High-temperature proton exchange membrane fuel cells(HT-PEMFC) possess distinct technical advantages of high output power, simplified water/heat management, increased tolerance to fuel impurities and diverse fuel sour...High-temperature proton exchange membrane fuel cells(HT-PEMFC) possess distinct technical advantages of high output power, simplified water/heat management, increased tolerance to fuel impurities and diverse fuel sources, within the temperature range of 120–200 ℃. However, for practical automobile applications, it was crucial to broaden their low-temperature operating window and enable cold start-up capability. Herein, gel-state phosphoric acid(PA) doped sulfonated polybenzimidazole(PBI) proton exchange membranes(PEMs) were designed and synthesized via PPA sol-gel process and in-situ sultone ring-opening reactions with various proton transport pathways based on absorbed PA, flexible alkyl chain connected sulfonic acid groups and imidazole sites. The effects of flexible alkyl sulfonic acid side chain length and content on PA doping level, proton conductivity, and membrane stability under different temperature and relative humidity(RH) were thoroughly investigated. The prepared gel-state membranes contained a self-assembled lamellar and porous structure that facilitated the absorption of a large amount of PA with rapid proton transporting mechanisms. At room temperature, the optimized membrane exhibited a proton conductivity of 0.069 S cm^(-1), which was further increased to 0.162 and 0.358 S cm^(-1)at 80 and 200 ℃, respectively, without additional humidification. The most significant contribution of this work was demonstrating the feasibility of gel-state sulfonated PBI membranes in expanding HT-PEMFC application opportunities over a wider operating range of 25 to 240 ℃.展开更多
为降低Li_(1+x)Al_(x)Ti_(2-x)(PO_(4))_(3)(LATP)电解质膜与锂金属负极之间的界面阻抗,抑制LATP与锂金属之间的副反应以及锂枝晶的生长,提高LATP电解质膜的性能,使用PVDF对LATP基电解质膜界面进行修饰,并研究其电化学性能。将LATP陶瓷...为降低Li_(1+x)Al_(x)Ti_(2-x)(PO_(4))_(3)(LATP)电解质膜与锂金属负极之间的界面阻抗,抑制LATP与锂金属之间的副反应以及锂枝晶的生长,提高LATP电解质膜的性能,使用PVDF对LATP基电解质膜界面进行修饰,并研究其电化学性能。将LATP陶瓷粉末与聚氧化乙烯、LIFSI混合均匀后浇筑成膜,将PVDF溶液均匀涂覆在电解质膜表面,干燥得到修饰后的电解质膜。通过电化学实验、充放电实验、表面表征等方法,研究PVDF修饰后电解质膜的性能。结果显示,PVDF影响了LATP的晶体结构,优化了锂离子迁移通道。修饰后电解质膜的室温离子电导率提升,室温下电化学窗口由3.74 V增加到4.10 V,锂离子迁移数由0.915提升到0.978,组装锂金属对称电池在0.05 m A/cm^(2)电流密度下的循环时间从45 h提升到280 h以上,有效抑制了锂枝晶的生长,提升了电解质膜与锂金属界面稳定性。在电流密度0.025、0.050、0.100、0.200 m A/cm^(2)下的极化电压分别为27、60、110、220 m V。在LFP|SSCEs-1|Li全电池中循环超过25圈后形成了良好的SEI界面。从第25圈到第100圈容量保持率为87%,库仑效率始终保持在95%以上。PVDF修饰层提升了LATP电解质膜的电化学性能以及和锂金属界面的稳定性,对全固态锂电池的应用具有积极意义。展开更多
基金supported by the National Natural Science Foundation of China (NSFC-22209147)。
文摘High-temperature proton exchange membrane fuel cells(HT-PEMFC) possess distinct technical advantages of high output power, simplified water/heat management, increased tolerance to fuel impurities and diverse fuel sources, within the temperature range of 120–200 ℃. However, for practical automobile applications, it was crucial to broaden their low-temperature operating window and enable cold start-up capability. Herein, gel-state phosphoric acid(PA) doped sulfonated polybenzimidazole(PBI) proton exchange membranes(PEMs) were designed and synthesized via PPA sol-gel process and in-situ sultone ring-opening reactions with various proton transport pathways based on absorbed PA, flexible alkyl chain connected sulfonic acid groups and imidazole sites. The effects of flexible alkyl sulfonic acid side chain length and content on PA doping level, proton conductivity, and membrane stability under different temperature and relative humidity(RH) were thoroughly investigated. The prepared gel-state membranes contained a self-assembled lamellar and porous structure that facilitated the absorption of a large amount of PA with rapid proton transporting mechanisms. At room temperature, the optimized membrane exhibited a proton conductivity of 0.069 S cm^(-1), which was further increased to 0.162 and 0.358 S cm^(-1)at 80 and 200 ℃, respectively, without additional humidification. The most significant contribution of this work was demonstrating the feasibility of gel-state sulfonated PBI membranes in expanding HT-PEMFC application opportunities over a wider operating range of 25 to 240 ℃.
文摘为降低Li_(1+x)Al_(x)Ti_(2-x)(PO_(4))_(3)(LATP)电解质膜与锂金属负极之间的界面阻抗,抑制LATP与锂金属之间的副反应以及锂枝晶的生长,提高LATP电解质膜的性能,使用PVDF对LATP基电解质膜界面进行修饰,并研究其电化学性能。将LATP陶瓷粉末与聚氧化乙烯、LIFSI混合均匀后浇筑成膜,将PVDF溶液均匀涂覆在电解质膜表面,干燥得到修饰后的电解质膜。通过电化学实验、充放电实验、表面表征等方法,研究PVDF修饰后电解质膜的性能。结果显示,PVDF影响了LATP的晶体结构,优化了锂离子迁移通道。修饰后电解质膜的室温离子电导率提升,室温下电化学窗口由3.74 V增加到4.10 V,锂离子迁移数由0.915提升到0.978,组装锂金属对称电池在0.05 m A/cm^(2)电流密度下的循环时间从45 h提升到280 h以上,有效抑制了锂枝晶的生长,提升了电解质膜与锂金属界面稳定性。在电流密度0.025、0.050、0.100、0.200 m A/cm^(2)下的极化电压分别为27、60、110、220 m V。在LFP|SSCEs-1|Li全电池中循环超过25圈后形成了良好的SEI界面。从第25圈到第100圈容量保持率为87%,库仑效率始终保持在95%以上。PVDF修饰层提升了LATP电解质膜的电化学性能以及和锂金属界面的稳定性,对全固态锂电池的应用具有积极意义。
