Dual-Cation Electrolyte System Using Quaternary Ammonium Salts and Ionic Liquid for High Power and High Energy Li4Ti5O12//AC Hybrid Capacitor System
Authors: Chikaoka Yu , Iwama Etsuro , Sakurai Masato , Ueda Tsukasa , Naoi Wako , Simon Patrice , Naoi Katsuhiko 
Published: December 2020

[Introduction]

The Use of thick electrodes (> 100 µm) is a simple approach to increase the energy density of electrochemical energy storage devices. However, the high ionic resistance in thick electrodes limits the high-power applications of such devices. “Dual-cation” electrolytes for thick-electrode hybrid capacitor systems, typically composed of Li4Ti5O12 (LTO, 200 µm) and activated carbon (AC, 400 µm) electrodes, have been developed[1]. A dual-cation electrolyte is composed of lithium tetrafluoroborate (LiBF4) and spiro-(1,1')-bipyrrolidinium tetrafluoroborate (SBPBF4) dissolved in propylene carbonate (PC). An SBP-based dual-cation electrolyte, comprising 1 M LiBF4 + 2 M SBPBF4 / PC, exhibits a higher total ionic conductivity (7.67 S cm-1) than the single-cation electrolyte (3.40 S cm-1), consisting of 1 M LiBF4 / PC, while Li+ conductivity decreases with an increase of SBPBF4 concentration. Our interesting finding was that the presence of SBP+, despite the low Li+ transport in the electrolyte bulk, reduces overvoltage associated with migration limitation in the thick LTO electrode, and thus enhances power density in LTO//AC hybrid capacitor systems.

In this study, we propose another dual-cation electrolyte using a 1-ethyl-3-methylimidazolium (EMI) cation in place of the SBP cation, which further enhances the power performance of LTO//AC hybrid capacitor systems. It has been shown that an EMI-based electrolyte exhibits a higher total ionic conductivity (10.9 S cm-1) than the SBP-based electrolyte. Herein we provide a detailed account of factors that improve the discharge properties of the EMI-based dual-cation electrolyte by using electrochemical and spectroscopic methods.

[Experimental]

The dual-cation electrolytes were prepared by dissolving 1 M LiBF4 and x M SBPBF4 (0 < x < 3) or x' M EMIBF4 (0 < x' < 4), in PC. The ionic conductivity of the prepared electrolytes was measured using a conductivity meter. The LTO(200 μm)//AC(400 μm) hybrid capacitor system assumed a coin type cell assembly; charge-discharge measurements were conducted at 1 mA cm-2 (at the charge) and 1 to 200 mA cm-2 (at the discharge). Pulsed Gradient Spin Echo (PGSE) NMR analysis was conducted to determine the self-diffusion coefficients of the Li(7Li), SBP (1H), and EMI (1H) cations and the BF4 (19F) anion in the electrolytes.. Electrochemical impedance spectroscopy (EIS) was performed to evaluate the resistance of the LTO electrode using LTO//LTO symmetric cells designed at both the delithiated (SOC of LTO = 0%) and lithiated (SOC of LTO = 25%) states.

[Results and discussion]

The results of the ionic conductivity for all electrolytes are shown in Figure 1. The EMI-based dual-cation electrolyte exhibited higher ionic conductivity than the SBP-based electrolyte. The results of the charge-discharge test (Figure 2) showed that the EMI-based dual-cation electrolyte exhibits optimal discharge properties among the electrolytes. Moreover, the PGSE NMR analysis results indicated that the self-diffusion coefficient for all ions including Li+ decreased with an increase in EMIBF4 concentration.

In contrast, the ionic resistance (R
ion) of the LTO negative electrode calculated from the EIS results at the delithiated state (SOC of LTO = 0%) yielded lower values for the EMI-based dual-cation electrolyte (11.1 Ω cm2) than that for the SBP-based (14.0 Ω cm2) and single-cation (27.1 Ω cm2) electrolytes. We also evaluated the charge-transfer resistance (R
ct) from the EIS results using LTO//LTO symmetric cells at the lithiated state (SOC of LTO = 25%). The R
ct was found to be lower in the EMI-based dual-cation electrolyte (1.71 Ω cm2) than that in the SBP-based (2.28 Ω cm2) and single-cation (3.57 Ω cm2) electrolytes. These results showed that charge-transfer reactions at the LTO electrodes occur more readily in the dual-cation electrolyte.

The results indicated that a reduction in R
ct occurs because ion potential suppression occurs owing to the accelerated ion transport in the electrode, as well as in our previous study[1]. The suppression of the ionic potential increased the Li+ concentration and reaction current at the collector side, which decreased the R
ct. This is because the advantage of an increase in total ionic conductivity is effective even when the transport ofLi+ is reduced in a thick-electrode system.

This study confirms that the use of the EMI-based electrolyte, which has a higher total ionic conductivity than the SBP-based electrolyte, exhibits a remarkable suppression of R
ion and R
ct. The use of thick electrodes, therefore, facilitates an increase in total ionic conductivity, which has a more desirable effect than that of high Li+ conductivity, especially in the EMI-based dual-cation electrolyte, wherein the power density of the thick-electrode LTO//AC hybrid capacitor systems was significantly improved.

[1] Y. Chikaoka et al., J. Phys. Chem. C, in press(doi.org/10.1021/acs.jpcc.0c01916).

Figure 1