
に酸素を通気する方法も、グリーンシートの有機バイン
ダー除去とアノード酸化防止の両方の目的を満たず代秦
として採用することも可能である。[Function] In order to remove the organic binder from a green sheet, the green sheet is usually heated at a high temperature for a long period of time by passing heated air through it. However, when incorporated into a fuel cell, there is a possibility that oxidation of the anode progresses at the same time, causing deterioration of the electrode. Therefore, in order to prevent heated air having a temperature higher than a predetermined temperature from being ventilated, and to promote decomposition and scattering of the organic binder, the heated air is pressurized to a pressure higher than atmospheric pressure and ventilated. A method of aerating an inert gas (carbon dioxide, nitrogen, etc.) to the anode and aerating air to the cathode, or a method of aerating oxygen instead of air, both removes the organic binder from the green sheet and prevents the oxidation of the anode. It is also possible to adopt it as Dynasty Qin if it does not meet the purpose of .

電解質が溶融して液体状態になる前に、７１〜リツクス
材の内部に残存する有機物およびガス（ガス化した有機
バインダーと通気した加熱ガス）を除去しておき、溶融
した電解質の含浸の障害とならないようにする必要があ
る。この目的で、電解質が溶融する前に、電解質板の内
部を大気圧以下に減圧する。Before the electrolyte melts into a liquid state, remove organic matter and gas (gasified organic binder and aerated heated gas) remaining inside the 71~ics material to prevent impregnation of the molten electrolyte. It is necessary to prevent this from happening. For this purpose, the interior of the electrolyte plate is depressurized below atmospheric pressure before the electrolyte is melted.

減圧した状態で電解質を溶融させて、その後、大気圧に
復圧して電解質をマトリックス材の内部へ、圧力差を駆
動力にして含浸する。The electrolyte is melted under reduced pressure, and then the pressure is returned to atmospheric pressure to impregnate the electrolyte into the matrix material using the pressure difference as a driving force.

復圧する場合の不活性ガスとしては、好ましくは電解質
への溶解炭が高い二酸化炭素を採用する。As the inert gas for pressure recovery, carbon dioxide is preferably used since it has a high amount of carbon dissolved in the electrolyte.

二酸化炭素が溶融した電解質の内部に気泡として残存し
ても、徐りに電解質にン容解して、最終曲には電解質で
均一に充填された電解質板が形成される。Even if carbon dioxide remains as bubbles inside the molten electrolyte, it will gradually dissolve into the electrolyte, and an electrolyte plate uniformly filled with electrolyte will be formed in the final song.

〔実施例〕〔Example〕

以下、電解質板の面積１００ｃ＋ｆｌ、電極面積６４ｃ
／の小形燃料電池を用いた場合の、本発明の詳細な説明
する。電池加熱プロセスを第１図に、電池加圧プロセス
を第２図に、燃料電池の配管系統図を第３図に示す。第
４図は、従来の方法で製作した燃料電池と本実施例によ
って製作した燃料電池の内部抵抗を比較したものである
。Below, the area of the electrolyte plate is 100c+fl, and the area of the electrode is 64c.
The present invention will be described in detail when a small fuel cell of / is used. The battery heating process is shown in FIG. 1, the battery pressurizing process is shown in FIG. 2, and the piping system diagram of the fuel cell is shown in FIG. 3. FIG. 4 compares the internal resistances of a fuel cell manufactured by a conventional method and a fuel cell manufactured by this example.

第１図において実施例の電池加熱プロセスを説明する。The battery heating process of the embodiment will be explained with reference to FIG.

