二价
热传导
快离子导体
离子电导率
离子
化学物理
空位缺陷
电导率
化学
扩散
材料科学
离子键合
无机化学
结晶学
电解质
物理化学
热力学
电极
有机化学
物理
复合材料
作者
Andrew J. Martinolich,Cheng-Wei Lee,I-Te Lu,Sarah C. Bevilacqua,Molleigh B. Preefer,Marco Bernardi,André Schleife,Kimberly A. See
标识
DOI:10.1021/acs.chemmater.9b00207
摘要
Next-generation batteries based on divalent working ions have the potential to both reduce the cost of energy storage devices and increase performance. Examples of promising divalent systems include those based on Mg2+, Ca2+, and Zn2+ working ions. Development of such technologies is slow, however, in part due to the difficulty associated with divalent cation conduction in the solid state. Divalent ion conduction is especially challenging in insulating materials that would be useful as solid-state electrolytes or protecting layers on the surfaces of metal anodes. Furthermore, there are no reports of divalent cation conduction in insulating, inorganic materials at reasonable temperatures, prohibiting the development of structure–property relationships. Here, we report Zn2+ conduction in insulating ZnPS3, demonstrating divalent ionic conductivity in an ordered, inorganic lattice near room temperature. Importantly, the activation energy associated with the bulk conductivity is low, 351 ± 99 meV, comparable to some Li+ conductors such as LTTO, although not as low as the superionic Li+ conductors. First-principles calculations suggest that the barrier corresponds to vacancy-mediated diffusion. Assessment of the structural distortions observed along the ion diffusion pathways suggests that an increase in the P–P–S bond angle in the [P2S6]4– moiety accommodates the Zn2+ as it passes through the high-energy intermediate coordination environments. ZnPS3 now represents a baseline material family to begin developing the structure–property relationships that control divalent ion diffusion and conduction in insulating solid-state hosts.
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