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Elucidation of Discharge Mechanism in CFx As a High Energy Density Cathode Material for Lithium Primary Battery

Tuesday, 31 May 2022: 09:20
West Meeting Room 110 (Vancouver Convention Center)
B. Sayahpour, S. Bai (University of California San Diego, La Jolla, CA 92093, USA), D. Cheng (University of California, San Diego), M. Zhang, W. Li, and Y. S. Meng (University of California San Diego, La Jolla, CA 92093, USA)
Fluorinated graphite (CFx) is a class of cathode materials with the high theoretical capacity (865 mAh g-1 in case of x=1) for primary (non-rechargeable) batteries. When using Li metal as the anode material, the system possesses a very low self-discharge rate (< 0.5% per year at 25 °C) compared to other current alternative chemistries. This system, with the proposed general governing reaction of CFx+Li→LiF+C, is one of the best candidates for a wide range of applications, such as implantable medical devices and equipment for extreme environment.

Although the lithium fluorinated graphite system has been under investigation for a few decades, there is still a lack of fundamental understanding of the reaction mechanism in this system. Here, a multiscale investigation on the CFx discharge mechanism was performed using a novel cathode structure to minimize the carbon and fluorine additives for precise cathode characterizations. Titration gas chromatography (TGC), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), cross-sectional focused ion beam (FIB), high-resolution transmission electron microscopy (HRTEM), and scanning transmission electron microscopy with electron energy loss spectroscopy (STEM-EELS) were utilized to investigate this system.

The results demonstrated that: (i) There is no lithium deposition or intercalation through the entire discharge. (ii) The CFx structure transforms to a hard-carbon like structure with less sp2 content by increasing depth of discharge. (iii) The crystalline LiF particles uniformly covered the layers of CFx structure with a size range of < 10 nm. A three-step discharge reaction mechanism is proposed in agreement with our electrochemical performances. This work deepens the understanding of CFx as a high energy density cathode material and highlights the need for future investigations on primary battery materials to advance performance.