Entropy-Driven Disorder and Aliovalent Substitution Induce Defects in Na3PnS4 (Pn = P, As, Sb) Solid-State Electrolytes: A Sluice Gate for Sodium Ions

IF 8.7 1区化学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

ACS Materials Letters Pub Date : 2025-09-10 DOI:10.1021/acsmaterialslett.5c00630

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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Abstract

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, Na_3−δP_0.32As_0.32Sb_0.32W_0.04S₄ (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.

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熵驱动无序和同价取代诱导Na3PnS4 （Pn = P, As, Sb）固态电解质中的缺陷：钠离子的闸门

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。

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来源期刊

ACS Materials Letters MATERIALS SCIENCE, MULTIDISCIPLINARY-

CiteScore

14.60

自引率

3.50%

发文量

261

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