JP4842448B2 - Packing material for polymer electrolyte fuel cell - Google Patents
Packing material for polymer electrolyte fuel cell Download PDFInfo
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- JP4842448B2 JP4842448B2 JP2001079012A JP2001079012A JP4842448B2 JP 4842448 B2 JP4842448 B2 JP 4842448B2 JP 2001079012 A JP2001079012 A JP 2001079012A JP 2001079012 A JP2001079012 A JP 2001079012A JP 4842448 B2 JP4842448 B2 JP 4842448B2
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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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Description
【０００１】
【発明の属する技術分野】
本発明は、小型の燃料電池として使用できる固体高分子型燃料電池用パッキング材に係り、特に耐酸性が良好で、長期の使用が可能で成形性にも優れた固体高分子型燃料電池用パッキング材に関する。
【０００２】
【従来の技術】
最近の環境問題や資源問題に対応して燃料電池の開発が活発に行われている。
特に燃料電池としては、小型、軽量化の要求から固体高分子型燃料電池が検討されている。このような電池用のセパレータとしては、より一層小型化が要求され、また多数のセパレータを重ね合せて使用することから、セパレータの少なくとも片側周縁部にパッキング材を設けるが、パッキング材としては耐久性に優れ、長期間使用できるパッキング材が要求されている。
【０００３】
このような固体高分子型燃料電池用パッキング材として、成形性、耐熱性、弾性に優れたシリコーンゴム製パッキング材が主に使用されている。さらにシリコーンゴムとしてはより一層成形性に優れた二液タイプの付加型液状シリコーンが使用されている。
【０００４】
【発明が解決しようとする課題】
上記の固体高分子型燃料電池に使用されている高分子電解質は、側鎖の末端にスルホン基を持つ炭化フッ素系の高分子膜を用いることができる。この電解質は水分を含んだ状態でプロトン伝導性を有する。そのため電池を作動させるためには、高分子電解質を常に水を含んだ状態にする必要がある。水分を含んだ状態での高分子電解質膜は、末端のスルホン基から解離する水素イオンにより、強い酸性を呈する。このため、固体高分子型燃料電池用パッキング材には耐酸性が要求される。
【０００５】
しかしながら、二液タイプの付加型液状シリコーンでは成形性には優れているが、耐酸性に劣り、長期の弾性を維持できないという問題があった。
【０００６】
【課題を解決するための手段】
本発明は、上述の問題点を解決したもので、その要旨とするところは、
固体高分子型燃料電池セパレータの少なくとも片側周縁部に位置するパッキング材であって、そのパッキング材が次のＡ液とＢ液を架橋反応させてなる付加型シリコーンからなり、熱架橋後、４０℃でパルスＮＭＲ法で測定した横緩和時間Ｔ２の分布が
２００μＳ以上の長時間領域Ｔ２Ｌ：５０〜９３％
２００μＳ未満の短時間領域Ｔ２Ｓ： ７〜５０％
になるようにしたことを特徴とする固体高分子型燃料電池用パッキング材である。
【０００７】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明に使用される液状シリコーンは、上記に示した化学構造式のＡ液及びＢ液を用い、通常この二液は成形直前に混合し、この混合時に触媒として通常白金系触媒が使用され、補強剤としてシリカ（比表面積＞８０ｍ２／ｇ）、や珪藻土、石英粉及び３次元網目構造をとるシリコーンレジンが使用される。
