Abstract
Organic-based cathode materials have attracted considerable attention for sustainable Na-ion batteries due to their great promise to overcome the issues arising from the insertion of large Na+ into the rigid structures of conventional transition-metal-containing inorganic electrodes. The structural flexibility as a result of weak intermolecular interactions and simple electron- and ion-storage mechanisms found in organic compounds ensure facile and reversible transport of Na ions. To address the general drawbacks of small-molecule organic electrodes such as material dissolution in commonly used organic electrolytes and poor electronic conductivity, we report the use of a nitrogen- and carbonyl-rich highly extended π-conjugated small molecule, hexaazatrianthranylene (HATA) embedded quinone (HATAQ), as a cathode for sodium-ion batteries. The unique hydrogen bonds between highly functionalized conjugated HATAQ molecules allow supramolecular graphite-like 2D layered arrangements in the solid state which help facilitate the structural stability during long-term cycling and promote charge transfer. The compound delivers a capacity as high as 460 mA h g−1 at 500 mA g−1 and an excellent capacity retention of 99% (∼138 mA h g−1) after 5000 cycles at an extremely high rate of 60 A g−1. The reaction kinetics and redox mechanism of the material have been elucidated by several characterization techniques together with density functional theory (DFT) studies. The insights gained in this work could pave the way for ultra-high-performance small-molecule organic cathodes for sustainable energy storage.
| Original language | English |
|---|---|
| Pages (from-to) | 16249-16257 |
| Number of pages | 9 |
| Journal | Journal of Materials Chemistry A |
| Volume | 10 |
| Issue number | 30 |
| DOIs | |
| State | Published - Jul 7 2022 |
Funding
This work was supported by the Ministry of Science and Technology (MOST) of Taiwan under grant MOST 109-2113-M-006-016 (to T.-H. C.) and the Young Scholar Fellowship Program MOST 109-2636-E-006-001 (to W. K.). This work was also financially supported by the Hierarchical Green-Energy Materials (Hi-GEM) Research Center, from the Featured Areas Research Center Program within the framework of the Higher Education Sprout Project by the Ministry of Education (MOE) and MOST (MOST 111-2634-F-006-008) in Taiwan (to W. K.). This research was supported in part by the High Education Sprout Project, Ministry of Education of the Headquarters of University Advancement at National Cheng Kung University (NCKU) (to T.-H. C. and W. K.). The research of A.S.I. was supported as part of the Fluid Interface Reactions, Structures and Transport, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences at Oak Ridge National Laboratory under contract # DE-AC05-00OR22725. I. P. was supported by the U.S. DOE, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under contract # DE-AC05-00OR22725. The 28-ID-1 beamline of the National Synchrotron Light Source II was used, which is a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by the Brookhaven National Laboratory under Contract # DE-SC0012704. This research used resources of the Computer and Data Environment for Science (CADES) at the Oak Ridge National Laboratory. The authors acknowledge the use of the ESCA000200 and SQUID001200 of MOST 110-2731-M-006-001 belonging to the Core Facility Center of NCKU. This manuscript has been authored in part by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US DOE. The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (https://energy.gov/downloads/doe-public-access-plan). This work was supported by the Ministry of Science and Technology (MOST) of Taiwan under grant MOST 109-2113-M-006-016 (to T.-H. C.) and the Young Scholar Fellowship Program MOST 109-2636-E-006-001 (to W. K.). This work was also financially supported by the Hierarchical Green-Energy Materials (Hi-GEM) Research Center, from the Featured Areas Research Center Program within the framework of the Higher Education Sprout Project by the Ministry of Education (MOE) and MOST (MOST 111-2634-F-006-008) in Taiwan (to W. K.). This research was supported in part by the High Education Sprout Project, Ministry of Education of the Headquarters of University Advancement at National Cheng Kung University (NCKU) (to T.-H. C. and W. K.). The research of A.S.I. was supported as part of the Fluid Interface Reactions, Structures and Transport, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences at Oak Ridge National Laboratory under contract # DE-AC05-00OR22725. I. P. was supported by the U.S. DOE, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under contract # DE-AC05-00OR22725. The 28-ID-1 beamline of the National Synchrotron Light Source II was used, which is a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by the Brookhaven National Laboratory under Contract # DE-SC0012704. This research used resources of the Computer and Data Environment for Science (CADES) at the Oak Ridge National Laboratory. The authors acknowledge the use of the ESCA000200 and SQUID001200 of MOST 110-2731-M-006-001 belonging to the Core Facility Center of NCKU. This manuscript has been authored in part by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US DOE. The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( https://energy.gov/downloads/doe-public-access-plan ).
| Funders | Funder number |
|---|---|
| CADES | ESCA000200, SQUID001200, 110-2731-M-006-001 |
| DOE Public Access Plan | |
| Data Environment for Science | |
| U.S. Department of Energy | |
| Office of Science | |
| Basic Energy Sciences | |
| Oak Ridge National Laboratory | DE-AC05-00OR22725 |
| Brookhaven National Laboratory | DE-SC0012704 |
| Ministry of Education | MOST 111-2634-F-006-008 |
| Division of Materials Sciences and Engineering | |
| Ministry of Science and Technology, Taiwan | 109-2636-E-006-001, MOST 109-2113-M-006-016 |
| National Cheng Kung University |
