Development of Intermediate Temperature Solid Oxide Fuel Cells employing New Electrolyte and Electrode

采用新型电解质和电极的中温固体氧化物燃料电池的开发

• 批准号: 15560611
• 负责人: HASHIMOTO Takuya
• 金额: $ 2.43万
• 依托单位: Nihon University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15560611/
• 关键词: solid oxide fuel cell; solid electrlyte; electrode material; defect structure; ion conductor; reduction expansion; thermodynamic stabiblity; 化学的安定性; 構造相転移; 電気伝導; 熱膨張特性; 過電圧

To develop solid oxide duel cells operating at temperatures lower than 700℃, stability and electrical property of various materials at high temperatures under various gas atmospheres were investigated. As new electrolyte materials, Ba_2In_2O_5 and La_<1-x>Sr_xGa_<1-y>Mg_yO_<3-δ> were estimated. The property of La_<0.6>Sr_<0.4>Co_<1-y>Ga_yO_<3-δ> and La_<1-x>Ca_xCrO_<3-δ> were analyzed from the viewpoint of cathode and interconnector materials, respectively.It was revealed that the phase of Ba_2In_2O_5 at temperatures more than 1070℃, which was discovered in this work, had high thermodynamic stability and oxide ion conductivity under oxygen partial pressure of 1〜10^<-4> atm ; however, it was not suitable for electrolyte materials since it decomposed at 900℃ under fuel gas atmosphere with oxygen partial pressures lower than 10^<-17> atm. On the contrary, La_<1-x>Sr_xGa_<1-y>Mg_yO_<3-δ> has high potential for new electalyte materials since it showed high thermal stability and oxide ion co … More nductivity under oxygen partial pressure of 1〜10^<-22> atm. It was also discovered that the structural phase transition of La_<1-x>Sr_xGa_<1-y>Mg_yO_<3-δ>, which is one of the problems for application, can be suppressed by partial substitution of Al for Ga site.La_<0.6>Sr_<0.4>Co_<1-y>Ga_yO_<3-δ> showed high oxide ion and hole conductivity under atmospheres for cathode electrode with oxygen partial pressure of 1〜10^<-4> atm. Since thermal expansion of La_<0.6>Sr_<0.4>Co_<1-y>Ga_yO_<3-δ> showed close behavior to those of electrolyte materials, it was estimated that La_<0.6>Sr_<0.4>Co_<1-y>Ga_yO_<3-δ> had high potential for new cathode materials. Prototype fuel cell employing La_<1-x>Sr_xGa_<1-y>Mg_yO_<3-δ>, La_<0.6>Sr_<0.4>Co_<1-y>Ga_yO_<3-δ> and Ni as electrolyte, cathode and anode, respectively, was developed and its property was estimated. We have succeeded in operation of the prototype cell at 600℃.We also analyzed property of La_<1-x>Ca_xCrO_<3-δ> as interconnectior under various gas atmospheres and revealed that the generation of oxide ion vacancy at temperatures more than 700℃ under reduction atmosphere caused the reduction expansion, which could be thermodynamically explained by ideal solution model. It was concluded that increase of electrical conductivity at less than 600℃ was necessary for application of La_<1-x>Ca_xCrO_<3-δ> as an interconector. Less

