Improved Electrochemical Performance in an Exfoliated Tetracyanonickelate-Based Metal-Organic Framework

Md Abdul Halim; Subrata Karmakar; Md Abdul Hamid; Chironjib Singha Samanta Chandan; Imteaz Rahaman; Michael E Urena; Ariful Haque; Maggie Yihong Chen; Christopher P Rhodes; Gary W Beall

doi:10.1021/acsami.3c14059

Improved Electrochemical Performance in an Exfoliated Tetracyanonickelate-Based Metal-Organic Framework

ACS Appl Mater Interfaces. 2023 Nov 22;15(46):53568-53583. doi: 10.1021/acsami.3c14059. Epub 2023 Nov 9.

Authors

Affiliations

¹ Materials Science, Engineering, and Commercialization, Texas State University, San Marcos, Texas 78666, United States.
² Department of Electrical Engineering, Texas State University, San Marcos, Texas 78666, United States.
³ Department of Biology, Texas State University, San Marcos, Texas 78666, United States.
⁴ Department of Chemistry and Biochemistry, Texas State University, San Marcos, Texas 78666, United States.

PMID: 37943692
DOI: 10.1021/acsami.3c14059

Abstract

Tetracyanonickelate (TCN)-based metal-organic frameworks (MOFs) show great potential in electrochemical applications such as supercapacitors due to their layered morphology and tunable structure. This study reports on improved electrochemical performance of exfoliated manganese tetracyanonickelate (Mn-TCN) nanosheets produced by the heat-assisted liquid-phase exfoliation (LPE) technique. The structural change was confirmed by the Raman frequency shift of the C≡N band from 2177 to 2182 cm^-1 and increased band gap from 3.15 to 4.33 eV in the exfoliated phase. Statistical distribution obtained from atomic force microscopy (AFM) shows that 50% of the nanosheets are single-to-four-layered and have an average lateral size of ∼240 nm² and thickness of ∼1.2-4.8 nm. High-resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) patterns suggest that the material maintains its crystallinity after exfoliation. It exhibits an almost 6-fold improvement in specific capacitance (from 13.0 to 72.5 F g^-1) measured at a scan rate of 5 mV s^-1 in 1 M KOH solution. Galvanostatic charge-discharge (GCD) measurement shows a capacity enhancement from ∼18 F g^-1 in the bulk phase to ∼45 F g^-1 in the exfoliated phase at a current density of 1 A g^-1. Bulk crystals exhibit an increasing trend of capacitance retention by ∼125% over 1000 charge-discharge cycles attributed to electrochemical exfoliation. Electrochemical impedance spectroscopy (EIS) demonstrates a 5-fold reduction in the total equivalent series resistance (ESR) from 4864 Ω (bulk) to 1089 Ω (exfoliated). The enhanced storage capacity in the exfoliated phase results from the combined effect of the electrochemical double-layer charge storage mechanism at the nanosheet-electrolyte interface and the Faradic process characteristic of the pseudocapacitive charge storage behavior.

Keywords: Nyquist plot; electrochemical performance; layered structure; liquid-phase exfoliation; metal−organic framework; pseudocapacitance; surface area; tetracyanonickelate.