電池温度が４００°Ｃ以下では、アノード、カソード共
に酸化ガスを通気して、約５０ｄｅｇ／ｈで昇温してい
る。電池温度が４００°Ｃを超える温度では、アノード
の酸化劣化を防止するために、アノードは不活性ガスを
通気している。炭酸塩の溶融温度（Ｂ点）の上下近傍の
温度範囲（Ａ点からＣ点）では、マトリックス内部へ電
解質が十分に含浸するように、約１０〜２０ｄｅｇ／ｈ
で昇温している。When the battery temperature is below 400°C, oxidizing gas is passed through both the anode and cathode to raise the temperature at about 50 deg/h. When the cell temperature exceeds 400° C., the anode is vented with an inert gas to prevent oxidative deterioration of the anode. In the temperature range (from point A to point C) near the melting temperature of carbonate (point B), the rate is approximately 10 to 20 deg/h so that the electrolyte is sufficiently impregnated into the matrix.
The temperature is rising.

その後、電池を発電温度（Ｄ点）まで加熱して、温度一
定に保持する。Thereafter, the battery is heated to the power generation temperature (point D) and kept at a constant temperature.

第２図において、実施例の電池加圧プロセスを説明する
。炭酸塩の溶融温度（Ｂ点）以下では、例えば、実施例
ではＡ点までは、燃料電池に通気するガスを７ａｔａに
加圧している。その後、炭酸塩の溶融温度（Ｂ点）に電
池温度が達する前に、電池雰囲気を、真空ポンプで大気
圧以下に減圧する。通常は、０．１　ｔｏｒｒ程度まで
減圧している。その後、電池温度が、炭酸塩の溶融温度
（Ｂ点）を超えた温度になった後、不活性ガスで、まず
大気圧まで復圧し、更に、大気圧より若干高めに電池内
部を加圧しておく。通常は、数１００ｍｍＨｚＯ程度に
保持する。Referring to FIG. 2, the battery pressurization process of the embodiment will be explained. Below the melting temperature of the carbonate (point B), for example up to point A in the embodiment, the gas vented to the fuel cell is pressurized to 7 ata. Thereafter, before the battery temperature reaches the melting temperature of the carbonate (point B), the battery atmosphere is reduced to below atmospheric pressure using a vacuum pump. Normally, the pressure is reduced to about 0.1 torr. Then, after the battery temperature exceeds the melting temperature of carbonate (point B), the pressure is first restored to atmospheric pressure using an inert gas, and then the inside of the battery is pressurized to a level slightly higher than atmospheric pressure. put. Normally, it is maintained at about several 100 mmHzO.

第３図において、実施例の電池配管系統およびガス変更
操作を説明する。カソードｌａ、アットｌｂ、電解質板
１ｃから構成される燃料電池１は圧力容器２の内部に収
納されている。カソード１ａには流量調圧弁３と流量計
６を介して酸化ガスが供給され、アノード１ｂには流量
調圧弁４と流量計７を介して燃料ガスが供給され、燃料
電池は、圧力容器の内部で、所定の温度と圧力で発電さ
れる。圧力容器には、流量調圧弁５と流量計８を介して
窒素が供給されている。各ガス系統の調圧弁９．１０．
１１には燃料電池の運転圧力と各ガス系統間の差圧を制
御している。遮断弁１２と１３は各ガス系統間を均圧す
る場合に使用する。また、真空ポンプ１４は、加熱・加
圧プロセスで燃料電池を一時的に減圧する場合に使用す
る。Referring to FIG. 3, the battery piping system and gas changing operation of the embodiment will be explained. A fuel cell 1 consisting of a cathode la, an at lb, and an electrolyte plate 1c is housed inside a pressure vessel 2. Oxidizing gas is supplied to the cathode 1a via a flow rate regulating valve 3 and a flow meter 6, and fuel gas is supplied to the anode 1b via a flow rate regulating valve 4 and a flow meter 7. Electricity is generated at a predetermined temperature and pressure. Nitrogen is supplied to the pressure vessel via a flow rate regulating valve 5 and a flow meter 8. Pressure regulating valve for each gas system 9.10.
11 controls the operating pressure of the fuel cell and the differential pressure between each gas system. The shutoff valves 12 and 13 are used to equalize the pressure between each gas system. Further, the vacuum pump 14 is used to temporarily reduce the pressure of the fuel cell during the heating and pressurizing process.

