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Fluoride shuttle batteries: On the performance of the BiF3 electrode in organic liquid electrolytes containing a mixture of lithium bis(oxalato)borate and triphenylboroxin
Solid State Ionics ( IF 3.0 ) Pub Date : 2020-11-02 , DOI: 10.1016/j.ssi.2020.115499
Asuman Celik Kucuk , Toshiro Yamanaka , Takeshi Abe

In a typical organic liquid electrolyte-based fluoride shuttle battery (FSB), a high concentration of a boron-based anion acceptor (AA) capable of binding specific anions is required to provide a sufficient amount of dissolved fluoride salt. In this study, and a mixture of lithium bis(oxalato)borate (LiBOB) and an AA, triphenylboroxin (TPhBX), was used as an organic liquid electrolyte. The tetraglyme (G4)-based electrolyte system (LiBOB0.25/TPhBX0.25/sat_CsF/G4) containing equal concentrations of LiBOB, TPhBX, and saturated cesium fluoride (CsF) was prepared. The potential effects of reducing the amount of the AA and using a mixture of LiBOB and TPhBX on the electrochemical compatibility of the BiF3 electrode were investigated through cyclic voltammetry, charge–discharge tests, and alternating current impedance measurements. The potential advantages of using the LiBOB/TPhBX mixture as an electrolyte additive include the fact that it increases ionic conductivity, widens the cathodic and anodic stability window, and enhances the electrochemical performance of the BiF3 positive electrode. Moreover, according to Raman microscopy, the direct insertion mechanism was found to be predominant for the FSB reaction mechanism of BiF3 microparticles in LiBOB0.25/TPhBX 0.25/sat_CsF/G4. These improvements can be attributed to the increase in fluorine anion mobility, which occurs when the cesium cation mobility is reduced; this, in turn, is a result of the stabilization of the cesium cation due to the interaction between LiBOB and TPhBX. Therefore, mixing equal concentrations of LiBOB and TPhBX can be a promising alternative method to ensure electrolyte stability and prevent the potential loss of active materials during the redox reactions.



中文翻译:

氟化物穿梭电池:BiF 3电极在含有双(草酸硼酸)硼酸锂和三苯基环硼酸锂混合物的有机液体电解质中的性能

在典型的有机液体电解质基氟化物穿梭电池(FSB)中,需要高浓度的能够结合特定阴离子的硼基阴离子受体(AA)以提供足够量的溶解的氟化物盐。在这项研究中,使用了双(草酸硼酸)硼酸锂(LiBOB)和AA三苯硼辛(TPhBX)的混合物作为有机液体电解质。制备了包含等浓度的LiBOB,TPhBX和饱和氟化铯(CsF)的基于四甘醇二甲醚(G4)的电解质体系(LiBOB 0.25 / TPhBX 0.25 / sat_CsF / G4)。减少AA量以及使用LiBOB和TPhBX的混合物对BiF 3电化学相容性的潜在影响电极通过循环伏安法,充放电测试和交流阻抗测量进行了研究。使用LiBOB / TPhBX混合物作为电解质添加剂的潜在优势包括以下事实:它增加了离子电导率,扩大了阴极和阳极稳定性窗口并增强了BiF 3正极的电化学性能。此外,根据拉曼显微镜,发现直接插入机制是LiBOB 0.25 / TPhBX 0.25中BiF 3微粒的FSB反应机理的主要部分。/ sat_CsF / G4。这些改善可以归因于氟阴离子迁移率的增加,当铯阳离子迁移率降低时会发生这种情况。这又是由于LiBOB和TPhBX之间相互作用而导致铯阳离子稳定的结果。因此,混合等浓度的LiBOB和TPhBX可以成为一种有希望的替代方法,以确保电解质的稳定性并防止氧化还原反应过程中活性物质的潜在损失。

更新日期:2020-11-02
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