JPS6341192B2 - - Google Patents
Info
- Publication number
- JPS6341192B2 JPS6341192B2 JP57047995A JP4799582A JPS6341192B2 JP S6341192 B2 JPS6341192 B2 JP S6341192B2 JP 57047995 A JP57047995 A JP 57047995A JP 4799582 A JP4799582 A JP 4799582A JP S6341192 B2 JPS6341192 B2 JP S6341192B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- fuel cell
- matrix
- electrolyte
- phosphoric acid
- 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
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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
- H01M8/04225—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells during start-up
-
- 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/043—Processes for controlling fuel cells or fuel cell systems applied during specific periods
- H01M8/04303—Processes for controlling fuel cells or fuel cell systems applied during specific periods applied during shut-down
-
- 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
- H01M8/04228—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells during shut-down
-
- 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04014—Heat exchange using gaseous fluids; Heat exchange by combustion of reactants
-
- 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04097—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with recycling of the reactants
-
- 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】
この発明は電解質固定型燃料電池のマトリツク
ス（電解液保持部材）中の電解質の晶析（結晶の
析出）を防止させる方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for preventing crystallization (crystal precipitation) of an electrolyte in a matrix (electrolyte holding member) of a fixed electrolyte fuel cell.
燃料ガスとして水素ガスまたはメタン、エタン
等の天然ガスを改質した改質水素ガスを用い、酸
化剤ガスとして酸素ガスまたは空気を用いる電解
液固定型燃料電池においては、電池内部での反応
ガスの混合（主に電極触媒面からマトリツクスを
通過し対極へ到達するガス洩れ）を防止する役割
をマトリツクスにもたせることが望ましい。この
マトリツクスはりん酸等の電解液を保持した状態
で高いガスふきぬけ圧力（0.5〜２Kg／cm2）を有
しなければならない。 In fixed electrolyte fuel cells that use hydrogen gas or reformed hydrogen gas obtained by reforming natural gas such as methane or ethane as the fuel gas and oxygen gas or air as the oxidant gas, the reaction gas inside the cell is It is desirable that the matrix has the role of preventing mixing (mainly gas leakage from the electrode catalyst surface through the matrix and reaching the counter electrode). This matrix must have a high gas bleed pressure (0.5 to 2 kg/cm 2 ) while retaining an electrolyte such as phosphoric acid.
電解液固定型燃料電池は、一般に第１図に示す
構成を有する。すなわち燃料電池１は、耐熱性、
耐蝕性および電気絶縁性を有する多孔性薄膜部材
にりん酸などの電解液を含浸させたマトリツクス
２と、前記マトリツクスにより隔置されたガス拡
散および電解液浸透性を有する多孔性の燃料電極
（水素電極）３および酸化剤電極（酸素電極また
は空気電極）４と、これら電極のガス側基材に接
触し集電の役割を果すとともにそれぞれの電極へ
反応ガスを供給するためのガス区画室５，６とを
形成するセパレータプレート（バイポーラプレー
ト）７，８とから成立つている。 A fixed electrolyte fuel cell generally has the configuration shown in FIG. That is, the fuel cell 1 has heat resistance,
A matrix 2 is formed by impregnating a porous thin film member with corrosion resistance and electrical insulation with an electrolyte such as phosphoric acid, and a porous fuel electrode (hydrogen electrode) 3 and oxidizer electrode (oxygen electrode or air electrode) 4, and a gas compartment 5 which contacts the gas side substrate of these electrodes and serves as a current collector and supplies a reactive gas to each electrode. 6 and separator plates (bipolar plates) 7 and 8.
電極は、ガスの拡散または透過を容易にするた
めの多孔性カーボン不織布基材３ａ，４ａ上にグ
ラフアイト粉末をポリテトラフルオロエチレン
（PTFE）で結合させた薄膜（撥水層）３ｂ，４
ｂと電極反応を容易に行わせるための貴金属を担
持したカーボン粉末触媒をPTFEで結合させた薄
層（触媒層）３ｃ，４ｃより構成されている。 The electrodes are thin films (water repellent layers) 3b, 4 in which graphite powder is bonded with polytetrafluoroethylene (PTFE) on porous carbon nonwoven fabric substrates 3a, 4a to facilitate gas diffusion or permeation.
It is composed of thin layers (catalyst layers) 3c and 4c in which a carbon powder catalyst supporting a noble metal is bonded with PTFE to facilitate the electrode reaction.