第３図の配管系統において、内部焼成−内部含浸方法で
、燃料電池を昇温する場合は、以下の順番にガスを変更
する。In the piping system of FIG. 3, when raising the temperature of the fuel cell by the internal firing-internal impregnation method, the gases are changed in the following order.

まず、電池温度が４０「Ｃ以下では、カソード１ａ、ア
ノード１ｂ、圧力容器２、共に加圧空気を０ 通気して、グリーンシートの有機バインダーを効果的に
分解飛散させる。この時、遮断弁１２と１３を開放して
、各ガス系統間に差圧がつかないようにしておくことで
、差圧制御が不要になる。First, when the battery temperature is below 40°C, pressurized air is vented to the cathode 1a, anode 1b, and pressure vessel 2 to effectively decompose and scatter the organic binder of the green sheet.At this time, the cutoff valve 12 By opening and 13 to prevent a pressure difference between each gas system, differential pressure control becomes unnecessary.

次に、電池温度が４００°Ｃを超えてＡ点に達するまで
は、アノードと圧力容器の通気ガスを空気から窒素に変
更する。この時、遮断弁１２は閉して、カソードと他の
ガス系統間は、調圧弁９．１０．１１で差圧制御する。Next, the ventilation gas for the anode and pressure vessel is changed from air to nitrogen until the cell temperature exceeds 400°C and reaches point A. At this time, the shutoff valve 12 is closed, and the pressure difference between the cathode and other gas systems is controlled by the pressure regulating valves 9, 10, and 11.

次に、電池温度がＡ点からＢ点の間は、カソードの通気
ガスを空気から窒素に変更する。この時遮断弁１２を再
び開放して、各ガス系統間を均圧する。そして、電池ガ
ス圧力を７ａｔａから大気圧に低下させ、更に、真空ポ
ンプ１４を起動して、電池ガス圧力を大気圧以下に減圧
する。各ガス系統間は均圧されているので、急激なガス
圧力の変化があっても、異常な差圧で電池がダメージを
受けることはない。Next, when the battery temperature is between point A and point B, the cathode ventilation gas is changed from air to nitrogen. At this time, the shutoff valve 12 is opened again to equalize the pressure between each gas system. Then, the battery gas pressure is lowered from 7ata to atmospheric pressure, and the vacuum pump 14 is further started to reduce the battery gas pressure to below atmospheric pressure. Since the pressure between each gas system is equalized, even if there is a sudden change in gas pressure, the battery will not be damaged by an abnormal pressure difference.

次に、電池温度がＢ点を超えると、各ガス系統間は均圧
した状態で、不活性ガスによりまず大気１ 圧まで復圧する。不活性ガスとしては、好ましくは、電
解質への溶解度が高い二酸化炭素を使用する。この後、
圧力容器の通気ガスを二酸化炭素から窒素に変更して、
各ガス系統間の差圧を制御しながら、電池ガス圧力を大
気圧より、若干高めにしておく。電池ガス圧力を大気圧
より高くしておくことで、大気の電池内部へのリークを
防ぐことができる。Next, when the battery temperature exceeds point B, the pressure in each gas system is equalized and the pressure is first restored to atmospheric pressure 1 using inert gas. Carbon dioxide, which has high solubility in the electrolyte, is preferably used as the inert gas. After this,
By changing the vent gas in the pressure vessel from carbon dioxide to nitrogen,
While controlling the differential pressure between each gas system, the battery gas pressure is kept slightly higher than atmospheric pressure. By keeping the battery gas pressure higher than atmospheric pressure, it is possible to prevent atmospheric air from leaking into the battery.

