摘要
钙钛矿型结构的质子导体材料由于其在中高温下具有较高的质子导电率且相对稳定,成为一种潜在的涉氢材料,目前其应用主要集中于固体燃料电池、氢气传感器、氢气的分离与提纯以及常压合成氨方面。随着能源的枯竭,氢气作为清洁能源引起了广泛的关注,科研工作者更加注重对氢气的利用。与其他类型以质子传导的电解质材料相比,钙钛矿型质子导体由于其较高的稳定性,低的质子传导活化能及较高的质子导电率,而成为众多科研工作者的研究重点。通过对近年来中高温ABO(A=Ca,Sr,Ba;B=Ce,Zr)基钙钛矿型质子导体陶瓷的典型应用及其稳定性和透氢性能的研究进展进行了归纳总结,并对质子导体电解质陶瓷的发展趋势进行了展望,为设计与制备高透氢性能、高稳定性及耐高温CO和水汽腐蚀的新型质子导体电解质陶瓷提供科学依据及参考。
With the aggravation of global climate instability,global warming have indeed affected people’s production and living activities.At the same time,as the heyday of the industrial revolution in the 21st century,the demand for resources and energy was increasingly strong,but thermal power generation would always rely on non-renewable energy,which would inevitably lead to energy crisis.In order to seek better development,the demand and application of clean energy were the development trend of the whole society and even the world.General Motors of the United States pointed out that hydrogen was used as a clean energy as early as 1970.As a clean new fuel,hydrogen have various preparation methods and simple preparation technology.It was very feasible as a new energy.At present,researchers have made extensive research on the preparation of hydrogen.The main goal at this stage was to solve a series of problems such as hydrogen storage and utilization.In order to use hydrogen on a large scale,the selection of materials for hydrogen storage and utilization should be as easy to prepare and low cost as possible.As hydrogen related material,proton conductor electrolyte ceramics played an important role in the production,purification and utilization of hydrogen.Proton conductor was a kind of conductor material that used proton as carrier to realize charge transfer process.At present,proton conductors were mainly divided into the following five categories.(1)Hydrated proton conductor,because this kind of proton conductor had a water layer in its structure,hydrogen ions could migrate in the water layer to show the characteristics of proton conductivity;However,because its proton transport process depended on the water layer,when the temperature increased,the proton conductivity of this type of proton conductor decreased due to the loss of crystalline water.(2)Hydrogen bonded proton conductor.Generally,when the temperature of this kind of proton conductor was lower than 200℃,the proton conductivity was relatively stable.Once the temperature was higher than 200℃,the proton conductivity was gradually weakened or even disappeared due to the gradual decomposition of solid compounds.(3)β-Al_(2)O_(3)type proton conductor was a layered Na^(+)conductor.After replacing Na^(+)with NH^(4+)or H_(3)O^(+),the obtained compound also had high proton conductivity at room temperature.(4)Hydrogen was inserted into compound proton conductors,but in this kind of proton conductors,proton conduction was not the main way of conduction,or electronic conduction was the main way.(5)Lattice defect proton conductor which was different from the above four types.The proton conductivity decreased at medium and high temperature.This type of proton conductor also had considerable proton conductivity in medium and high temperature environment and was relatively stable.Because lattice defect proton conductor was a relatively stable functional ceramic material that could be used in medium and high temperature,more and more researchers focused on this type of proton conductor.Proton conductor materials with perovskite structure have become a potential hydrogen related material because of their high proton conductivity and relative stability at medium and high temperatures.At present,their applications were mainly focused on solid fuel cells,hydrogen sensors,hydrogen separation and purification and atmospheric pressure synthesis of ammonia.At present,the proton conductors widely studied are mainly divided into three categories.First,Ba based proton conductors,such as BaCeO_(3)and BaZrO_(3).At present,BaCeO_(3)series ceramics had the highest proton conductivity.However,such ceramic materials showed oxygen ion conductivity in the presence of O_(2)or water vapor,and their stability was poor in the presence of CO_(2)or H_(3)O.Second,Sr based proton conductors SrCeO_(3)and SrZrO_(3),as the first discovered SrCeO_(3)materials with proton conductivity,although its total conductivity was lower than BaCeO_(3),its proton conductivity was higher at high temperature.The conductivity of doped SrZrO_(3)was lower than that of corresponding doped SrCeO_(3),but the doped material was still a pure proton conductor at 900℃,and its stability to CO_(2)at high temperature was higher than that of SrCeO_(3).Third,Ca based proton conductor CaZrO_(3),as the first proton conductor to be commercialized,although its conductivity was lower than that of doped SrCeO_(3)based and doped BaCeO_(3)based materials,CaZrO_(3)based system had high mechanical properties and chemical stability,which made it have great advantages in practical application.In this paper,the typical applications,stability and hydrogen permeability of medium and high temperature ABO_(3)(A=Ca,Sr,Ba;B=Ce,Zr)based perovskite proton conductor ceramics in recent years were summarized,and the development trend of proton conductor electrolyte ceramics was prospected.The new proton conductor electrolyte ceramics with high stability and high temperature CO_(2)and water vapor corrosion resistance provided scientific basis and reference.
作者
刘民
任宇梅
于庆河
米菁
郝雷
Liu Min;Ren Yumei;Yu Qinghe;Mi Jing;Hao Lei(College of Material Science and Technology,Liaoning Technology University,Fuxin 123000,China;National Engineering Research Center of Nonferrous Metals Materials and Products for New Energy,GRINM Group Co.,Ltd.,Beijing 100088,China;GRIMAT Engineering Institute Co.,Ltd.,Beijing 101407,China)
出处
《稀有金属》
EI
CAS
CSCD
北大核心
2022年第9期1244-1253,共10页
Chinese Journal of Rare Metals
基金
国家科技部重点基础研发计划项目(2016YFB0600103)资助。
关键词
质子导体
钙钛矿结构
应用
性能
proton conductors
perovskite structure
application
performance
