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Isothermal Sulfur Condensation into Carbon Scaffolds: Improved Loading, Performance, and Scalability for Lithium–Sulfur Battery Cathodes

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† ‡ Department of Mechanical Engineering and Interdisciplinary Materials Science Program, Vanderbilt University, Nashville, Tennessee 37235, United States
*E-mail [email protected] (C.L.P.).
Cite this: J. Phys. Chem. C 2017, 121, 14, 7718–7727
Publication Date (Web):March 23, 2017
Copyright © 2017 American Chemical Society

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    Here we demonstrate an isothermal technique that enables rapid vapor infiltration of sulfur into carbon templates to overcome scalability and performance bottlenecks associated with common melt infiltration techniques. Building on straightforward thermodynamic principles of capillary condensation, self-limited sulfur loadings up to 82 wt % can be achieved in as little as 10 min at temperatures between 155 and 175 °C. We demonstrate a broad range of device performance criteria using a carbon black–single-walled carbon nanotube binder-free cathode framework, including a side-by-side comparison to melt infiltrated electrodes with 74 wt % loading that shows improved capacity (1015 mAh/g vs 768 mAh/g), ∼92% capacity retention after 200 cycles at 0.5 C, and ∼98% Coulombic efficiency as a result of enhanced uniformity and conductivity. Further, we demonstrate this technique over a range of different electrodes (1) electrodes with high sulfur loading (82 wt %) with high initial discharge capacity of 1340 mAh/g, (2) electrodes with high areal loading of 8 mg/cm2 sulfur with >6.5 mAh/cm2 areal capacity, and (3) electrodes based on carbons with microporous confining pores. Most importantly, this vapor infiltration approach requires over 5× less energy input and enables over 60× greater throughput than standard melt infiltration, enabling integration into roll-to-roll rapid processing schemes without compromising device performance. This technique liberates cost and manufacturing barriers to commercialization of Li–S batteries at larger scales while opening new avenues to infiltrate preformed cathode assemblies with sulfur for assessment at lab scales.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.7b01117.

    • Comparative analysis with state-of-the-art devices, thermogravimetric analysis, vapor pressure/temperature relation, additional analysis of high specific and areal loading devices, details on fits to the electrochemical impedance spectroscopy data, power consumption assessment comparison between isothermal vapor infiltration and melt infiltration, TEM analysis of materials produced by condensation using temperature gradients, SEM and STEM EDS of both vapor infiltrated and melt infiltrated materials, additional details on the kinetics and thermodynamics of isothermal vapor infiltration, device data and material characterization of a microporous sulfur confining cathode, and STEM EDS maps of capillary filled MWCNTs (PDF)

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