摘要
Y掺杂的BaZrO_(3)因其优异的化学稳定性而被广泛研究。然而,较高的烧结温度限制了其应用。为改善BaZrO_(3)的烧结活性,对Y-BaZrO_(3)采用Pr^(3+)和Ni^(2+)进行共掺杂,并对其微观形貌及电化学性能进行研究。Ni与材料形成固溶体,Pr^(3+)的掺杂增大了晶粒尺寸,这对致密化过程极为重要。XPS、Raman和EPR结果表明,少量Pr^(3+)掺杂可以增加材料的氧空位含量,并通过加速水的解离和吸附促进质子进入,从而促进质子传导。然而,过量Pr^(3+)掺杂导致的高浓度氧空位会产生缺陷缔合反应,使低温下的电导率略有下降。随着温度的升高,氢分离膜的氢渗透性也增加。此外,BaZr_(0.66)Y_(0.2)Pr_(0.1)Ni_(0.04)O_(3–δ)的氢渗透性高于BaZr_(0.71)Y_(0.2)Pr_(0.05)Ni_(0.04)O_(3–δ),在1 173 K时,氢渗透性达到2.60×10^(–8 )mol·cm^(–2)·s^(–1)。
Y-doped BaZrO_(3) proton conductor has been extensively studied due to its outstanding chemical stability.However,the high sintering temperature has limited its practical application.To enhance the sintering activity of BaZrO_3,we co-doped Y-BaZrO_(3with) Pr~(3+)and Ni~(2+),and investigated its microscopic morphology and electrochemical properties.The introduction of Ni forms a solid solution with the sample,while Pr~(3+)doping increases the grain size,a critical factor for the densification process.XPS,Raman and EPR results reveal that a small amount of Pr~(3+)doping significantly raises the concentration of oxygen vacancies in the materials.This increase promotes proton incorporation by accelerating the dissociation and adsorption of water,thereby facilitating the proton conduction.However,it’s important to note that excessive Pr~(3+)doping leads to a high concentration of oxygen vacancies,which triggers a defect association reaction.Consequently,this results in a slight decrease in conductivity at low temperatures.On the other hand,as the temperature increases,the hydrogen permeability of the membrane increases also rises.Moreover,the hydrogen permeability of BaZr_(0.66)Y_(0.2)Pr_(0.1)Ni_(0.04)O_(3–δ) is found to be higher than that of Ba Zr_(0.71)Y_(0.2)Pr_(0.05)Ni_(0.04)O_(3–δ),with the former reaching2.60×10~(–8 )mol·cm~(–2)·s~(–1) at 1 173 K.Notably,these membranes exhibit remarkable in CO_2-containing atmosphere indicating excellent resistance to CO_2.
作者
王靖
杨春利
张浩
申清涛
曹伟际
李俊
姚伟
王雷
WANG Jing;YANG Chunli;ZHANG Hao;SHEN Qingtao;CAO Weiji;LI Jun;YAO Wei;WANG Lei(College of Materials Science and Engineering,Xi′an University of Architecture and Technology,Xi′an 710055,China)
出处
《硅酸盐学报》
EI
CAS
CSCD
北大核心
2023年第12期3083-3094,共12页
Journal of The Chinese Ceramic Society
基金
陕西省自然科学基础研究计划(2021JQ-497)。
关键词
氧空位
质子电导率
氢分离膜
oxygen vacancy
proton conductivity
hydrogen separation membrane
