Madhusudan Chaudhary, , , Muskaan Rawat, , , Elisabeth Springl, , , Daniel Weindl, , , Diganta Sarkar, , , Aiden Yu, , , Dmitry Vrublevskiy, , , Tom Nilges, , , Arthur Mar, , and , Vladimir K. Michaelis*,
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引用次数: 0
摘要
含钠硫族化合物是有吸引力的候选固体电解质；然而，它们的离子电导率仍然是一个挑战。同时应用异价和价取代可以通过产生大量的位点紊乱和高空位浓度来增强离子电导率。为了阐明促进钠离子传导的机理，以三元硫化物Na3PnS4 （Pn = P, As, Sb）为原料，通过高温反应制备了一系列混合pnicogen固溶体，包括熵驱动的w取代相Na3−δP0.32As0.32Sb0.32W0.04S4 （N-PASS-W）。N-PASS-W具有10 mS cm-1的高离子电导率和0.15 eV的低活化能。利用PXRD和NMR建立了N-PASS-W的原子水平模型，其中离子跳变发生在正方结构（P4′21c）的两个Na位点上。还建立了其他成员的结构和离子电导率之间的关系，以评估晶体相，阳离子大小和位置紊乱的影响。
Entropy-Driven Disorder and Aliovalent Substitution Induce Defects in Na3PnS4 (Pn = P, As, Sb) Solid-State Electrolytes: A Sluice Gate for Sodium Ions
Sodium-containing chalcogenides are attractive candidates for use as solid-state electrolytes; however, their ionic conductivities remain a challenge. Simultaneously applying isovalent and aliovalent substitution can enhance ionic conductivity by generating substantial site disorder and high vacancy concentrations. To elucidate the mechanism that facilitates sodium ion conduction, a series of mixed-pnicogen solid solutions were prepared from the parent ternary sulfides Na3PnS4 (Pn = P, As, Sb) by high-temperature reactions, including an entropy-driven W-substituted phase, Na3−δP0.32As0.32Sb0.32W0.04S4 (N-PASS-W). N-PASS-W exhibits a very high ionic conductivity of 10 mS cm–1 and a low activation energy of 0.15 eV. Using PXRD and NMR spectroscopy, an atomic-level model for N-PASS-W was proposed, in which ion hopping occurs over two Na sites within a tetragonal structure (P4̅21c). Relationships were also established between the structure and ionic conductivities of the other members to evaluate the influence of crystalline phase, cation size, and site disorder.
期刊介绍：
ACS Materials Letters is a journal that publishes high-quality and urgent papers at the forefront of fundamental and applied research in the field of materials science. It aims to bridge the gap between materials and other disciplines such as chemistry, engineering, and biology. The journal encourages multidisciplinary and innovative research that addresses global challenges. Papers submitted to ACS Materials Letters should clearly demonstrate the need for rapid disclosure of key results. The journal is interested in various areas including the design, synthesis, characterization, and evaluation of emerging materials, understanding the relationships between structure, property, and performance, as well as developing materials for applications in energy, environment, biomedical, electronics, and catalysis. The journal has a 2-year impact factor of 11.4 and is dedicated to publishing transformative materials research with fast processing times. The editors and staff of ACS Materials Letters actively participate in major scientific conferences and engage closely with readers and authors. The journal also maintains an active presence on social media to provide authors with greater visibility.
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