JP2004043745A - Fluororubber composition - Google Patents
Fluororubber composition Download PDFInfo
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- JP2004043745A JP2004043745A JP2002206400A JP2002206400A JP2004043745A JP 2004043745 A JP2004043745 A JP 2004043745A JP 2002206400 A JP2002206400 A JP 2002206400A JP 2002206400 A JP2002206400 A JP 2002206400A JP 2004043745 A JP2004043745 A JP 2004043745A
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- Prior art keywords
- fluororubber
- gas
- fuel cell
- weight
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- 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.)
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Classifications
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- 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)
- Gasket Seals (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【0001】
【産業上の利用分野】
本発明は固体高分子型燃料電池において発生する生成水及び反応に用いられるガス、並びに冷却水をシールするためのガスケット材料に関するものである。
【0002】
【従来技術の内容】
従来、固体高分子型燃料電池は、平板状の電極構造体の両側にセパレーターが積層されたものが一つのセルとなり複数のセルが積層されて燃料電池のスタックとして構成されている。電極構造体は、正極側の電極触媒層(カソード)と負極側の電極触媒層(アノード)との間に高分子電解膜がはさまれ、各電極触媒層の外側にガス拡散層が配置された積層体である。セパレータは電子伝達機能を有する材料からなるもので電極構造体への対向面にはガス通路が形成され少なくとも一方のセパレータの表面には冷媒通路が形成されている。これら通路はいずれも溝状であってガス通路には、燃料ガスである水素ガスと酸素や空気等の酸化剤ガスがそれぞれ独立して流され、冷媒通路には水エチレングリコール等の冷媒が流される。
セパレータは、各ガス通路間の突起部がガス拡散層に接触する状態で電極構造体に積層される。
【0003】
このような燃料電池によると例えば負極側に配されたセパレータのガス通路に燃料ガスを流し、正極側に配されたセパレータのガス通路に酸化剤ガスを流すと電気化学反応が起こって電気が発生する。
当該燃料電池の作動中においては、ガス拡散層は電気化学反応によって生成した電子を電極触媒層とセパレータとの間で伝達させると同時に燃料ガス及び酸化剤ガスを拡散させる。
また負極側の電極触媒層は燃料ガスに化学反応を起こさせプロトンと電子を発生させ、正極側の電極触媒層は酸素とプロトンと電子から水を生成し、電解膜はプロトンをイオン伝導させる。そして、正負の電極触媒層を通して電力が取り出される。
【0004】
上記のような燃料電池においては燃料ガス、酸化剤ガスおよび冷媒を、それぞれ独立したガス通路及び冷媒通路に流通させる必要があることから、これら通路をシールによって隔絶している。シールする部位としては、燃料電池スタックの構造により若干異なるが、例えば燃料電池スタックを貫通するガス通路の連通口の周囲、電極構造体の周縁部、セパレータの表面に設けられた冷媒通路の周囲、セパレータ表面の周縁部等が挙げられる。
そしてこれらの箇所のシール材にはシリコーン系、フッ素系、エチレンプロピレン系、イソブチレン・イソプロピレン系などの有機ゴムからなる弾性材料が用いられており現在ではシリコーン系が主流となっている。
【0005】
【発明が解決しようとする課題】
燃料電池に用いられるガスケットでは上述したような燃料ガス、酸化剤ガス、冷媒をシールすることが必要であり、さらには電気化学反応によって発生した生成水をシールすることも要求される。この電気化学反応によって発生した生成水の中には電解膜中に含まれるフッ素イオンや硫酸イオンが溶出するため生成水は酸性を示し運転状況によってはガスケット材料に影響を与えることがある。また設計上低温から高温領域に至るまで非常にわずかな締め代によってシール性を維持することが必要であり極度に圧縮永久歪みの良好な材料が必要とされている。
そのためガスケット材料にはガス透過性、ガスシール性、耐冷媒性、低温性、低圧縮永久歪み性、耐フッ酸、耐硫酸性等が要求されるがすべてを満足する材料は今のところ見あたらず低温性、低圧縮永久歪み性を重視し、シリコーン系の有機弾性材料を用いているのが現状である。
【0006】
しかしながらシリコーン系の材料はその構造上、酸、アルカリによって加水分解を起こすという致命的な欠点を持っており電気化学反応によって発生する生成水の中に含まれるフッ酸と硫酸に侵され、シール性が損なわれるという問題点を有しており、かかる問題点を克服する材料の出現が望まれていた。