マトリツクス２は耐熱、耐蝕性、非電導性を有
する微粉末を少量のPTFEで結合させた薄膜であ
る。前記マトリツクスには、○イ電解液による高湿
潤性、○ロ大きな電解液保持力、○ハ高いガスふきぬ
け圧力、○ニ機械的強度が大きい事などの特性を有
することが望まれる。 Matrix 2 is a thin film made of heat-resistant, corrosion-resistant, and non-conductive fine powder bonded with a small amount of PTFE. It is desired that the matrix has the following properties: (i) high wettability with electrolyte, (b) large electrolyte holding power, (b) high gas blowing pressure, and (d) high mechanical strength.
かかる燃料電池において、電解液としてりん酸
が使用される場合には、マトリツクスに含浸させ
るりん酸は一般に95〜100wt％の濃度のものが使
用され、通常の運転条件下（温度150〜200℃）で
はマトリツクス中に保持されているりん酸の濃度
は100〜105wt％となる。ところで、前記濃度の
りん酸は第２図に示されたような氷晶温度を有す
る。縦軸は温度、横軸は濃度である。すなわちり
ん酸濃度100wt％で氷晶温度は約42℃、102wt％
で約35℃、105wt％で約30℃となる。このような
氷晶温度を有する濃度のりん酸を保持したマトリ
ツクスからなる燃料電池を休止状態（電池の温度
が大気に等しい温度状態で運転休止する）に放置
した場合には、マトリツクスおよび電極触媒層反
応界面に保持されたりん酸は氷晶温度以下であ
り、結晶析出が起る。りん酸に濡れやすくしかも
りん酸の保持力を高めるために撥水性を有する
PTFE結合剤を可能な限り少ない量で作製してい
るマトリツクスにおいて、このりん酸の結晶析出
が起ると、マトリツクス膜に亀裂および層間剥離
および構造破壊などをもたらし、○イ電解液保持力
の低下、○ロ絶縁抵抗の低下、○ハマトリツクス強度
の低下、○ニ電池内部での反応ガスの漏洩および混
合などに伴う電池性能低下の限因となる。 In such fuel cells, when phosphoric acid is used as the electrolyte, the phosphoric acid impregnated into the matrix is generally used at a concentration of 95 to 100 wt%, and under normal operating conditions (temperature 150 to 200°C). In this case, the concentration of phosphoric acid retained in the matrix is 100 to 105 wt%. By the way, phosphoric acid at the above concentration has an ice crystal temperature as shown in FIG. The vertical axis is temperature and the horizontal axis is concentration. In other words, when the phosphoric acid concentration is 100wt%, the ice crystal temperature is approximately 42℃, 102wt%.
It becomes about 35℃ at 105wt%, and about 30℃ at 105wt%. If a fuel cell made of a matrix containing phosphoric acid at such a concentration of ice crystal temperature is left in a dormant state (operation is stopped with the cell temperature equal to that of the atmosphere), the matrix and electrode catalyst layer may The phosphoric acid retained at the reaction interface is below the ice crystal temperature, and crystal precipitation occurs. Easily wetted by phosphoric acid and has water repellency to increase phosphoric acid retention
When this phosphoric acid crystal precipitation occurs in a matrix made with the smallest possible amount of PTFE binder, it causes cracks, delamination, and structural destruction in the matrix film, resulting in a decrease in electrolyte retention ability. , (b) A decrease in insulation resistance, (b) a decrease in hamatrix strength, and (b) a decrease in battery performance due to leakage and mixing of reactant gases inside the battery.
この発明は前述の欠点を除去することを目的と
する。この目的は、本発明によれば、りん酸等の
電解質を保持するマトリツクスを燃料電極と酸化
剤電極とで挟持してなる燃料電池を、運転休止時
に電解質が晶析する温度以上に保温することによ
つて達成される。かかる方法により、りん酸の結
晶析出を防止し、ひいては前述の電池性能低下の
原因を除去することが可能となる。 The invention aims to obviate the aforementioned drawbacks. According to the present invention, the purpose of this is to keep a fuel cell formed by sandwiching a matrix holding an electrolyte such as phosphoric acid between a fuel electrode and an oxidizer electrode above the temperature at which the electrolyte crystallizes during suspension of operation. achieved by. By such a method, it is possible to prevent crystal precipitation of phosphoric acid and, in turn, eliminate the cause of the deterioration in battery performance described above.
