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Analytical Multimode Scanning and Transmission Electron Imaging and Tomography of Multiscale Structural Architectures of Sulfur Copolymer-Based Composite Cathodes for Next-Generation High-Energy Density Li–S Batteries

Published online by Cambridge University Press:  24 November 2016

Vladimir P. Oleshko ,
Andrew A. Herzing ,
Christopher L. Soles ,
Jared J. Griebel ,
Woo J. Chung ,
Adam G. Simmonds  and
Jeffrey Pyun
Vladimir P. Oleshko*
Affiliation:
Materials Science and Engineering Division, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA
Andrew A. Herzing
Affiliation:
Materials Measurement Science Division, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA
Christopher L. Soles
Affiliation:
Materials Science and Engineering Division, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA
Jared J. Griebel
Affiliation:
Department of Chemistry & Biochemistry, University of Arizona, Tucson, AZ 85721, USA
Woo J. Chung
Affiliation:
Department of Chemistry & Biochemistry, University of Arizona, Tucson, AZ 85721, USA
Adam G. Simmonds
Affiliation:
Department of Chemistry & Biochemistry, University of Arizona, Tucson, AZ 85721, USA
Jeffrey Pyun
Affiliation:
Department of Chemistry & Biochemistry, University of Arizona, Tucson, AZ 85721, USA
*
*Corresponding author. vladimir.oleshko@nist.gov
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Abstract

Poly[sulfur-random-(1,3-diisopropenylbenzene)] copolymers synthesized via inverse vulcanization represent an emerging class of electrochemically active polymers recently used in cathodes for Li–S batteries, capable of realizing enhanced capacity retention (1,005 mAh/g at 100 cycles) and lifetimes of over 500 cycles. The composite cathodes are organized in complex hierarchical three-dimensional (3D) architectures, which contain several components and are challenging to understand and characterize using any single technique. Here, multimode analytical scanning and transmission electron microscopies and energy-dispersive X-ray/electron energy-loss spectroscopies coupled with multivariate statistical analysis and tomography were applied to explore origins of the cathode-enhanced capacity retention. The surface topography, morphology, bonding, and compositions of the cathodes created by combining sulfur copolymers with varying 1,3-diisopropenylbenzene content and conductive carbons have been investigated at multiple scales in relation to the electrochemical performance and physico-mechanical stability. We demonstrate that replacing the elemental sulfur with organosulfur copolymers improves the compositional homogeneity and compatibility between carbons and sulfur-containing domains down to sub-5 nm length scales resulting in (a) intimate wetting of nanocarbons by the copolymers at interfaces; (b) the creation of 3D percolation networks of conductive pathways involving graphitic-like outer shells of aggregated carbons; (c) concomitant improvements in the stability with preserved meso- and nanoscale porosities required for efficient charge transport.

Keywords

S(T)EMtomographyEELSEDXSLi–S batteries
Type
Materials Applications
Information
Microscopy and Microanalysis , Volume 22 , Issue 6 , December 2016 , pp. 1198 - 1221
Copyright
© Microscopy Society of America 2016 

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