したがってかかる発明は、上述したガス透過性、ガスシール性、耐冷媒性、低温性等を有し且つ生成水中に含まれるフッ酸、硫酸に対し耐性のある材料を提供し長期に渡って安定したシール性を保持することを目的として開発されたものである。
【0007】
【課題を解決するための手段】
本発明は一般式
【化1】
で示される加熱硬化型のフッ素ゴムに補強性を有する充填剤とフッ素ゴムを加硫させるための加硫剤としての過酸化物、並びに架橋密度を増加させる共架橋剤とによって構成されるゴム組成物によって達成される。
【0008】
【発明の実施の形態】
本発明に用いられるフッ素ゴムとしては一般式
【化1】
で示される加熱硬化型のフッ素ゴムを用い、充填剤として粒径が200〜600ミリミクロンのサーマルブラックを3重量部から35重量部添加し、加硫剤として過酸化物を0.5〜10重量部、共架橋剤としてTAIC(トリアリルイソシアネート)を0.5〜6重量部配合したものをロールあるいは密閉式混合機によって混合し、ロールあるいは押し出し機等によって所定の形状に加工し成形に供する。成形にあたっては加圧加熱型のプレスによる圧縮成形、その他トランスファー成形、射出成形等任意の成形機を用いて所定の形状に加工することが出来る。以上の方法によって加工されたフッ素ゴム組成物は
150℃〜250℃、好ましくは200℃にて1〜8時間2次加硫を行った後製品として供される。
【0009】
【実施例】
次に実施例について本発明を説明する。実施例 フッ素ゴム(ダイキン工業製、ダイエルLT−302)、比較例 シリコーンゴム(東レ・ダウコーニング社製、SH747U)に表1に示される各配合成分を加え、オープンロールにて混練した後、シート状にし、加圧プレスを用いて、170℃、3分間の条件下でシート(150×150×2mm)とOリング(線径3.4mm、内径25mm)をそれぞれ加硫成形した。
得られた加硫物について、実施例1、2のフッ素ゴムに関しては200℃、4時間の熱処理(オーブン加硫)を行い、JIS K−6251、JIS K−6253、JIS K−6262に準拠して物性試験を行った。ここで表1の圧縮永久歪み試験は上述で得られたOリングを25%圧縮し、圧縮した治具ごと3000ppmの濃度のフッ酸水溶液(90℃)及びPH=2に調整した硫酸水溶液に表1に示される時間浸漬後、治具を開放し、圧縮永久歪みを測定した。また低温シール性試験は上述で得られたOリングを専用の試験治具に30%にて圧縮し、−35℃の条件下、圧力0.5Mpaの空気を治具内に入れ、Oリングからの空気洩れの有無を評価した。
【0010】
【表1】
【0011】
【発明の効果】
本発明によって得られたフッ素ゴム組成物は耐フッ酸性、耐硫酸性に優れた耐性を示すだけでなく本来要求されるべきガス透過性、ガスシール性、耐冷媒性、低圧縮永久歪み性、低温性等を満足し燃料電池用のパッキン材料として十分に使用することのできるものである。[0001]
[Industrial application fields]
The present invention relates to a product material generated in a polymer electrolyte fuel cell, a gas used for a reaction, and a gasket material for sealing cooling water.
[0002]
[Contents of prior art]
Conventionally, a polymer electrolyte fuel cell is configured as a fuel cell stack in which a separator is laminated on both sides of a flat electrode structure to form one cell and a plurality of cells are laminated. In the electrode structure, a polymer electrolyte membrane is sandwiched between a positive electrode catalyst layer (cathode) and a negative electrode catalyst layer (anode), and a gas diffusion layer is disposed outside each electrode catalyst layer. Laminated body. The separator is made of a material having an electron transfer function, and a gas passage is formed on the surface facing the electrode structure, and a refrigerant passage is formed on the surface of at least one of the separators. Each of these passages is groove-shaped, and hydrogen gas, which is a fuel gas, and an oxidant gas such as oxygen or air flow independently through the gas passage, and a coolant such as water ethylene glycol flows through the coolant passage. It is.
