A Piperidinium-Based Ester-Functionalized Task-Specific Ionic Liquid As Electrolytes in Li/LiFePO4 Batteries
Authors: Yang Peixia , Pan Xiaona , Zhang Jinqiu , An Maozhong 
Published: February 2020

Lithium batteries are the most attractive candidate to replace the traditional energy resources due to their high working voltage, high specific energy and long cycle life [1,2]. However, the widely use have been limited by their safety issues, especially under the condition of abusing or overcharging. In order to solve this issue, it is significant to screen a safe material as lithium batteries electrolyte.
Room temperature ionic liquids (RTILs) have aroused much attention for use in lithium batteries, owing to their low volatility, inflammability, wide electrochemical window and high ionic conductivity [3]. Particularly, their excellent thermal stability makes them key to solve the safety issues of lithium batteries at high temperatures and their physicochemical properties can be tuned by introducing functionalized groups onto the cation or anion of RTILs. The functionalized task-special ionic liquids can reduce the viscosity and enhance their ionic conductivity of RTILs. In this study, a piperidinium-based ionic liquid, N-methyl-N-methoxycarbonylpiperidinium bis(trifluoromethanesulfonyl)imide ([MMOCPip][TFSI]), was synthesized by anion exchange reaction and used as an additive to electrolyte of Li-ion battery. The electrochemical performance of the electrolytes had been evaluated by electrochemical tests, such as the line sweep voltammetry, cyclic voltammetry and impedance spectroscopy.
The N-methyl-N-methoxycarbonylpiperidinium bis(trifluoromethanesulfonyl)imide ([MMOCPip][TFSI]) ionic liquid was prepared by mixing equimolar N-methyl-N-methoxycarbonylpiperidinium bromide ([MMOCPip][Br]) and bis(trifluoromethanesulfonyl)imide lithium at room temperature in deionized water and by stirring for several hours until a hydrophobic [MMOCPip][TFSI] layer was formed below the water phase [4]. The ionic conductivity of [MMOCPip][TFSI] was 0.77 mS·cm-1 (25℃) and 2.41 mS·cm-1 (60℃), however, after adding 0.1 M LiTFSI, the ionic conductivity decreased to 0.51 mS·cm-1 (25℃) and 1.85 mS·cm-1 (60℃), respectively. The electrochemical window was 0.5 V~5.8 V (vs. Li+/Li), which was enough widely that could be used as common electrode material. The Li-ion transference number of ionic Liquid electrolyte containing 0.1 M LiTFSI was 0.56. The battery tests indicated that the [MMOCPip][TFSI] obviously improved the cyclability of the LiFePO4 cell. For the Li/ LiFePO4 half-cells, after 20 cycles at room temperature at 0.1 C, the discharge capacity was 109.7 mAh·g-1 with 98.7% capacity retention in the [MMOCPip][TFSI]/0.1 M LiTFSI electrolyte. The good electrochemical performance demonstrated that the [MMOCPip][TFSI] could be used as electrolyte additive for lithium batteries.

Keywords: Ionic liquid; Li-ion battery; Ionic conductivity; Transference number

Reference:

[1] Wongittharoma N, Wang CH, Wang YC, Fey GTK, Li HY, Wu TY, Lee TC, Chang JK (2014). Charge-storage performance of Li/LiFePO4 cells with additive incorporated ionic liquid electrolytes at various temperatures. J Power Sources. 260: 268–275.
[2] Yang J, Zhou XY, Zou YL, Tang JJ (2011). A hierarchical porous carbon material for high power, lithium ion batteries. Electrochim Acta. 56: 8576–8581.
[3] Pandian S, Raju SG., Hariharan KS, Kolake SM, Park DH, Lee MJ (2015). Functionalized ionic liquids as electrolytes for lithium-ion batteries. J Power Sources. 286: 204-209.
[4] Yang PX, Cui WY, Li LB, Liu L, An MZ (2012). Characterization and properties of ternary P(VdF-HFP)-LiTFSI-EMITFSI ionic liquid polymer electrolytes. Solid State Sciences. 14(5), 598–606.

Figure 1