Investigation of Unusual Conductivity Behavior and Ion Dynamics in Hexamethylguanidinium Bis(fluorosulfonyl)imide-Based Electrolytes for Sodium Batteries
Investigation of Unusual Conductivity Behavior and Ion Dynamics in Hexamethylguanidinium Bis(fluorosulfonyl)imide-Based Electrolytes for Sodium Batteries
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钠电池用六甲基胍双(氟磺酰基)亚胺基电解质异常导电行为和离子动力学的研究
DOI：
10.1021/acs.jpcc.1c01777
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Pringle, Jennifer M.
中科院分区：
文献类型：
--
作者：
Biernacka, Karolina;Makhlooghiazad, Faezeh;Popov, Ivan;Zhu, Haijin;Chotard, Jean-Noël;Forsyth, Craig M.;Yunis, Ruhamah;O’Dell, Luke A.;Sokolov, Alexei P.;Pringle, Jennifer M.
开发可替代当前有机电解质的不易燃、化学和热稳定的电解质将支持改进和更安全的储能技术。有机离子塑料晶体（OIPC）及其盐混合物是有希望的固态候选电池应用。在这项工作中，六甲基胍双（氟磺酰基）酰亚胺（[HMG][FSI]）OIPC的钠电池的上下文中，其中钠双（氟磺酰基）酰亚胺（NaFSI）盐与OIPC混合，以提高离子电导率。用差示扫描量热法（DSC）研究了纯OIPC的热行为及钠盐的加入对OIPC热行为的影响。宽带介电谱（BDS）实验，沿着与电化学阻抗谱（EIS）用于研究离子电导率，表明该系统具有不寻常的温度依赖性的电导率行为相比，其他OIPC系统。在阶段II中测量的电导率在加热循环期间高于在冷却时测量的电导率。固态核磁共振（NMR）光谱结合XRD和建模被用来研究这种行为的分子起源。在含有5 mol % NaFSI的OIPC中也观察到该行为。脉冲场梯度核磁共振谱（PFG-NMR）结合线宽分析被用来检查离子动力学。[HMG]+阳离子相对于[FSI]−阴离子的扩散系数几乎低2个数量级，并且结合非常窄的23 Na线宽，后两种离子的动力学似乎与较大的[HMG]+阳离子解耦，这表明在这种电解质中高Na+传输的可能性。我们的研究有助于对钠电池OIPC基固体电解质动力学的基本理解，并突出了外部参数（如材料的热历史）的复杂性和重要性。
The development of nonflammable, chemically and thermally stable electrolytes that can replace current organic electrolytes will support improved and safer energy storage technologies. Organic ionic plastic crystals (OIPCs) and their salt mixtures are promising solid-state candidates for battery applications. In this work, the hexamethylguanidinium bis(fluorosulfonyl)imide ([HMG][FSI]) OIPC is investigated in the context of sodium batteries, where sodium bis(fluorosulfonyl)imide (NaFSI) salt is mixed with the OIPC to enhance the ionic conductivity. The thermal behavior of the neat OIPC and the effect of sodium salt addition were investigated by differential scanning calorimetry (DSC). Broadband dielectric spectroscopy (BDS) experiments, along with electrochemical impedance spectroscopy (EIS) used to study ion conductivity, showed this system to have unusual temperature-dependent conductivity behavior in comparison to other OIPC systems. The conductivity measured in phase II was higher during the heating cycle compared to that measured upon cooling. Solid-state nuclear magnetic resonance (NMR) spectroscopy combined with XRD and modeling was used to investigate the molecular origin of this behavior. This behavior was also observed in the OIPC containing 5 mol % NaFSI. Pulsed field gradient nuclear magnetic resonance spectroscopy (PFG-NMR) combined with line width analysis was used to examine the ion dynamics. The [HMG]+cation has almost a 2 orders of magnitude lower diffusion coefficient relative to the [FSI]−anion, and combined with the very narrow23Na line width, it appears that the dynamics of the two latter ions are decoupled from the larger [HMG]+cation, suggesting the possibility of high Na+transport in this electrolyte. Our study contributes to the fundamental understanding of dynamics in OIPC-based solid electrolytes for sodium batteries and highlights the complexity and importance of external parameters such as the thermal history of the material.
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