The separator is laminated on the electrode structure in a state in which the protrusions between the gas passages are in contact with the gas diffusion layer.
[0003]
According to such a fuel cell, for example, when a fuel gas is caused to flow through the gas passage of the separator disposed on the negative electrode side and an oxidant gas is caused to flow through the gas passage of the separator disposed on the positive electrode side, an electrochemical reaction occurs and electricity is generated. To do.
During operation of the fuel cell, the gas diffusion layer transmits electrons generated by the electrochemical reaction between the electrode catalyst layer and the separator, and simultaneously diffuses the fuel gas and the oxidant gas.
The electrode catalyst layer on the negative electrode side causes a chemical reaction to the fuel gas to generate protons and electrons, the electrode catalyst layer on the positive electrode side generates water from oxygen, protons and electrons, and the electrolytic membrane conducts protons in ionic conduction. Then, electric power is taken out through the positive and negative electrode catalyst layers.
[0004]
In the fuel cell as described above, since the fuel gas, the oxidant gas, and the refrigerant need to be circulated through independent gas passages and refrigerant passages, these passages are isolated by a seal. The part to be sealed varies slightly depending on the structure of the fuel cell stack.For example, the periphery of the gas passage through the fuel cell stack, the periphery of the electrode structure, the periphery of the refrigerant passage provided on the surface of the separator, Examples include the peripheral portion of the separator surface.
The sealing material at these locations is made of an elastic material made of organic rubber such as silicone, fluorine, ethylene propylene, isobutylene / isopropylene, and the silicone is the mainstream at present.
[0005]
[Problems to be solved by the invention]
Gaskets used in fuel cells need to seal the fuel gas, oxidant gas, and refrigerant as described above, and also require the generated water generated by the electrochemical reaction to be sealed. The generated water generated by this electrochemical reaction elutes fluorine ions and sulfate ions contained in the electrolytic membrane, so that the generated water is acidic and may affect the gasket material depending on the operating conditions. In addition, it is necessary to maintain the sealing performance by a very small tightening allowance from a low temperature to a high temperature range by design, and a material having extremely good compression set is required.
Therefore, gas permeability, gas seal, refrigerant resistance, low temperature, low compression set, hydrofluoric acid, sulfuric acid resistance, etc. are required for gasket materials, but no materials that satisfy all of them are found so far. At present, silicone-based organic elastic materials are used with emphasis on low-temperature properties and low compression set.
[0006]
However, silicone-based materials have a fatal defect that they are hydrolyzed by acids and alkalis due to their structure. They are affected by hydrofluoric acid and sulfuric acid contained in the water produced by the electrochemical reaction, resulting in a sealing property. Thus, there has been a demand for the appearance of a material that overcomes this problem.
Therefore, the invention provides a material having the above-described gas permeability, gas sealing property, refrigerant resistance, low temperature property and the like and resistant to hydrofluoric acid and sulfuric acid contained in the generated water, and is stable for a long time. It was developed for the purpose of maintaining sealing performance.
[0007]
[Means for Solving the Problems]
The present invention is represented by the general formula:
A rubber composition comprising a filler having a reinforcing property, a peroxide as a vulcanizing agent for vulcanizing the fluororubber, and a co-crosslinking agent for increasing the crosslinking density Achieved by things.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The fluororubber used in the present invention is represented by the general formula:
Is used, and 3 to 35 parts by weight of thermal black having a particle size of 200 to 600 millimicrons is added as a filler, and a peroxide is added as a vulcanizing agent in an amount of 0.5 to 10%. A mixture of 0.5 to 6 parts by weight of TAIC (triallyl isocyanate) as a co-crosslinking agent is mixed with a roll or a closed mixer, processed into a predetermined shape with a roll or an extruder, and used for molding. . In the molding, it can be processed into a predetermined shape using an arbitrary molding machine such as compression molding by a pressurizing and heating type press, other transfer molding, injection molding or the like. The fluororubber composition processed by the above method is used as a product after secondary vulcanization at 150 ° C. to 250 ° C., preferably 200 ° C. for 1 to 8 hours.