【００１０】
本発明においては、前述した白金系触媒、補強剤を含む上記Ａ液とＢ液が熱架橋することにより得られる組成物のパルスＮＭＲ法により４０℃で測定した横緩和時間（以下「Ｔ２」という）の分布が次のようになる必要がある。
即ちＴ２を２００μＳ以上の長時間領域（以下「Ｔ２Ｌ」という）と２００μＳ未満の短時間領域（以下「Ｔ２Ｓ」という）の２領域に分けた場合、Ｔ２Ｌが５０〜９３％とＴ２Ｓが７〜５０％、好ましくはＴ２Ｌが７０〜９３％、Ｔ２Ｓが７〜３０％にすることで、優れた耐酸性を有することを見出したものである。
【００１１】
このＴ２Ｌが５０％未満でＴ２Ｓが５０％を越える場合は、得られる組成物は柔軟性に劣り硬く脆くなるという問題がある。また、Ｔ２Ｌが９０％を越えＴ２Ｓが１０％未満では、耐酸性に劣るという問題がある。
Ｔ２Ｌ及びＴ２Ｓを上記範囲内に入れるには、架橋剤の使用量や補強剤の種類、使用量を検討することにより適宜決めることが可能である。
【００１２】
パルスＮＭＲによるＴ２の測定には種々の方法があるが、不均一系の固体に対して精度良くＴ２が測定できるソリッドエコー法による測定が好ましい。
Ｔ２Ｌ及びＴ２Ｓの割合は測定信号（ＦＩＤ）を次式（１）に近似してＴ２Ｌ及びＴ２Ｓにおける信号強度を求め、その割合から求めることが出来る。
【００１３】
Ｔ２Ｌ領域の割合：Ｍｌ／（Ｍｌ＋Ｍｓ）×１００（％）
Ｔ２Ｓ領域の割合：Ｍｓ／（Ｍｌ＋Ｍｓ）×１００（％）
【００１４】
これらの測定方法や解析方法に関しては例えば「高分子の磁気共鳴」高分子実験学１８、高分子学会高分子実験学編集委員会編、共立出版株式会社（１９７５）などに詳しく記載されている。
【００１５】
本発明の液状シリコーンを用いたパッキング材の成形方法は、射出成形方法やプレス成形方法及びセパレータの少なくとも片面に近接して吐出ノズルを設け、セパレータと吐出ノズルを相対移動させながら、液状シリコーンを吐出ノズルから吐出し、ついで硬化させる方法によれば良い。
【００１６】
成形後のシリコーンゴム層の厚みは０．０５ｍｍ〜４．０ｍｍの範囲とすることが好ましく、０．０５ｍｍ未満では弾力効果が出にくく、パッキング材としての利用性に劣り、４．０ｍｍを超えるものでは燃焼電池、特に固体高分子型燃料電池のパッキング材用としての用途では小型化しずらく、またコスト高になり易い。
【００１７】
なお、上述したセパレータの表面には、密着性の点から各種プライマー層を設けても良い。このプライマー層はスプレー法やディッピング法等の通常の方法により被覆すればよい。プライマー層の厚みは０．０１μｍ〜５．０μｍの範囲であることが好ましく、０．０１μｍ未満では、塗布厚さの調整が困難であり、５．０μｍを越えるものでは、密着性の改良効果が少ない。
【００１８】
さらに、成形後のシリコーンゴム層の硬度は２０〜７０、好ましくは３０〜６０の範囲とすることが好ましい。硬度の測定方法はＪＩＳＫ６３０１スプリング式硬さ試験Ａ形に準拠して行なう。
この硬度が２０未満ではゴム反発力が低く初期シール力が足らずシール不良を起こし、７０を超えると硬くなりすぎてセパレータを何枚も重ねる際に重ねにくい傾向にある。
【００１９】
【実施例】
以下、実施例について説明するが、本発明はこれに限定されるものではない。
Ａ液及びＢ液中にビニル基を、またＢ液中には、Ａ液及びＢ液中に含まれた合計ビニル基モル量を上まわる水素基を含ませ、Ａ液及びＢ液（重量比でＡ液：Ｂ液＝１：１）中の合計ビニル基モル量を架橋剤量とした。
【００２０】
また、表１に示す如く、架橋剤量０．６モル％、補強剤として煙霧質シリカ（乾式シリカ）１３重量％を添加した試料Ｎｏ．１、架橋剤量０．５モル％、補強剤として煙霧質シリカ（乾式シリカ）１３重量％を添加した試料Ｎｏ．２、架橋剤量０．７モル％、補強剤としてシリコーンレジン１３重量％を添加した試料Ｎｏ．３、架橋剤量２．０モル％、補強剤として煙霧質シリカ（乾式シリカ）６重量％を添加した試料Ｎｏ．４の原料を作成した。
