Introduction The lithium-air battery (LAB), which has ten times the energy density of conventional lithium-ion batteries (LIB), is one of the promising candidates for the next-generation storage batteries, and there are great expectations for its development [1]. However, the reaction mechanism of the cathode reaction is still unclear, and the type of Li2O2 that is the product of the cathode in discharging is still unknown. The main reason for this is considered to be that it was difficult to directly observe the compounds generated at the cathode during LAB operation. By improving the laboratory XRD and the observation cell, we succeeded in operando XRD measurements of the cathode reaction in the LAB. In addition, under general conditions, the cathode product was Li1.5O2 with some Li missing from the crystal lattice of Li2O2 [2]. Here, we describe the details and discuss the reaction mechanism. Experimental An electrochemical cell covered with a Kapton® dome was constructed to allow constant oxygen flow to the cathode side of the LAB, and was attached to the diffractomator of a Rigaku Ultima IV XRD measurement system. A Cu Ka was used as the incident x-ray, a high-speed one-dimensional detector was used as the detector, a Ketjen black free-standing film was used as the cathode material, and tetraglyme solution with 0.5 M LiTFSI + 0.5 M LiNO3 + 0.2 M LiBr was used as the electrolyte solution. The LAB was discharged and charged at a constant current density of 0.4 mA/cm2 for 10 hours (4.0 mAh/cm2) each, and the XRD profile was recorded every 20 minutes. Each XRD profile was subjected to Rietveld analysis using Rigaku’s SmartLab Studio II software to determine the cathode product and its crystal structure. Results and discussion In the XRD profile measured during discharging, a lot of peaks due to the cell parts were observed. But, several peaks due to the cathode product were also observed. As a result of detailed Rietveld analysis of these peaks, the cathode product at the discharging capacity of 4.0 mAh/cm2 was not Li2O2 but Li1.5O2. Instead of the normal LiO2 with a rectangular crystal structure, LiO2 with a hexagonal crystal structure, which is the same as that of Li2O2, was observed immediately after the discharge. As the discharge progressed, Li was added to it, and the lattice constant gradually extended in the c-axis direction, forming Li1.5O2 at a discharge of 4.0 mAh/cm2. In the presentation, the charging process and the charge-discharge cycle characteristics would also be discussed.
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