[0009]
【Example】
Next, the present invention will be described with reference to examples. Examples Fluororubber (Daikin Industries, Daiel LT-302), Comparative Example Silicone rubber (manufactured by Dow Corning Toray, SH747U) was added with each compounding component shown in Table 1 and kneaded with an open roll, then sheet Using a pressure press, a sheet (150 × 150 × 2 mm) and an O-ring (wire diameter 3.4 mm, inner diameter 25 mm) were respectively vulcanized and molded at 170 ° C. for 3 minutes.
About the obtained vulcanizates, the fluororubbers of Examples 1 and 2 were subjected to heat treatment (oven vulcanization) at 200 ° C. for 4 hours, in accordance with JIS K-6251, JIS K-6253, and JIS K-6262. The physical property test was conducted. Here, the compression set test shown in Table 1 is obtained by compressing the O-ring obtained above by 25% and adding the compressed jig to a 3000 ppm concentration hydrofluoric acid aqueous solution (90 ° C.) and a sulfuric acid aqueous solution adjusted to PH = 2. After immersion for the time indicated in 1, the jig was opened and compression set was measured. In the low temperature sealability test, the O-ring obtained above was compressed at 30% into a dedicated test jig, and air at a pressure of 0.5 Mpa was placed in the jig under the condition of -35 ° C. The presence or absence of air leakage was evaluated.
[0010]
[Table 1]
[0011]
【The invention's effect】
The fluororubber composition obtained by the present invention not only exhibits excellent resistance to hydrofluoric acid and sulfuric acid, but also inherently required gas permeability, gas sealability, refrigerant resistance, low compression set, It satisfies the low temperature property and can be sufficiently used as a packing material for a fuel cell.
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP2002206400A JP2004043745A (en) | 2002-07-16 | 2002-07-16 | Fluororubber composition |
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JP2002206400A JP2004043745A (en) | 2002-07-16 | 2002-07-16 | Fluororubber composition |
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JP2004043745A true JP2004043745A (en) | 2004-02-12 |
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JP2002206400A Pending JP2004043745A (en) | 2002-07-16 | 2002-07-16 | Fluororubber composition |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008195947A (en) * | 2008-03-07 | 2008-08-28 | Nok Corp | Fluororubber composition |
JP2015115149A (en) * | 2013-12-11 | 2015-06-22 | パナソニックIpマネジメント株式会社 | Manufacturing method of fuel cell member |
KR20170092549A (en) * | 2014-11-28 | 2017-08-11 | 아사히 가라스 가부시키가이샤 | Fluororubber compositions and crosslinked fluororubber article |
CN112795118A (en) * | 2020-12-30 | 2021-05-14 | 广州机械科学研究院有限公司 | Insulating fluororubber material and preparation method and application thereof |
-
2002
- 2002-07-16 JP JP2002206400A patent/JP2004043745A/en active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008195947A (en) * | 2008-03-07 | 2008-08-28 | Nok Corp | Fluororubber composition |
JP2015115149A (en) * | 2013-12-11 | 2015-06-22 | パナソニックIpマネジメント株式会社 | Manufacturing method of fuel cell member |
KR20170092549A (en) * | 2014-11-28 | 2017-08-11 | 아사히 가라스 가부시키가이샤 | Fluororubber compositions and crosslinked fluororubber article |
KR102445981B1 (en) | 2014-11-28 | 2022-09-21 | 에이지씨 가부시키가이샤 | Fluororubber compositions and crosslinked fluororubber article |
CN112795118A (en) * | 2020-12-30 | 2021-05-14 | 广州机械科学研究院有限公司 | Insulating fluororubber material and preparation method and application thereof |
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