【００２１】
上記試料Ｎｏ．１〜４の液状シリコーンゴム原料を使用して下記方法にてパッキング材を得た。
原料をビーカー中で攪拌混合し、２時間真空乾燥機内で真空脱泡した。その後、所定の形状（１００ｍｍ×１００ｍｍ×０．５ｍｍ）の金型に充填し、再度２時間乾燥機中で真空脱泡した。
次に上型で蓋をしプレス機を用いて１５０℃の加熱温度で８．８２×１０６Ｐａ（９０ｋｇｆ／ｃｍ２）の圧力で１０分間加圧した。その後、２００℃で４時間加熱（２次加硫）し得られたシートを１ｃｍ×２ｃｍの試験片に打ち抜いた。
得られた試験片を、パルスＮＭＲ測定及びマイクロウエーブオーブン耐酸性試験を行い、その結果を表１に示した。
【００２２】
パルスＮＭＲ測定方法：
測定機器としてＮＭＲ装置（日本電子社製「ＴＮＭ−ＭＵ２５Ａ」）を用い、次の条件で測定した。
観測核：１Ｈ
観測周波数：２５ＭＨｚ
測定温度：４０℃
測定に用いたパルス列：ソリッドエコー法（例えば、「高分子実験講座」１２巻、高分子の磁気共鳴、共立出版、１９７５年参照）によった。
９０°パルス幅：２μＳ
回復時間（静磁場方向の磁化が平衡値に回復するのに要する時間）：２．５Ｓ
積算回数：３２回
ＮＭＲサンプル管：外径１０φ、内径８φ、パイレックスガラス製
【００２３】
マイクロウエーブオーブン耐酸性試験方法：
▲１▼ 縦１ｃｍ、横２ｃｍ、厚み０．５ｍｍの試験片３枚と１規定（Ｎ）の硫酸１０ｍｌを四フッ化エチレン樹脂（テフロン）製容器に入れる。
▲２▼更に上記容器をポリエーテルイミド樹脂（ウルテム）製耐熱耐圧容器に入れキャップを取り付け密閉した後、マイクロウエーブオーブンに入れる。
▲３▼ マイクロウエーブオーブンの条件を出力４０％（２０Ｗ）、加熱時間６０分、圧力６．７６×１０５Ｐａ（１００ＰＳＩ）に設定して、試験片を加熱する。
▲４▼加熱終了後、容器を室温まで冷却し、試験片を１枚取り出しサンプリングする。（試験１回目）
▲５▼再び上記▲２▼〜▲４▼を繰り返し、試験片を１枚取り出しサンプリングする。（試験２回目）
▲６▼更に再び上記▲２▼〜▲４▼を繰り返し、試験片を１枚取り出しサンプリングする。（試験３回目）
尚、上記マイクロウエーブオーブン装置は、ＣＥＭ社（米国）製圧力コントロールマイクロウエーブオーブンＤＳ−２０００を使用した。
【００２４】
試験後の試験片が試験前と同じものを○、一部白濁しているものを△、全面に白濁しているものを×とした。
【００２５】
【表１】
表１から本発明において規定するＴ２Ｌが５０〜９３％、Ｔ２Ｓが７〜５０％になるように作成した試料Ｎｏ．３及び試料Ｎｏ．４はマイクロウエーブオーブン試験を３回（１８０分）行っても、白濁等の外観変化は見られず、耐酸性が良く、長期の耐久性に優れていることがわかる。
これに対して、Ｔ２Ｌが９３％を越え、Ｔ２Ｓが７％未満の試料Ｎｏ．１及びＮｏ．２はマイクロウエーブオーブン試験１回目で試験片に白濁が見られ耐酸性に劣っていることがわかる。
【００２７】
【発明の効果】
上述したように、本発明のパッキング材は、耐酸性が良く、長期間弾性を維持できて耐久性に優れており、長期の使用が可能な固体高分子型燃料電池用パッキング材として好適に使用できる。[0001]
BACKGROUND OF THE INVENTION
TECHNICAL FIELD The present invention relates to a packing material for a polymer electrolyte fuel cell that can be used as a small fuel cell, and particularly has good acid resistance, can be used for a long time, and has excellent moldability. Regarding materials.