第４図は、加熱プロセスをいろいろと変化させた場合の
従来例と、本実施例により燃料電池を製作した場合を内
部抵抗で比較した結果である。電解質板１ｃの両端の内
部抵抗をミリオームメータ（４３２８Ａ、　Ｙ　ＨＰ）
で測定した、１ｋＨｚでの純抵抗成分である。内部抵抗
は、想定した抵抗値と電解質板の面積との積で示しであ
る。電解質板の厚みなどの要因によって若干のバラツキ
はあるが、小形燃料電池による本実施例では、従来例の
約１７２から２７３に内部抵抗が低下する。FIG. 4 shows the results of comparing the internal resistance of a conventional example in which the heating process was varied in various ways and a fuel cell manufactured according to the present example. Measure the internal resistance at both ends of the electrolyte plate 1c using a milliohmmeter (4328A, Y HP).
This is the pure resistance component at 1kHz, measured at The internal resistance is expressed as the product of the assumed resistance value and the area of the electrolyte plate. Although there is some variation due to factors such as the thickness of the electrolyte plate, in this example using a small fuel cell, the internal resistance decreases from about 172 in the conventional example to 273.

溶融炭酸塩型燃料電池は、発電効率を上げるために反応
ガスを加圧して運転する予定になってお２ す、圧力容器に収納されて運転される。従って、本実施
例のように、燃料電池を加熱するプロセスで通気ガスを
加圧および一時的に大気圧以下に減圧する場合にも、運
転用の圧力容器を使用できるので、装置設備としてはコ
ストアップにはならない。A molten carbonate fuel cell is housed in a pressure vessel and is operated under pressure to increase the efficiency of power generation. Therefore, even when pressurizing the vent gas and temporarily reducing the pressure below atmospheric pressure in the process of heating the fuel cell, as in this example, the pressure vessel for operation can be used, which reduces the cost of equipment. It won't go up.

〔発明の効果］ 本発明によれば、以下に記載されるような効果がある。〔Effect of the invention] According to the present invention, there are effects as described below.

大気圧以上に加圧した空気を電解質板に通気するので、
有機バインダーの分解・飛散を効果的に行うことができ
る。また、加熱酸素を通気する場合、加熱酸素を加圧し
て通気する場合は、有機バインダーの分解・飛散が一層
効果的になる。更に、所定の温度以上では、アノードに
は不活性ガスを通気することで、アノードの酸化劣化を
防止する。Since air pressurized above atmospheric pressure is vented through the electrolyte plate,
The organic binder can be effectively decomposed and dispersed. Further, when heated oxygen is aerated, or when heated oxygen is aerated under pressure, the decomposition and scattering of the organic binder becomes more effective. Further, at temperatures above a predetermined temperature, an inert gas is passed through the anode to prevent oxidative deterioration of the anode.

また、炭酸塩電解質の溶融温度以下で電池ガス圧力を大
気圧以下に減圧することで、有機バインダーの分解ガス
、残存している通気ガスを効果的に除去できる。また、
炭酸塩電解質の溶融温度以上３ で、不活性ガスで復圧することで、電解質をマトリック
ス材の内部へ、圧力差を駆動力にして含浸できる。また
、復圧する不活性ガスとして、電解質への溶解度が高い
二酸化炭素を使用することで、不活性ガスが電解質板内
部に残存しても、電解質内へ溶解して気泡として残存す
る可能性は少ない。Further, by reducing the cell gas pressure to below atmospheric pressure at a temperature below the melting temperature of the carbonate electrolyte, decomposition gas of the organic binder and remaining ventilation gas can be effectively removed. Also,
By restoring the pressure with an inert gas at a temperature higher than the melting temperature of the carbonate electrolyte, the electrolyte can be impregnated into the matrix material using the pressure difference as a driving force. In addition, by using carbon dioxide, which has high solubility in the electrolyte, as the inert gas for pressure recovery, even if the inert gas remains inside the electrolyte plate, there is little possibility that it will dissolve into the electrolyte and remain as bubbles. .