第３図はこの発明の実施例を示すもので、燃料
電池１０は燃料電極１３と酸化剤電極１４とこれ
ら電極を隔置し電解液区画室を形成するマトリツ
クス１２およびそれぞれの電極へ反応ガスを供給
するためのガス区画室１５および１６より構成さ
れている。このような構成を有する燃料電池にお
いて、電池の運転時には、燃料ガスは燃料供給バ
ルブ１７および流量計１８を経油し、ガス区画室
１５へ供給され、燃料排出バルブ１９より排出さ
れる。一方、酸化剤ガスは酸化剤供給バルブ２０
および流量計２１を経由し、ガス区画室１６へ供
給され、酸化剤排出バルブ２２へ排出される。 FIG. 3 shows an embodiment of the invention, in which a fuel cell 10 includes a fuel electrode 13, an oxidizer electrode 14, a matrix 12 that separates these electrodes and forms electrolyte compartments, and a reactant gas supplied to each electrode. It consists of gas compartments 15 and 16 for supplying gas. In a fuel cell having such a configuration, during operation of the cell, fuel gas passes through the fuel supply valve 17 and the flow meter 18, is supplied to the gas compartment 15, and is discharged from the fuel discharge valve 19. On the other hand, the oxidant gas is supplied by the oxidant supply valve 20
The gas is supplied to the gas compartment 16 via the flow meter 21 and discharged to the oxidizer discharge valve 22.
運転休止時には、燃料ガス系統では燃料供給バ
ルブ１７を閉じることにより燃料ガスの供給を遮
断し、N2（窒素ガス）供給バルブ２３よりN2ガ
スをガス区画室１５および配管系に供給し、燃料
ガスのパージ後、N2ガスを加圧充填させる。一
方、酸化剤ガス系統においては、酸化剤供給バル
ブ２０および酸化剤排出バルブ２２を閉じ、酸化
剤ガスの供給と外気の進入を遮断するとともに、
ヒーター２５を加熱し、循環バルブ２６と循環フ
アン２４とにより、酸化剤ガス系統、とくにガス
区画室１６を加熱する。この加熱温度はマトリツ
クス内に保持されたりん酸が結晶析出温度以下に
ならない程度に保てばよい。空冷式の燃料電池に
おいては、循環フアン２４により常時反応に必要
な空気量の数倍もの空気を流しており、また燃料
電池の起動時には燃料電池を運転温度まで予備加
熱するためのヒーターが循環系内に配置されるの
が常であるので、かかるタイプの燃料電池では上
述のりん酸保温のための特別な機器を必要としな
い利点が得られる。 When the operation is stopped, the fuel gas system closes the fuel supply valve 17 to cut off the supply of fuel gas, and supplies N 2 gas from the N 2 (nitrogen gas) supply valve 23 to the gas compartment 15 and the piping system to supply fuel. After purging the gas, fill with N2 gas under pressure. On the other hand, in the oxidizing gas system, the oxidizing agent supply valve 20 and the oxidizing agent discharge valve 22 are closed to cut off the oxidizing gas supply and the entry of outside air, and
The heater 25 is heated, and the oxidant gas system, particularly the gas compartment 16, is heated by the circulation valve 26 and the circulation fan 24. The heating temperature may be maintained at such a level that the temperature of the phosphoric acid held within the matrix does not drop below the crystallization temperature. In an air-cooled fuel cell, the circulation fan 24 constantly flows air several times the amount of air required for the reaction, and when the fuel cell is started, a heater is installed in the circulation system to preheat the fuel cell to operating temperature. This type of fuel cell has the advantage of not requiring any special equipment for keeping the phosphoric acid warm, as described above.
なお、実施例では酸化剤ガス系統からの加熱に
ついて述べたが、燃料ガス系統でN2ガスを加熱
循環させるようにして電池を保温してもよいこと
はいうまでもない。 Although heating from the oxidant gas system has been described in the embodiment, it goes without saying that the battery may be kept warm by heating and circulating N 2 gas in the fuel gas system.
さらに、変形例としては、燃料電池が水冷、油
冷系統を有する場合には、ここにヒータを設ける
か、あるいは既設のヒータを利用して、電池休止
中にりん酸が所定温度以上となるよう加熱を行う
ようにしてもよい。 Furthermore, as a modification, if the fuel cell has a water cooling or oil cooling system, a heater may be installed here, or an existing heater may be used to ensure that the phosphoric acid reaches a predetermined temperature or higher while the cell is inactive. Heating may also be performed.