[0002]
[Prior art]
Fuel cells are being actively developed in response to recent environmental and resource issues.
In particular, as a fuel cell, a polymer electrolyte fuel cell has been studied from the demand for reduction in size and weight. As such a battery separator, further downsizing is required, and since a large number of separators are overlapped and used, a packing material is provided on the peripheral edge of at least one side of the separator. There is a demand for packing materials that are excellent in quality and can be used for a long time.
[0003]
As such a polymer electrolyte fuel cell packing material, a silicone rubber packing material excellent in moldability, heat resistance and elasticity is mainly used. Further, as the silicone rubber, a two-component type addition type liquid silicone having further excellent moldability is used.
[0004]
[Problems to be solved by the invention]
As the polymer electrolyte used in the above polymer electrolyte fuel cell, a fluorocarbon polymer membrane having a sulfone group at the end of the side chain can be used. This electrolyte has proton conductivity in a state containing moisture. Therefore, in order to operate a battery, it is necessary to always make the polymer electrolyte contain water. The polymer electrolyte membrane in a state containing moisture exhibits strong acidity due to hydrogen ions dissociated from the terminal sulfone group. For this reason, acid-proof is requested | required of the packing material for polymer electrolyte fuel cells.
[0005]
However, although the two-component type addition type liquid silicone is excellent in moldability, it has poor acid resistance and cannot maintain long-term elasticity.
[0006]
[Means for Solving the Problems]
The present invention solves the above-mentioned problems, and the gist thereof is as follows.
A packing material located on at least one peripheral edge of the polymer electrolyte fuel cell separator, the packing material comprising an addition type silicone obtained by cross-linking reaction of the following liquid A and liquid B, and after thermal crosslinking, Long time region T2L in which the distribution of transverse relaxation time T2 measured by pulsed NMR method is 200 μS or more: 50 to 93%
Short-time region T2S of less than 200 μS: 7 to 50%
It is the packing material for solid polymer type fuel cells characterized by becoming.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The liquid silicone used in the present invention uses the liquid A and liquid B of the chemical structural formula shown above, and usually the two liquids are mixed immediately before molding, and a platinum-based catalyst is usually used as a catalyst during the mixing. Silica (specific surface area> 80 m 2 / g), diatomaceous earth, quartz powder and silicone resin having a three-dimensional network structure are used as reinforcing agents.
[0010]
In the present invention, the transverse relaxation time (hereinafter referred to as “T2”) measured at 40 ° C. by the pulse NMR method of the composition obtained by thermally crosslinking the above-described platinum solution and the solution B containing the platinum-based catalyst and the reinforcing agent. ) Distribution must be as follows:
That is, when T2 is divided into two regions, a long time region of 200 μS or more (hereinafter referred to as “T2L”) and a short time region of less than 200 μS (hereinafter referred to as “T2S”), T2L is 50 to 93% and T2S is 7 to 50. %, Preferably T2L is 70 to 93% and T2S is 7 to 30%, and has been found to have excellent acid resistance.
[0011]
When this T2L is less than 50% and T2S exceeds 50%, there is a problem that the resulting composition is inferior in flexibility and hard and brittle. Further, when T2L exceeds 90% and T2S is less than 10%, there is a problem that the acid resistance is poor.