以上のような効果があり、実施例の小形燃料電池では、
電解質板の内部抵抗を従来のものに比較して著しく低減
（例えば、従来の約１７２から２７３）する効果があっ
た。また、溶融炭酸塩型燃料電池は圧力容器に収納され
て運転されるので、加熱・加圧プロセスで、通気ガスを
加圧及び減圧する場合にも運転用の圧力容器を使用でき
る。従って、本発明を実施するに当って、装置設備がコ
ストアップすることはない。With the above-mentioned effects, the small fuel cell of the example has
This has the effect of significantly reducing the internal resistance of the electrolyte plate compared to the conventional one (for example, from about 172 to 273 in the conventional one). Further, since the molten carbonate fuel cell is operated while being housed in a pressure vessel, the pressure vessel for operation can also be used when pressurizing and depressurizing vent gas in the heating and pressurizing process. Therefore, when implementing the present invention, the cost of equipment and equipment does not increase.

また、本発明を適用しているのは、電解質板の取扱いが
容易な、内部焼成−内部含浸方法の電池製作技術である
。本発明を適用することで、内部抵抗の低減した、電解
質面積の大きい溶融炭酸塩型燃料電池を製作することが
できる。Furthermore, the present invention is applied to a battery manufacturing technology using an internal firing-internal impregnation method, which allows easy handling of electrolyte plates. By applying the present invention, a molten carbonate fuel cell with reduced internal resistance and a large electrolyte area can be manufactured.

４4

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

第１図は、本発明の一実施例である小形燃料電池の加熱
プロセスを示すグラフである。第２図は同しく、加圧プ
ロセスを示すグラフである。第３図は、燃料電池の配管
系統図を示す。第４図は、本発明の一実施例による小形
燃料電池の電解質板の抵抗を、従来の製作方法による燃
料電池の抵抗と比較した、本発明の効果を示す一例であ
る。FIG. 1 is a graph showing a heating process for a small fuel cell according to an embodiment of the present invention. FIG. 2 is also a graph showing the pressurization process. FIG. 3 shows a piping system diagram of the fuel cell. FIG. 4 is an example showing the effect of the present invention, comparing the resistance of an electrolyte plate of a small fuel cell according to an embodiment of the present invention with the resistance of a fuel cell manufactured using a conventional manufacturing method.

Claims (1)

