Few-Layer Graphene As an Electrode, Electrode Additive and an Interfacial Layer in Aqueous Supercapacitors
Authors: Williams Rhys , Sukumaran Sivakkumaran , Abbas Qaisar , Hunt Michael 
Published: November 2022

The intermittent nature of many renewable energy sources such as wind and solar, coupled with fluctuations in energy demand, creates a pressing need for efficient, low-cost energy storage technologies. Supercapacitors are promising candidates to play a role in next-generation energy storage systems. They have a higher power density and better cycle life (although lower energy density) than batteries making them ideal for rapid energy storage and deployment [1]. Activated carbon is a favoured electrode material due to high surface area, although low conductivity requires use of a conductive additive (often carbon black), reducing available surface area for charge storage. In contrast, the high conductivity and specific surface area of graphene has made it a promising material for electrochemical double layer supercapacitors (EDLCs) [2], however, performance is limited by restacking of the graphene sheets, reducing available surface area.
In this work, high-shear exfoliated few layer graphene (FLG) [3] is investigated both as an electrode material and as a conductive additive/interfacial layer for EDLCs. FLG suspensions were produced under a variety of exfoliation conditions, with platelet thickness and linear dimension determined from Raman spectroscopy based on metrics developed by Backes et al. [4] and through scanning electron microscopy (SEM).
The FLG suspensions were used in three ways: i) to create thin ‘graphene paper’ electrodes; ii) as a conductive additive, mixed into the activated carbon electrode material; iii) deposited onto the back of (and diffused within) activated carbon electrodes. These electrodes were investigated by Raman spectroscopy and Scanning Electron Microscopy, before being assembled into symmetric two-terminal aqueous cells then evaluated by cyclic voltammetry (CV), galvanostatic charge/discharge (GCD), and electrochemical impedance spectroscopy (EIS), and their electrochemical performance related to structure and composition.
As expected, pure FLG electrodes often showed excellent low series resistance values, however specific capacitance was low, due to restacking. Directly mixing 5% FLG into activated carbon as a conventional conductive additive led to a specific capacitance of 63 F/g (from CV at 10 mV/s), and a series resistance of 19 W (from GCD at 1 A/g) - markedly inferior to those with 5% carbon black as a conductive additive (95 F/g and 2 Ohm) and inferior even to electrodes with no conductive additive (87 F/g and 10 Ohm).
However, post fabrication deposition/infusion of FLG offers comparable performance to carbon black (90 F/g and 1 Ohm) at 7% FLG by weight. As the quantity of FLG is increased the specific capacitance decreases sharply. This behaviour is attributed to FLG restacking on the rear of the electrode, so adding mass whilst providing limited additional capacitance, and compression of the electrode.
Adding high-shear exfoliated FLG to activated carbon electrodes shows promise for obtaining the benefits of both materials. At present, FLG/activated carbon electrodes can match the performance of those produced from activated carbon with a carbon black conductive additive and, with further optimization, we expect will be able to exceed them.
Figure: a) Cross sectional SEM image of activated carbon electrode with graphene interfacial layer; b) magnified cross sectional SEM image of graphene interfacial layer; c) cyclic voltammograms at 10 mV/s of the different electrodes mentioned in the abstract.
References:
[1] A. Gonzalez, E. Goikolea, J.A. Barrena and R. Mysyk; ‘Review on supercapacitors: Technologies and materials’, Renewable and Sustainable Energy Reviews,
58, 1189-1206 (2016).
[2] M.F. El-Kady, Y. Shao, and R.B. Kaner; ‘Graphene for batteries, supercapacitors and beyond’, Nature Reviews Materials
1, 16033 (2016).
[3] K.R. Paton et al.; ‘Scalable production of large quantities of defect-free few-layer graphene by shear exfoliation in liquids’, Nature Materials, 13, 624-630 (2014).
[4] C. Backes et al. ‘Spectroscopic metrics allow in-situ measurement of mean size and thickness of liquid-exfoliated graphene nanosheets’, Nanoscale
8, 4311-4323 (2016).

Figure 1