In order to put T2L and T2S within the above range, it is possible to appropriately determine the amount of crosslinking agent used, the type of reinforcing agent, and the amount used.
[0012]
There are various methods for measuring T2 by pulsed NMR, but measurement by a solid echo method capable of measuring T2 with high accuracy for a heterogeneous solid is preferable.
The ratio of T2L and T2S can be obtained from the ratio of the measurement signal (FID) obtained by approximating the measurement signal (FID) to the following equation (1) to obtain the signal intensity at T2L and T2S.
[0013]
T2S region ratio: Ms / (Ml + Ms) × 100 (%)
[0014]
These measurement methods and analysis methods are described in detail in, for example, “Polymer Magnetic Resonance” Polymer Experimental Studies 18, edited by the Society of Polymer Science, Polymer Experimental Studies Editorial Committee, Kyoritsu Publishing Co., Ltd. (1975).
[0015]
The method for molding a packing material using liquid silicone according to the present invention includes an injection molding method, a press molding method, and a discharge nozzle provided close to at least one surface of the separator. A method of discharging from the nozzle and then curing may be used.
[0016]
The thickness of the silicone rubber layer after molding is preferably in the range of 0.05 mm to 4.0 mm, and if it is less than 0.05 mm, the elastic effect is difficult to be obtained, and the utilization as a packing material is inferior, and the thickness exceeds 4.0 mm Then, it is difficult to reduce the size and the cost tends to be high for use as a packing material for a combustion cell, particularly a polymer electrolyte fuel cell.
[0017]
In addition, you may provide various primer layers on the surface of the separator mentioned above from the point of adhesiveness. This primer layer may be coated by a usual method such as a spray method or a dipping method. The thickness of the primer layer is preferably in the range of 0.01 μm to 5.0 μm. If the thickness is less than 0.01 μm, it is difficult to adjust the coating thickness. If the thickness exceeds 5.0 μm, the adhesion improving effect is improved. Few.
[0018]
Furthermore, the hardness of the silicone rubber layer after molding is preferably in the range of 20 to 70, preferably 30 to 60. The hardness is measured in accordance with JISK6301 spring type hardness test A type.
If the hardness is less than 20, the rubber repulsive force is low and the initial sealing force is insufficient, resulting in a sealing failure. If it exceeds 70, the rubber becomes so hard that it tends to be difficult to stack many separators.
[0019]
【Example】
Hereinafter, although an example is described, the present invention is not limited to this.
A liquid group and B liquid contain vinyl groups, and B liquid contains hydrogen groups that exceed the total amount of vinyl groups contained in A liquid and B liquid. The total vinyl group molar amount in A liquid: B liquid = 1: 1) was defined as the amount of the crosslinking agent.
[0020]
In addition, as shown in Table 1, the sample No. 1 was obtained by adding 0.6% by mole of a crosslinking agent and 13% by weight of fumed silica (dry silica) as a reinforcing agent. 1. Sample No. 1 containing 0.5 mol% of a crosslinking agent and 13 wt% of fumed silica (dry silica) as a reinforcing agent was added. 2. Sample No. 2 containing 0.7 mol% of a crosslinking agent and 13 wt% of a silicone resin as a reinforcing agent. 3. Sample No. 2 containing 2.0 mol% of a crosslinking agent and 6 wt% of fumed silica (dry silica) as a reinforcing agent was added. 4 raw materials were prepared.
[0021]
Sample No. above. The packing material was obtained by the following method using 1-4 liquid silicone rubber raw materials.
The raw materials were stirred and mixed in a beaker and vacuum degassed in a vacuum dryer for 2 hours. Then, it filled with the metal mold | die of a predetermined | prescribed shape (100 mm x 100 mm x 0.5 mm), and vacuum-defoamed again for 2 hours in the dryer.
