Preparation and Evaluation of Proton Conductive Membranes for Medium Temperature Fuel Cells

中温燃料电池质子传导膜的制备与评价

• 批准号: 14550669
• 负责人: MATSUDA Atsunori
• 金额: $ 2.3万
• 依托单位: Toyohashi University of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14550669/
• 关键词: Proton conductor; Inorganic-organic composite; Thermally stable polymer; Fuel cell; Medium temperature range; Phosphosilicate gel; Sol-gel method; Polyimide; 無機-有機複合体; ホスドホシリケートゲル; ゾル-ゲル法

Solid state proton-conductive membranes with high conductivity in the medium temperature range (100-200ーC) even under low humidity are highly required as the electrolytes for PEFCs. Since the operation of PEFCs in the medium temperature range improves the utilization of total electric power generated in the cells. and depresses the poisoning of Pt catalysts with CO in the fuel gases. In addition, working of PEFCs under low humidity permits to reduce the weight and volume of humidifiers. In the present work, proton conducting membranes based on sol-gel derived phosphosilicate (P_2O_5-SiO_2) gel have been fabricated for the application to medium temperature fuel cells as an electrolyte.Two types of proton conductive membranes, which show high conductivities even at medium temperatures with low humidity, have been successfully prepared. One is a composite sheet composed of phosphosilicate gel powder and organic polymer such as heat resistant polyimide. The other is a hybrid sheet in which inorganic and organic components derived from an organosilane such as 3-Glycidoxypropyltrimethoxysilane and phosphoric acid are covalently bonded.Fuel cells using a composite sheet composed of phosphosilicate (P_2O_5-SiO_2, P/Si=1 in mole ratio) gel powder and polyimide operated up to 150ーC under a relatively low water vapor, pressure. Maximum power density of the fuel cell increased with increasing operation temperature and was 28 mW cm^<-2> at 150 ℃ and 18 %RH. With respect to the hybrid type, fuel cells using a hybrid sheet derived from 3-Glycidoxypropyltrimethoxysilane and phosphoric, acid also continuously operated at 130 ℃.It was found that the addition of tin and tantalum as well as aluminum improved the chemical durability of phosphosilicate gels by depressing the leaching of phosphoric acid from the gels. At the same time, the improvement of durability of the gels resulted in a decrease in the proton conductivity.

由于PEFC在中温范围内运行提高了总电的利用率，因此非常需要在中温范围（100-200℃）甚至在低湿度下也具有高电导率的固态质子导电膜作为PEFC的电解质。此外，PEFC 在低湿度下工作还可以减少加湿器的重量和体积。目前的工作，基于溶胶-凝胶衍生的磷硅酸盐（P_2O_5-SiO_2）凝胶的质子传导膜已被制备用于中温燃料电池作为电解质。两种类型的质子传导膜，即使在中温下也表现出高电导率一种是由磷硅酸盐凝胶粉末和有机聚合物（例如耐热聚酰亚胺）组成的复合片材，另一种是无机聚合物的混合片材。 3-缩水甘油氧基丙基三甲氧基硅烷等有机硅烷和磷酸衍生的有机成分以共价键结合。使用由磷硅酸盐（P_2O_5-SiO_2，摩尔比P/Si=1）凝胶粉末和聚酰亚胺组成的复合片的燃料电池在高达150℃的温度下运行-C在相对较低的水蒸气压力下，燃料电池的最大功率密度随着工作温度的升高而增加，为28。在150℃和18％RH下的mW cm^ -2 对于混合型，使用源自3-缩水甘油氧基丙基三甲氧基硅烷和磷酸的混合片的燃料电池也在130℃下连续运行。锡、钽以及铝的添加通过抑制磷酸从凝胶中的浸出而提高了磷硅酸盐凝胶的化学耐久性。同时，凝胶耐久性的提高导致质子电导率的降低。

项目成果

忠永清治, 他: "中温作動燃料電池用プロトン伝導性無機-有機複合体電解質膜(解説)"工業材料. 51. 35-38 (2003)

Seiji Tadanaga 等人：“用于中温操作燃料电池的质子传导无机-有机复合电解质膜（评论）”工业材料。51. 35-38 (2003)。

A.Matsuda et al.: "Phosphosilicate Gels as a Solid State Proton Conductor at Elevated Temperature and Low Humidity"Journal of Ceramic Society of Japan. 110. 131-134 (2002)

A.Matsuda 等人：“在高温和低湿度下作为固态质子导体的磷硅酸盐凝胶”日本陶瓷学会杂志。

A.Matsuda et al.: "Sol-Gel Derived Porous Silica Gels Impregnated with Sulfuric Acid : Pore Structure and Proton Coductivities at Medium Temperatures"Journal of Electrochemical Society. 149. E292-E297 (2002)

A.Matsuda 等人：“用硫酸浸渍的溶胶-凝胶衍生的多孔硅胶：中温下的孔结构和质子电导率”电化学学会杂志。

K.Tadanaga, et al.: "Inorganic-Organic Hybrid Films from 3-Glycidoxypropyltrimethoxysilane and Orthophosphoric Acid as Medium Temperature Fuel Cells"Electrochemistry Communications. 5・[8]. 644-646 (2003)

K. Tadanaga 等人：“作为中温燃料电池的 3-缩水甘油氧基丙基三甲氧基硅烷和正磷酸的无机-有机混合薄膜”电化学通讯 5·[8]（2003 年）。

松田厚範, 他(分担執筆): "最新燃料電池部材その最先端技術と信頼性評価"技術情報協会. 234 (2003)

Atsunori Matsuda 等人（撰稿人）：“当前最新燃料电池组件的尖端技术和可靠性评估”技术信息协会 234 (2003)。