また、場合によつては、燃料電池の周囲全体を
加熱することによつてりん酸を所定温度以上に保
つようにすることも考えられる。 In some cases, it may be possible to maintain the phosphoric acid at a predetermined temperature or higher by heating the entire area around the fuel cell.
なお、実施例ではりん酸を電解質とした例につ
いて述べたが、同様な析出傾向を示す他の電解質
を用いる場合にも本発明は適用可能である。 Although the examples have been described using phosphoric acid as the electrolyte, the present invention is also applicable to cases where other electrolytes exhibiting similar precipitation tendencies are used.
このように、本発明によれば燃料電池の運転休
止時に燃料電池の電解質を保温することにより、
電解質の析出を防止し、マトリツクス膜の亀裂、
層間剥離などが生じなくなり、電解液保持力の低
下、絶縁抵抗の低下、マトリツクス強度の低下な
いしは電池内部での反応ガスの漏洩および混合に
伴う電池性能低下原因を除去することが可能とな
る。 As described above, according to the present invention, by keeping the electrolyte of the fuel cell warm when the fuel cell is out of operation,
Prevents electrolyte precipitation, cracks in matrix membrane,
Delamination and the like will not occur, making it possible to eliminate the causes of deterioration in battery performance due to a decrease in electrolyte holding power, a decrease in insulation resistance, a decrease in matrix strength, or leakage and mixing of reactive gases inside the battery.
第１図は本発明の適用可能な燃料電池の要部断
面図、第２図はりん酸の氷晶温度特性図、第３図
は本発明の実施例の流体回路図である。
１０……燃料電池、１２……マトリツクス、１
５，１６……ガス区画室、２４……循環フアン、
２５……ヒーター。
FIG. 1 is a sectional view of a main part of a fuel cell to which the present invention can be applied, FIG. 2 is a diagram of ice crystal temperature characteristics of phosphoric acid, and FIG. 3 is a fluid circuit diagram of an embodiment of the present invention. 10 ...Fuel cell, 12...Matrix, 1
5, 16...Gas compartment, 24...Circulation fan,
25...Heater.
Claims (1)
燃料電極と酸化剤電極とで挟持してなる燃料電池
を、運転休止時に電解質が晶析する温度以上に保
温することを特徴とする燃料電池の運転方法。 ２ 特許請求の範囲第１項記載の方法において、
加熱した酸化剤を供給してマトリツクスを保温す
ることを特徴とする燃料電池の運転方法。[Claims] 1. A fuel cell in which a matrix holding an electrolyte such as phosphoric acid is sandwiched between a fuel electrode and an oxidizer electrode is kept at a temperature higher than the temperature at which the electrolyte crystallizes during suspension of operation. How to operate a fuel cell. 2. In the method described in claim 1,
A method of operating a fuel cell characterized by supplying a heated oxidizing agent to keep a matrix warm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57047995A JPS58164161A (en) | 1982-03-25 | 1982-03-25 | Operation stopping method of fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57047995A JPS58164161A (en) | 1982-03-25 | 1982-03-25 | Operation stopping method of fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58164161A JPS58164161A (en) | 1983-09-29 |
| JPS6341192B2 true JPS6341192B2 (en) | 1988-08-16 |
Family
ID=12790893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57047995A Granted JPS58164161A (en) | 1982-03-25 | 1982-03-25 | Operation stopping method of fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58164161A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59214166A (en) * | 1983-05-18 | 1984-12-04 | Toshiba Corp | Phosphoric-acid-type fuel cell |
| JPS6093762A (en) * | 1983-10-28 | 1985-05-25 | Hitachi Ltd | phosphoric acid fuel cell |
| JPS60177568A (en) * | 1984-02-23 | 1985-09-11 | Mitsubishi Electric Corp | Fuel cell power generating system |
-
1982
- 1982-03-25 JP JP57047995A patent/JPS58164161A/en active Granted
Non-Patent Citations (2)
| Title |
|---|
| IMPROVEMENT OF FUEL-CEL TECHNOLOGY BASE=1978 * |
| POWER SYSTEMS DIVISION=1978 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58164161A (en) | 1983-09-29 |
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