Next, it was covered with an upper mold, and pressurized using a press at a heating temperature of 150 ° C. and a pressure of 8.82 × 10 6 Pa (90 kgf / cm 2 ) for 10 minutes. Thereafter, the sheet obtained by heating (secondary vulcanization) at 200 ° C. for 4 hours was punched into a 1 cm × 2 cm test piece.
The obtained test pieces were subjected to pulse NMR measurement and microwave oven acid resistance test, and the results are shown in Table 1.
[0022]
Pulse NMR measurement method:
An NMR apparatus (“TNM-MU25A” manufactured by JEOL Ltd.) was used as a measuring instrument, and measurement was performed under the following conditions.
Observation nucleus: 1H
Observation frequency: 25 MHz
Measurement temperature: 40 ° C
Pulse train used for measurement: Solid echo method (see, for example, “Polymer Experiment Course”, Vol. 12, Magnetic Resonance of Polymers, Kyoritsu Shuppan, 1975).
90 ° pulse width: 2μS
Recovery time (time required for the magnetization in the direction of the static magnetic field to recover to the equilibrium value): 2.5S
Integration count: 32 times NMR sample tube: 10φ outer diameter, 8φ inner diameter, made of Pyrex glass
Microwave oven acid resistance test method:
(1) Three test pieces each having a length of 1 cm, a width of 2 cm, and a thickness of 0.5 mm and 10 ml of 1 N (N) sulfuric acid are placed in a container made of tetrafluoroethylene resin (Teflon).
(2) Further, the container is placed in a heat-resistant pressure-resistant container made of polyetherimide resin (Ultem), sealed with a cap, and then placed in a microwave oven.
{Circle around (3)} The conditions of the microwave oven are set to output 40% (20 W), heating time 60 minutes, pressure 6.76 × 10 5 Pa (100 PSI), and the test piece is heated.
(4) After heating, the container is cooled to room temperature, and one specimen is taken out and sampled. (First test)
(5) The above steps (2) to (4) are repeated again, and one specimen is taken out and sampled. (2nd test)
{Circle around (6)} Repeat steps {circle around (2)} to {circle around (4)} again to take out one specimen and sample it. (3rd test)
The microwave oven apparatus used was a pressure control microwave oven DS-2000 manufactured by CEM (USA).
[0024]
The test piece after the test was the same as that before the test, ◯ that was partially cloudy, and x that was cloudy on the entire surface.
[0025]
[Table 1]
Sample No. 1 prepared from Table 1 so that T2L specified in the present invention is 50 to 93% and T2S is 7 to 50%. 3 and Sample No. No. 4 shows that even when the microwave oven test is performed three times (180 minutes), no change in appearance such as cloudiness is observed, the acid resistance is good, and the long-term durability is excellent.
On the other hand, sample Nos. With T2L exceeding 93% and T2S less than 7%. 1 and no. It can be seen that No. 2 is inferior in acid resistance because cloudiness is seen in the test piece in the first microwave oven test.
[0027]
【The invention's effect】
As described above, the packing material of the present invention has good acid resistance, can maintain elasticity for a long time, has excellent durability, and is suitably used as a packing material for a polymer electrolyte fuel cell that can be used for a long time. it can.
Claims (1)
熱架橋後、４０℃でパルスＮＭＲ法で測定した横緩和時間Ｔ２の分布が、
２００μｓ以上の長時間領域Ｔ２Ｌ：７９〜９０％、
２００μｓ未満の短時間領域Ｔ２Ｓ：１０〜２１％
になるようにしたことを特徴とする固体高分子型燃料電池用パッキング材。
After thermal crosslinking, the distribution of transverse relaxation time T2 measured by pulse NMR at 40 ° C.
Long-term region T2L of 200 μs or more: 79 to 90 %,
Short-time region T2S of less than 200 μs : 10 to 21 %
A packing material for a polymer electrolyte fuel cell, characterized in that
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| JP4485552B2 (en) | 2007-08-03 | 2010-06-23 | 本田技研工業株式会社 | Manufacturing method of fuel cell separator |
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