Largely pseudocapacitive two-dimensional conjugated metal–organic framework anodes with lowest unoccupied molecular orbital localized in nickel-bis(dithiolene) linkages

DOI: 10.1021/jacs.2c12684

Authors: Panpan Zhang (uazhong University of Science and Technology; Technische Universität Dresden) , Mingchao Wang (Technische Universität Dresden) , Yannan Liu (Technische Universität Dresden; Max Planck Institute of Microstructure Physics) , Yubin Fu (Technische Universität Dresden; Max Planck Institute of Microstructure Physics) , Mingming Gao (Huazhong University of Science and Technology) , Gang Wang (Technische Universität Dresden; Technische Universität Dresden) , Faxing Wang (Technische Universität Dresden) , Zhiyong Wang (Technische Universität Dresden; Max Planck Institute of Microstructure Physics) , Guangbo Chen (echnische Universität Dresden) , Sheng Yang (Technische Universität Dresden; Shanghai Jiao Tong University) , Youwen Liu (Huazhong University of Science and Technology) , Renhao Dong (Technische Universität Dresden; Shandong University) , Minghao Yu (Technische Universität Dresden) , Xing Lu (Huazhong University of Science and Technology) , Xinliang Feng (Technische Universität Dresden; Max Planck Institute of Microstructure Physics)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society , VOL 15

State: Published (Approved)
Published: March 2023

Abstract: Although two-dimensional conjugated metal–organic frameworks (2D c-MOFs) provide an ideal platform for precise tailoring of capacitive electrode materials, high-capacitance 2D c-MOFs for non-aqueous supercapacitors remain to be further explored. Herein, we report a novel phthalocyanine-based nickel-bis(dithiolene) (NiS4)-linked 2D c-MOF (denoted as Ni2[CuPcS8]) with outstanding pseudocapacitive properties in 1 M TEABF4/acetonitrile. Each NiS4 linkage is disclosed to reversibly accommodate two electrons, conferring the Ni2[CuPcS8] electrode a two-step Faradic reaction with a record-high specific capacitance among the reported 2D c-MOFs in non-aqueous electrolytes (312 F g–1) and remarkable cycling stability (93.5% after 10,000 cycles). Multiple analyses unveil that the unique electron-storage capability of Ni2[CuPcS8] originates from its localized lowest unoccupied molecular orbital (LUMO) over the nickel-bis(dithiolene) linkage, which allows the efficient delocalization of the injected electrons throughout the conjugated linkage units without inducing apparent bonding stress. The Ni2[CuPcS8] anode is used to demonstrate an asymmetric supercapacitor device that delivers a high operating voltage of 2.3 V, a maximum energy density of 57.4 Wh kg–1, and ultralong stability over 5000 cycles.

Subject Areas: Materials, Chemistry, Energy


Instruments: B18-Core EXAFS

Other Facilities: P65 at PETRA III; BL14W1 and BL15U1 at Shanghai Synchrotron Radiation Facility (SSRF)

Added On: 12/03/2023 20:23

Discipline Tags:

Energy Storage Energy Energy Materials Chemistry Materials Science Chemical Engineering Engineering & Technology Metal-Organic Frameworks Metallurgy Organometallic Chemistry

Technical Tags:

Spectroscopy X-ray Absorption Spectroscopy (XAS) Extended X-ray Absorption Fine Structure (EXAFS)