Unravelling the Proton Conduction Mechanism from Room Temperature to 553 K in a 3D Inorganic Coordination Framework.
Unravelling the Proton Conduction Mechanism from Room Temperature to 553 K in a 3D Inorganic Coordination Framework.
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DOI：
10.1021/acs.inorgchem.5b01801
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发表时间：
2015-10
影响因子：
4.6
通讯作者：
Yaxing Wang;Z. Tao;Xuemiao Yin;Jie Shu;Lanhua Chen;Daopeng Sheng;Z. Chai;T. Albrecht‐Schmitt
中科院分区：
文献类型：
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作者：
Yaxing Wang;Z. Tao;Xuemiao Yin;Jie Shu;Lanhua Chen;Daopeng Sheng;Z. Chai;T. Albrecht‐Schmitt
制备在中温（393-573 K）下具有功能和稳定性的质子传导材料是燃料电池发展的焦点。纯无机材料HNd（IO 3）4具有致密的三维骨架结构，在353 K和95%相对湿度下，其最大电导率可达4.6 × 10（-4）S·cm（-1），在373 ~ 553 K湿N2气氛下，其电导率可达8.0 × 10（-5）S·cm（-1）。HNd（IO 3）4表现出多种改进，包括高热稳定性、在水中的低溶解度和对还原性气氛的耐受性。在这样一个宽的温度范围内的质子导电性来源于结构中的固有释放的质子和所得到的一维氢键网络证实的键价和计算和固态NMR分析。此外，在不同的温度范围内观察到两个不同的活化能（低于373 K时为0.23 eV，从373至553 K时为0.026 eV），表明两种类型的质子运动是质子扩散的原因，如在测试的燃料电池组件中的温度相关开路电压滞后以及可变温度和双量子过滤固体所进一步证明的，状态NMR测量。
The preparation of proton-conducting materials that are functional and stable at intermediate temperatures (393-573 K) is a focal point of fuel cell development. The purely inorganic material, HNd(IO3)4, which possesses a dense 3D framework structure, can reach a maximum of 4.6 × 10(-4) S·cm(-1) at 353 K and 95% relative humidity and exhibit a high conductivity of 8.0 × 10(-5) S·cm(-1) from 373 to 553 K under the flow of wet N2. HNd(IO3)4 exhibits a variety of improvements including high thermal stability, low solubility in water, and resistance to reducing atmosphere. The proton conductivity in such a wide temperature range originates from the intrinsic liberated protons in the structure and the resulting 1D hydrogen-bonding network confirmed by bond valence sum calculation and solid-state NMR analysis. Moreover, two different activation energies are observed in different temperature regions (0.23 eV below 373 K and 0.026 eV from 373 to 553 K), indicating that two types of proton motion are responsible for proton diffusion, as further domenstrated by temperature-dependent open-circuit voltage hysteresis in a tested fuel cell assembly as well as variable-temperature and double quantum filtered solid-state NMR measurements.