Abstract A new concentrated ternary salt ether‐based electrolyte enables stable cycling of lithium metal battery (LMB) cells with high‐mass‐loading (13.8 mg cm−2, 2.5 mAh cm−2) NMC622 (LiNi0.6Co0.2Mn0.2O2) cathodes and 50 μm Li anodes. Termed “CETHER‐3,” this electrolyte is based on LiTFSI, LiDFOB, and LiBF4with 5 vol% fluorinated ethylene carbonate in 1,2‐dimethoxyethane. Commercial carbonate and state‐of‐the‐art binary salt ether electrolytes were also tested as baselines. With CETHER‐3, the electrochemical performance of the full‐cell battery is among the most favorably reported in terms of high‐voltage cycling stability. For example, LiNixMnyCo1–x–yO2(NMC)‐Li metal cells retain 80% capacity at 430 cycles with a 4.4 V cut‐off and 83% capacity at 100 cycles with a 4.5 V cut‐off (charge at C/5, discharge at C/2). According to simulation by density functional theory and molecular dynamics, this favorable performance is an outcome of enhanced coordination between Li+and the solvent/salt molecules. Combining advanced microscopy (high‐resolution transmission electron microscopy, scanning electron microscopy) and surface science (X‐ray photoelectron spectroscopy, time‐of‐fight secondary ion mass spectroscopy, Fourier‐transform infrared spectroscopy, Raman spectroscopy), it is demonstrated that a thinner and more stable cathode electrolyte interphase (CEI) and solid electrolyte interphase (SEI) are formed. The CEI is rich in lithium sulfide (Li2SO3), while the SEI is rich in Li3N and LiF. During cycling, the CEI/SEI suppresses both the deleterious transformation of the cathode R‐3m layered near‐surface structure into disordered rock salt and the growth of lithium metal dendrites. 
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                            Revisiting Discharge Mechanism of CF x as a High Energy Density Cathode Material for Lithium Primary Battery
                        
                    
    
            Abstract Lithium/fluorinated graphite (Li/CFx) primary batteries show great promise for applications in a wide range of energy storage systems due to their high energy density (>2100 Wh kg–1) and low self‐discharge rate (<0.5% per year at 25 °C). While the electrochemical performance of the CFxcathode is indeed promising, the discharge reaction mechanism is not thoroughly understood to date. In this article, a multiscale investigation of the CFxdischarge mechanism is performed using a novel cathode structure to minimize the carbon and fluorine additives for precise cathode characterizations. Titration gas chromatography, X‐ray diffraction, Raman spectroscopy, X‐ray photoelectron spectroscopy, scanning electron microscopy, cross‐sectional focused ion beam, high‐resolution transmission electron microscopy, and scanning transmission electron microscopy with electron energy loss spectroscopy are utilized to investigate this system. Results show no metallic lithium deposition or intercalation during the discharge reaction. Crystalline lithium fluoride particles uniformly distributed with <10 nm sizes into the CFxlayers, and carbon with lower sp2content similar to the hard‐carbon structure are the products during discharge. This work deepens the understanding of CFxas a high energy density cathode material and highlights the need for future investigations on primary battery materials to advance performance. 
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                            - Award ID(s):
- 2011924
- PAR ID:
- 10448288
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Energy Materials
- Volume:
- 12
- Issue:
- 5
- ISSN:
- 1614-6832
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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