Grinderslev Jakob B, Skov Lasse N, Sørensen Daniel R, Kantor Innokenty, Jørgensen Mads R V, Jensen Torben R
Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University, Langelandsgade 140, DK-8000 Aarhus C, Denmark.
MAX IV laboratory, Lund University, Fotongatan 2, SE 211 00 Lund, Sweden.
Dalton Trans. 2022 Oct 25;51(41):15806-15815. doi: 10.1039/d2dt02513b.
Metal -boranes have recently received significant attention as solid-state electrolytes due to their high thermal and electrochemical stability, and the weak interaction between the cat- and anion, facilitating fast ionic conductivity. Here we report a synthesis method for obtaining a novel mixed -carborane compound, [NH(CH)][(CBH)(CBH)(CBH)]. The crystal structures are investigated for [NH(CH)][CBH] and [NH(CH)][(CBH)(CBH)(CBH)], revealing that the latter forms a solid solution isostructural to [NH(CH)][CBH]. The compounds exhibit polymorphism as a function of temperature, and we report the discovery of four polymorphs of [NH(CH)][CBH] and four isostructural solid solution [NH(CH)][(CBH)(CBH)(CBH)], along with a high-temperature decomposition intermediate of the latter. The α-polymorph is an ordered structure, with increasing amounts of disorder for the β- and γ-polymorphs, while the high temperature δ- and ε-polymorphs at > 476 K are fully disordered on both the cation and anion site. These new compounds may be used as precursors for new types of solid-state ionic conductors.
金属硼烷由于其高热稳定性和电化学稳定性，以及阳离子和阴离子之间的弱相互作用有利于快速离子传导，最近作为固态电解质受到了广泛关注。在此，我们报告一种合成新型混合碳硼烷化合物[NH(CH)][(CBH)(CBH)(CBH)]的方法。对[NH(CH)][CBH]和[NH(CH)][(CBH)(CBH)(CBH)]的晶体结构进行了研究，结果表明后者形成了与[NH(CH)][CBH]同构的固溶体。这些化合物表现出随温度变化的多晶型现象，我们报告发现了[NH(CH)][CBH]的四种多晶型以及[NH(CH)][(CBH)(CBH)(CBH)]的四种同构固溶体，同时还发现了后者的一种高温分解中间体。α-多晶型是一种有序结构，β-和γ-多晶型的无序程度逐渐增加，而在>476 K时的高温δ-和ε-多晶型在阳离子和阴离子位点上都是完全无序的。这些新化合物可用作新型固态离子导体的前驱体。
