1. Introduction: Lithium ion batteries (LIBs) are used in the variety of fields including vehicles, stationary energy storage, and portable devices. Since the conventional LIBs contain volatile and flammable electrolyte liquid, they potentially have a risk on safety relevant to the electrolyte, e.g. ignition of electrolyte leaked from the mechanically crashed or short-circuited batteries. To overcome the safety issue, we have been developing a “less volatile electrolyte” with a volatilization temperature higher than 100 °C, and incorporating the electrolyte into the cells consisting of Si-based anode and Ni-Co-Mn oxide (NCM) cathode for realizing the high energy density of 300 Wh/kg [1]. The electrolyte used in the previous research consisted of equimolar mixture of lithium bis(trifluoromethanesulfonyl)imide(LiTFSA) and tetraglyme(G4) as main solvent with a high volatilization temperature, propylene carbonate (PC) as low viscos solvent to enhance ionic conductivity, vinylene carbonate(VC) and tetrabutylammonium hexafluorophosphate (TBAPF6) as additives to form passivation layer on anode and cathode surface [2]. A issue to be solved for the less volatile LIB was improvement in durability during charge-discharge test. We have analyzed the formation and growth mechanism of solid-electrolyte interphase forming on the graphite-based anode and revealed that the G4 and PC successively decomposed on the electrode surface to lower the capacity during the charge-discharge cycle test. Based on the analysis, we aim to modify the composition of the electrolyte constituents to enhance the durability. In this research, the effect of sulfolane(SL)-based electrolyte, which has been extensively investigated in Dokko et al. [3], on the capacity retention during charge-discharge test of less volatile LIB with Si-based anode and NMC-based cathode.2. Experimental: As for SL-based less volatile electrolyte, the mixed solution of Li(SL)3TFSA, butylene carbonate(BC), VC, and TBAPF6, was prepared. The thermal properties of the electrolyte was evaluated by thermogravimetric analysis(TGA) and differential scanning calorimetry(DSC). For investigating cycle durability, the laminated cell composed of Si-graphite anode and high-Ni content NCM cathode are fabricated. The apparent area of the both electrodes was ca 10 cm2, and the designed energy amount was ca. 0.1Wh. The SL-based electrolyte solution was added into the laminated cell. In the cycle test, constant current charge corresponding to 0.5 CA was applied for the cell up to 4.2V, while constant voltage charge was successively conducted until the current decreased to 0.05 CA. The fully-charged cell was discharged at 0.5 CA to 2.5 V. At every 20 cycles, the rated capacity was obtained from discharge curve where from 4.2 V to 2.5 V at the discharge current of 0.05 CA. To discuss the degradation mechanism of the laminated cell, the microstructure of the anode after the 100 cycle was analyzed by using field emission scanning electron microscopy (FE-SEM).3. Results and Discussions: In TGA, the volatilization temperature of the SL-based electrolyte was 140 °C, which was higher than the G4-based electrolyte (105 °C). Also, DSC revealed that the heat generation originating from the oxidative reaction of the SL-based electrolyte with a charged cathode was quite lower than that of the G4-based electrolyte [4]. Figure 1 shows the capacity retention of the laminated cell depending on the cycle number. In the figure, Cell-G4 contained Li(G4)TFSA-45%PC-3%VC-2.5%TBAPF6 as the electrolyte, and Cell-SL1 and Cell-SL2 did Li(SL)3TFSA-20%BC-3%VC-2.5%TBAPF6 and Li(SL)3TFSA-20%BC-6%VC-2.5%TBAPF6, respectively. The capacity of Cell-SL1 is higher than that of Cell-G4 until 60 cycles, however, it rapidly decreased after 60 cycles. FE-SEM revealed that the microstructure of anode in Cell-SL1 was likely to be deteriorated, which probably resulted from the volume change of the anode during the cycle. We also found that the microstructure deterioration can be suppressed by increase the concentration of VC additive, which enhanced the capacity retention in Fig.1(Cell-SL2). These results indicated that the SL-based electrolyte is a promising candidate to ensure the sufficient durability of the less-volatile LIB with a high energy density.Acknowledgement: The part of this research was financially supported by Innovative Science and Technology Initiative for Security(JPJ004596), Acquisition, Technology & Logistics Agency (ATLA) of Japan.
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