为了研制出工作温度低于70 0℃的固体氧化物双电池，研究了各种材料在不同气体气氛下的高温稳定性和电性能。对新型电解液材料Ba2In2O5和La_&lt；1-x&gt；Sr_xGa_&lt；1-y&gt；Mg_yO_&lt；3-δ&gt；进行了评价。La_&lt；0.6&gt；Sr_&lt；0.4&gt；Co_&lt；1-y&gt；Ga_yO_&lt；3-δ&gt；和La_xCrO_3-δ&gt；1-x&gt；结果表明，在1070℃以上的Ba2In2O5相具有较高的热力学稳定性，在氧分压为1~10；-4atm的条件下具有较高的氧离子导电性，但在氧分压低于10atm的燃气气氛中，它在900℃时分解，不适合作电解液材料。相反，La_&lt；1-x&gt；Sr_xGa_&lt；1-y&gt；Mg_yO_&lt；3-δ&gt；具有很高的热稳定性和氧离子共价性，因此在新的电催化材料中具有很大潜力。在氧分压为1~10；-22大气压时有较高的电导率。研究还发现，Al部分替代Ga-La_&lt；1-x&gt；Sr_xGa_&lt；1-y&gt；Mg_yO_&lt；3-δ&gt；，可以抑制site.La_&lt；0.6&gt；Sr_&lt；0.4&gt；Co_&lt；1-y&gt；Ga_yO_&lt；3-δ&gt；的结构相变，这是应用中存在的问题之一氧分压为1~10；-4大气压的阴极电极在大气压下表现出较高的氧离子和空穴电导率。由于La_&lt；0.6&gt；Sr_&lt；0.4&gt；Co_&lt；1-y&gt；Ga_yO_&lt；3-δ&gt；的热膨胀行为与电解液材料的热膨胀行为相近，因此La_&lt；0.6&gt；Sr_&lt；0.4&gt；Co_&lt；1-y&gt；Ga_yO_&lt；3-δ&gt；被认为是一种很有潜力的新型正极材料。研制了以La_&lt；1-x&gt；Sr_xGa_&lt；1-y&gt；Mg_yO_&lt；3-δ&gt；，La_&lt；0.6&gt；Sr_&lt；0.4&gt；Co_&lt；1-y&gt；Ga_yO_&lt；3-δ&gt；为电解液、以镍为阴极、以镍为阳极的燃料电池样机，并对其性能进行了评价。并分析了La_&lt；1-x&gt；Ca_xCrO_&lt；3-δ&gt；作为互连体在不同气体气氛下的性质，揭示了还原气氛下700℃以上温度下氧化物离子空位的产生是导致还原膨胀的原因，可用理想溶液模型进行热力学解释。结果表明，La_xCrO_3-℃&Gt；1-x&Gt；3-δ&gt；较少

项目成果

S.Wang et al.: "Structural Analysis of Ce_<1-x>MxO_<2-0.5x-δ> (M=Gd,Sm,Y) by High Temperature XRD under Various Oxygen Partial Pressures"Journal of the Electrochemical Society. 151・2. E46-E50 (2004)

S. Wang等：“在不同氧分压下通过高温XRD对Ce_<1-x>MxO_<2-0.5x-δ> (M=Gd,Sm,Y)进行结构分析”电化学会杂志151·2。

Electrical conductivity and crystal structure of Ba_2In_2O_5 at high temperatures under various oxygen partial pressure.

不同氧分压下高温Ba_2In_2O_5的电导率和晶体结构

• 发表时间: 2005
• 期刊: Journal of the Electrochemical Society (in press)
• 作者: M.Yoshinaga et al.;M.Yoshinaga et al.
• 通讯作者: M.Yoshinaga et al.

Electrical conductivity and crystal structure of Ba_2In_2O_5 at high temperatures under various oxygen partial pressures.

不同氧分压下高温Ba_2In_2O_5的电导率和晶体结构。

• 发表时间: 2005
• 期刊: Journal of the Electrochemical Society (in press)
• 作者: M.Yoshinaga et al.

Preparation, thermal expansion and electrical conductivity of La_<0.6>Sr_<0.4>Co_<1-x>Ga_xO_<3-δ>(x=0.0-0.4) as a new cathode material of SOFC

新型SOFC正极材料La_<0.6>Sr_<0.4>Co_<1-x>Ga_xO_<3-δ>(x=0.0-0.4)的制备、热膨胀及电导率

• 发表时间: 2004
• 期刊: Solid State Ionics 174
• 作者: M.Yoshinaga et al.;M.Yoshinaga et al.;T.Shibasaki et al.;S.Wang et al.;S.Wang et al.;S.Wang et al.
• 通讯作者: S.Wang et al.

Preparation, thermal expansion and electrical conductivity of La_<0.6>Sr_<0.4>Co_<1-x>Ga_xO_<3-δ> (x=0.0-0.4) as a new cathode material of SOFC

新型SOFC正极材料La_<0.6>Sr_<0.4>Co_<1-x>Ga_xO_<3-δ>(x=0.0-0.4)的制备、热膨胀及电导率

• 发表时间: 2004
• 期刊: Solid State Ionics 174
• 作者: M.Yoshinaga et al.;M.Yoshinaga et al.;T.Shibasaki et al.;S.Wang et al.;S.Wang et al.
• 通讯作者: S.Wang et al.