TY - JOUR
T1 - Toward a Reversible Calcium-Sulfur Battery with a Lithium-Ion Mediation Approach
AU - Yu, Xingwen
AU - Boyer, Mathew J.
AU - Hwang, Gyeong S.
AU - Manthiram, Arumugam
N1 - Funding Information:
This work was primarily supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under award number DE-SC0005397. The computational work was supported by Robert A. Welch Foundation grant F-1535 and the authors thank the Texas Advanced Computing Center (TACC) for providing HPC resources. The authors also thank Sanjay Nanda and Qiang Xie for their assistance, respectively, with the XPS data collection and TGA.
Publisher Copyright:
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/4/11
Y1 - 2019/4/11
N2 - Calcium represents a promising anode for the development of high-energy-density, low-cost batteries. However, a lack of suitable electrolytes has restricted the development of rechargeable batteries with a Ca anode. Furthermore, to achieve a high energy density system, sulfur would be an ideal cathode to couple with the Ca anode. Unfortunately, a reversible calcium-sulfur (Ca-S) battery has not yet been reported. Herein, a basic study of a reversible nonaqueous room-temperature Ca-S battery is presented. The reversibility of the Ca-S chemistry and high utilization of the sulfur cathode are enabled by employing a Li + -ion-mediated calcium-based electrolyte. Mechanistic insights pursued by spectroscopic, electrochemical, microscopic, and theoretical simulation (density functional theory) investigations imply that the Li + -ions in the Ca-electrolyte stimulate the reactivation of polysulfide/sulfide species. The coordination of lithium to sulfur reduces the formation of sturdy Ca-S ionic bonds, thus boosting the reversibility of the Ca-S chemistry. In addition, the presence of Li + -ions facilitates the ionic charge transfer both in the electrolyte and across the solid electrolyte interphase layer, consequently reducing the interfacial and bulk impedance of Ca-S batteries. As a result, both the utilization of active sulfur in the cathode and the discharge voltage of Ca-S batteries are significantly improved.
AB - Calcium represents a promising anode for the development of high-energy-density, low-cost batteries. However, a lack of suitable electrolytes has restricted the development of rechargeable batteries with a Ca anode. Furthermore, to achieve a high energy density system, sulfur would be an ideal cathode to couple with the Ca anode. Unfortunately, a reversible calcium-sulfur (Ca-S) battery has not yet been reported. Herein, a basic study of a reversible nonaqueous room-temperature Ca-S battery is presented. The reversibility of the Ca-S chemistry and high utilization of the sulfur cathode are enabled by employing a Li + -ion-mediated calcium-based electrolyte. Mechanistic insights pursued by spectroscopic, electrochemical, microscopic, and theoretical simulation (density functional theory) investigations imply that the Li + -ions in the Ca-electrolyte stimulate the reactivation of polysulfide/sulfide species. The coordination of lithium to sulfur reduces the formation of sturdy Ca-S ionic bonds, thus boosting the reversibility of the Ca-S chemistry. In addition, the presence of Li + -ions facilitates the ionic charge transfer both in the electrolyte and across the solid electrolyte interphase layer, consequently reducing the interfacial and bulk impedance of Ca-S batteries. As a result, both the utilization of active sulfur in the cathode and the discharge voltage of Ca-S batteries are significantly improved.
KW - calcium-sulfur chemistry
KW - electrochemical mechanism
KW - electrochemical performance
KW - lithium-ion mediation
KW - rechargeable batteries
UR - http://www.scopus.com/inward/record.url?scp=85061584773&partnerID=8YFLogxK
U2 - 10.1002/aenm.201803794
DO - 10.1002/aenm.201803794
M3 - Article
AN - SCOPUS:85061584773
SN - 1614-6832
VL - 9
JO - Advanced Energy Materials
JF - Advanced Energy Materials
IS - 14
M1 - 1803794
ER -