【特許請求の範囲】 １、無機繊維と有機バインダーから構成されるマトリッ
クス材、および、このマトリックス材に含浸する炭酸塩
電解質からなる電解質板に、電池内部で、大気圧以上に
加圧し、かつ、前記電解質の溶融温度以下で前記有機バ
インダーをガス化するに足る温度に加熱した空気を通気
接触せしめることにより、前記電解質板中の有機バイン
ダーをガス化させることを特徴とする溶融炭酸塩型燃料
電池の処理方法。 ２、無機繊維と有機バインダーから構成されるマトリッ
クス材、および、このマトリックス材に含浸する炭酸塩
電解質からなる電解質板に、電池内部で、前記電解質の
溶融温度以下で前記有機バインダーをガス化するに足る
温度に加熱した酸素ガスを通気接触せしめることにより
、前記電解質板中の有機バインダーをガス化させること
を特徴とする溶融炭酸塩型燃料電池の処理方法。 ３、酸素ガスが、大気圧以上に加圧した酸素ガスである
ことを特徴とする請求項２記載の溶融炭酸塩型燃料電池
の処理方法。 ４、電解質板に空気又は酸素ガスを通気接触せしめて前
記電解質板中の有機バインダーをガス化する処理をする
際に、アノードに不活性ガスを通気することを特徴とす
る請求項１乃至請求項３のいずれかの項記載の溶融炭酸
塩型燃料電池の処理方法。 ５、請求項１乃至請求項４のいずれかの項記載の溶融炭
酸塩型燃料電池の処理方法により、電解質板中の有機バ
インダーをガス化した後、炭酸塩電解質の溶融温度以下
で大気圧以下に減圧し、ついで、炭酸塩電解質の溶融温
度以上で、復圧することを特徴とする溶融炭酸塩型燃料
電池の処理方法。 ６、復圧を二酸化炭素で行うことを特徴とする請求項５
記載の溶融炭酸塩型燃料電池の処理方法。[Claims] 1. A matrix material composed of inorganic fibers and an organic binder, and an electrolyte plate composed of a carbonate electrolyte impregnated into this matrix material are pressurized to a pressure higher than atmospheric pressure inside the battery, and A molten carbonate fuel cell characterized in that the organic binder in the electrolyte plate is gasified by bringing air into contact with air heated to a temperature sufficient to gasify the organic binder at a temperature lower than the melting temperature of the electrolyte. processing method. 2. A matrix material composed of inorganic fibers and an organic binder, and an electrolyte plate composed of a carbonate electrolyte impregnated into this matrix material, in which the organic binder is gasified at a temperature below the melting temperature of the electrolyte inside the battery. A method for treating a molten carbonate fuel cell, characterized in that the organic binder in the electrolyte plate is gasified by bringing oxygen gas heated to a sufficient temperature into contact with the gas. 3. The method for treating a molten carbonate fuel cell according to claim 2, wherein the oxygen gas is oxygen gas pressurized above atmospheric pressure. 4. Claims 1 to 4, characterized in that when the electrolyte plate is brought into contact with air or oxygen gas to gasify the organic binder in the electrolyte plate, an inert gas is aerated to the anode. 3. The method for treating a molten carbonate fuel cell according to any one of 3. 5. After the organic binder in the electrolyte plate is gasified by the method for treating a molten carbonate fuel cell according to any one of claims 1 to 4, the temperature is lower than the melting temperature of the carbonate electrolyte and lower than atmospheric pressure. 1. A method for processing a molten carbonate fuel cell, which comprises reducing the pressure to a temperature equal to or higher than the melting temperature of the carbonate electrolyte, and then returning the pressure to a temperature higher than the melting temperature of the carbonate electrolyte. 6. Claim 5, characterized in that the pressure recovery is performed using carbon dioxide.
A method of processing the described molten carbonate fuel cell.
JP1175641A 1989-07-10 1989-07-10 Method for treating molten carbonate type thermal battery Expired - Fee Related JPH07123049B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1175641A JPH07123049B2 (en) 1989-07-10 1989-07-10 Method for treating molten carbonate type thermal battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1175641A JPH07123049B2 (en) 1989-07-10 1989-07-10 Method for treating molten carbonate type thermal battery

Publications (2)

Publication Number Publication Date
JPH0343963A true JPH0343963A (en) 1991-02-25
JPH07123049B2 JPH07123049B2 (en) 1995-12-25

Family

ID=15999639

Family Applications (1)

Application Number Title Priority Date Filing Date
JP1175641A Expired - Fee Related JPH07123049B2 (en) 1989-07-10 1989-07-10 Method for treating molten carbonate type thermal battery

Country Status (1)

Country Link
JP (1) JPH07123049B2 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62115669A (en) * 1985-11-14 1987-05-27 Ishikawajima Harima Heavy Ind Co Ltd Manufacturing method of stacked fuel cell
JPS6445064A (en) * 1987-08-12 1989-02-17 Fuji Electric Res Manufacture of electrolyte tile for molten carbonate fuel cell
JPS6471072A (en) * 1987-09-09 1989-03-16 Toppan Printing Co Ltd Manufacture of electrolyte tile for molten carbonate fuel cell
JPH01120774A (en) * 1987-11-02 1989-05-12 Toppan Printing Co Ltd Manufacture of electrolyte tile of molten carbonate fuel cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62115669A (en) * 1985-11-14 1987-05-27 Ishikawajima Harima Heavy Ind Co Ltd Manufacturing method of stacked fuel cell
JPS6445064A (en) * 1987-08-12 1989-02-17 Fuji Electric Res Manufacture of electrolyte tile for molten carbonate fuel cell
JPS6471072A (en) * 1987-09-09 1989-03-16 Toppan Printing Co Ltd Manufacture of electrolyte tile for molten carbonate fuel cell
JPH01120774A (en) * 1987-11-02 1989-05-12 Toppan Printing Co Ltd Manufacture of electrolyte tile of molten carbonate fuel cell

Also Published As

Publication number Publication date
JPH07123049B2 (en) 1995-12-25

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