Operando Analysis of Bi/BiF3 Electrode Reaction in Li+/F- Hybrid Electrolyte By Synchrotron Radiation Diffraction

Abstract

1.IntroductionIn recent years, the development of innovative batteries that exceed the performance of lithium-ion batteries has been desired. One of the candidates is a fluoride shuttle battery (FSB). It is an anion-based, rechargeable batteries operating under fluoride shuttling, and rests upon the foundation of a redox-active fluoride ion transporting electrolyte of high electrochemical stability. To realize the FSB, we have developed a lactone-based Li+/F- hybrid electrolyte, in which Li+ and F- ions that normally cannot coexist in organic solvents form some complexes soluble in GBL. The thus reformed electrolyte, together with its delicate and unique anion accepting (AA) function, largely expands the negative potential window to or beyond the standard redox potential of Li+/Li. In this study, in order to clarify the electrochemical behaviors of BiF3/Bi electrode combined with the electrolyte, the operando analysis was carried out by the synchrotron radiation diffraction (SRD) measurement.2. ExperimentalThe BiF3 powder mixed with acetylene-black and PVdF was used as the working electrode. The activated carbon and Ag metal were used as the counter and reference electrodes, respectively. The Al-laminated half-cell composed of above-mentioned electrodes was assembled using a newly developed hybridized electrolyte. Thus prepared cell was pre-discharged (0th cycle) in advance in the potential range of -1.5 V – 1.0 V at ca. 0.04C. Then, several charge/discharge cycles were repeated with the same conditions. SRD was measured with BL28XU beam line at Super Photon ring-8, Japan during the whole charge/discharge process. High-energy X-ray with a wavelength of 0.049592 nm was used to obtain 2D diffraction patterns. The exposure time was set to 10 s, and several thousand diffraction profiles were obtained during the discharge/charge process. In order to analyze the obtained enormous profiles data in conjunction with the charge/discharge curves and their differential curves (V-dQ/dV), an analysis software called “Profile Chaser” was newly developed. By using the software, all the profiles of electrode during charge/discharge processes are loaded automatically in the computer. The profiles were successively displayed on a monitor as a series of profiles in conjunction of compositions estimated from the charge/discharge curves, so that the profile change was traced from the monitor.3. Results and discussionsFig.1 shows the SRD profile changes in the discharge process of 0th and 1st cycles. In both cycles, the intensity of 111 diffraction of BiF3 decreased and that of 012 diffraction of Bi increased as the discharge reaction proceeded. However, the formation of BiF3 was hardly observed in the charge process. It indicates that the bismuth fluoride formed in the charge process is amorphous or solved in the electrolyte. Figure 1