Effect of β-Cyclodextrin on Physicochemical Properties of an Ionic Liquid Electrolyte Composed of N-Methyl-N-Propylpyrrolidinium bis(trifluoromethylsulfonyl)amide

2019-02-23 18:14:19 adman 7

Ionic liquids (ILs) are promising electrolyte materials for developing next-generation rechargeable batteries. In order to improve their properties, several kinds of additives have been investigated. In this study, β-cyclodextrin (β-CD) was chosen as a new additive in IL electrolytes because it can form an inclusion complex with bis(trifluoromethylsulfonyl)amide (TFSA) anions. We prepared the composites by mixing N-methyl-N-propylpyrrolidinium bis(trifluoromethylsulfonyl)amide/LiTFSA and a given amount of triacetyl-β-cyclodextrin (Acβ-CD). The thermal behaviors and electrochemical properties of the composites were analyzed by several techniques. In addition, pulse field gradient NMR measurements were conducted to determine the self-diffusion coefficients of the component ions. The addition of Acβ-CD to the IL electrolytes results in the decrease in the conductivity value and the increase in the viscosity value. In contrast, the addition of Acβ-CD to the IL electrolytes induced an improvement in the anodic stability because of the formation of an inclusion complex between the Acβ-CD and TFSA anions. CDs are potential candidates as additives in IL electrolytes for electrochemical applications.



Figure 1. Chemical structures of [C3mpyr][TFSA], and Acβ-CD


The effect of Acβ-CD on the properties of [C3mpyr][TFSA]/LiTFSA was investigated by means of several techniques. The chemical shift of the CF3 group of the TFSA anion shifted to a lower magnetic field with the increase in the Acβ-CD content. With the addition of Acβ-CD to the IL electrolyte, the Tm of the IL disappeared and the viscosity increased. These results suggest that an inclusion complex is formed between Acβ-CD and the TFSA anion. In contrast, the tLi+ and DLi values decreased with the increase in the Acβ-CD content in the composites. The anodic stability of [C3mpyr][TFSA]/LiTFSA was significantly improved after adding a certain amount of Acβ-CD. Li plating and stripping in the [C3mpyr][TFSA]/LiTFSA/Acβ-CD composite were repeatedly observed. According to these results, Acβ-CD will be an interesting additive for improving the electrochemical stability of ILs. It is known that there are three kinds of CD, α-CD, β-CD, and γ-CD, which have different cavity sizes. The physicochemical properties of various ILs with different anions could be controlled by choosing suitable CD derivatives.