TY - JOUR
T1 - Trisulfide-Bond Acenes for Organic Batteries
AU - Hu, Peng
AU - He, Xuexia
AU - Ng, Man Fai
AU - Ye, Jun
AU - Zhao, Chenyang
AU - Wang, Shancheng
AU - Tan, Kejie
AU - Chaturvedi, Apoorva
AU - Jiang, Hui
AU - Kloc, Christian
AU - Hu, Wenping
AU - Long, Yi
N1 - P.H. acknowledges financial support from the National Natural Science Foundation of China (No. 51803168) and the Youth Innovation Team of Shaanxi Universities. H.J. and C.K. gratefully acknowledge the Singapore Ministry of Education for support via an AcRT RG125/4 grant. This research is partially supported (except M.-F.N. and J.Y.) by grants from the Singapore Ministry of Education (MOE) Academic Research Fund Tier one RG200/17, and the National Research Foundation, Prime Minister's Office, Singapore under its Campus of Research Excellence and Technological Enterprise (CREATE) programme. M.-F.N. and J.Y. would like to acknowledge the A*STAR Computational Resource Centre (ACRC) and National Supercomputing Center (NSCC) in Singapore for allowing the use of its high-performance computing facilities. X.H. acknowledges financial support from the National Natural Science Foundation of China (No. 51702203). W.H. acknowledges financial support from the Ministry of Science and Technology of the People's Republic of China (Grant Nos. 2017YFA0204503 and 2016YFB0401100), the National Natural Science Foundation of China (Grant Nos. 51725304, 51633006, 51703159, 51733004, and 91433115), and the Strategic Priority Research Program (Grant No. XDB12030300) of the Chinese Academy of Sciences. H.J. is very grateful to Prof. Denis Fichou for profound discussions.
Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/9/16
Y1 - 2019/9/16
N2 - The molecular design of organic battery electrodes is a big challenge. Here, we synthesize two metal-free organosulfur acenes and shed insight into battery properties using first-principles calculations. A new zone-melting chemical-vapor-transport (ZM-CVT) apparatus was fabricated to provide a simple, solvent-free, and continuous synthetic protocol, and produce single crystals of tetrathiotetracene (TTT) and hexathiapentacene (HTP) at a large scale. Single crystals of HTP showed better Li-ion battery performance and higher cycling stability than those of TTT. A two-step, three-electron lithiation mechanism instead of the commonly depicted two-electron mechanism is proposed for the HTP Li-ion battery. The superior performance of HTP is linked to unique trisulfide bonding scenarios, which are also responsible for the formation of empty channels along the stacking direction. In-depth theoretical analysis suggests that organosulfur acenes are potential prototypes for organic battery materials with tunable properties, and that the tuning of sulfur bonds is critical in designing these new materials.
AB - The molecular design of organic battery electrodes is a big challenge. Here, we synthesize two metal-free organosulfur acenes and shed insight into battery properties using first-principles calculations. A new zone-melting chemical-vapor-transport (ZM-CVT) apparatus was fabricated to provide a simple, solvent-free, and continuous synthetic protocol, and produce single crystals of tetrathiotetracene (TTT) and hexathiapentacene (HTP) at a large scale. Single crystals of HTP showed better Li-ion battery performance and higher cycling stability than those of TTT. A two-step, three-electron lithiation mechanism instead of the commonly depicted two-electron mechanism is proposed for the HTP Li-ion battery. The superior performance of HTP is linked to unique trisulfide bonding scenarios, which are also responsible for the formation of empty channels along the stacking direction. In-depth theoretical analysis suggests that organosulfur acenes are potential prototypes for organic battery materials with tunable properties, and that the tuning of sulfur bonds is critical in designing these new materials.
KW - density functional theory
KW - non-covalent interactions
KW - organic batteries
KW - organic semiconductors
KW - organosulfur acenes
KW - symmetry-adapted perturbation theory (SAPT)
UR - https://www.scopus.com/pages/publications/85070760671
U2 - 10.1002/anie.201906301
DO - 10.1002/anie.201906301
M3 - Journal article
C2 - 31317598
AN - SCOPUS:85070760671
SN - 1433-7851
VL - 58
SP - 13513
EP - 13521
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 38
ER -