Enhancing sp3 content in diamond-like carbon thin film electrodes by pulsed laser annealing for durable charge storage performance

Abstract

In this work, diamond-like carbon (DLC) thin film electrodes were grown on Si substrate by pulsed laser deposition (PLD) technique, and the implication of pulsed laser annealing (PLA) treatment on their electrochemical supercapacitor performance was examined by three electrode systems in 1 M Na2SO4 electrolyte solutions. The SEM micrographs exhibit a sheet-like wrinkled surface of DLC film on Si which later transformed into tiny hierarchical heap-like structures with enhanced surface roughness. The Raman spectra confirm signature of the D and G peaks of pristine DLC film at ~1352 cm−1 (1356 cm−1 after PLA) and 1591 cm−1 (1589 cm−1 after PLA), and appearance of minor T2g (diamond) (1332 cm−1) peaks with an increment of the sp3 content after PLA treatment. The X-ray photoelectron spectroscopy (XPS) spectra were deconvoluted into three different contributions CC (sp2), CC (sp3), and CO, and their sp3 percentages were estimated ~48.9 %, and 64.7 % before and after annealing. The area under cyclic voltammetry (CV) curve and galvanostatic charging discharging (GCD) performance of PLA-treated DLC film were improved and the highest areal-specific capacitance was obtained to be ~48.25 mF/cm2 for scan rate of 5 mV/s and 36.01 mF/cm2 for current density of 2 mA/cm2, respectively. Excellent charging discharging cyclic stability of PLA treated electrode was observed over 5000 cycles, and Coulombic efficiency and capacitance retention were determined to be ~93.5 % and ~ 97.3 %, respectively. The electrochemical impedance spectroscopy (EIS) was performed to obtain the Nyquist plot (Z′vs.Z′′) of both electrodes before and after the stability test, and a small degradation in impedance was observed. The Nyquist plots were fitted with the well-known Randles equivalent circuit model Rs(Cdl(RctZw)) and substantial curtailment of Warburg resistance (Zw) in PLA-induced DLC electrode signifies the dominance of the diffusion-controlled region in the charging-discharging process. Minor changes in the Nyquist plot before and after the stability test manifest the enduring charge kinetics of both electrodes and PLA-treated DLC exhibits better cyclic stability. PLA techniques have a great impact on upgrading the areal-specific capacitance, capacitance retention with high Coulombic efficiency, and stability with negligible impedance loss of the DLC film electrodes.