High-Energy Electrochemical Capacitors Utilizing Chemically Reduced Graphite Oxide As Negative Electrode Material

Abstract

Taking into account power needs for portable devices, the energy storage through electrochemical reactions seems to be a crucial technology, especially due to the growing technological advances requirements. Electrochemical capacitors have attracted great attention as promising energy storage devices because of their high power density and cycle life noticeably longer than batteries [i],[ii]. Recently, extensive works have been focused on enhancing both the energy and power density accompanied by reasonable cost of device production as well as its environment-friendly character. One of the approaches is idea initiated in 2001 [iii], of improving capacitors performance by merging advantages of capacitors and lithium-ion batteries. This procedure was aimed to increase the energy of the capacitor while maintaining the level of supplied power. Starting from 2001 till now in the literature we can find examples of different methods involving various electrode materials [iv],[v],[vi],[vii],[viii],[ix],[x]. Asymmetric supercapacitors composed of battery-type electrode and a high surface area carbon electrode [xi] combine the advantages and reduces the drawback of redox and capacitive based systems. Therefore, the asymmetric design offers the advantages of supercapacitors (power rate, cycle life) and batteries (energy density) [xii]. This work is focused on high-energy electrochemical capacitors utilizing chemically reduced graphite oxide (CRGO) as a negative electrode material and activated carbon (AC) with the well-developed surface area as a positive electrode material. For comparison, electrochemical characteristic of capacitors utilizing graphite negative electrode was also performed. The pre-lithiation process, made by electrochemical intercalation of lithium ions into graphite, has been chosen as the main method of negative electrode material preparing. Performed electrochemical measurements, i.e., cyclic voltammetry and galvanostatic charging/discharging presented improved energy efficiency compared with results for symmetric cells (i.e. AC/AC capacitor). All measurements were performed in the organic electrolyte to provide a wide range of operating voltage. In the case of the hybrid system energy density has been improved and exceed 90 Wh kg-1 accompanied by good power profile. Additionally, good cycle performance was also achieved. Chemically reduced graphite oxide (CRGO) displays excellent performance at current densities up to 8 A g-1and, therefore, it can be considered as a very promising material for high energy Lithium-ion capacitors (LICs). Moreover, for more detailed analysis, measurements in three-electrode cells were also conducted. Fig. 1 shows an example of cyclic voltammetry curves for two systems composed of activated carbon cathode and graphite or CRGO anode. For graphite anode, Faradaic reactions can be observed in very narrow working range (134 mV) comparing to the positive electrode (1266 mV). CRGO characteristics merge two mechanisms of lithium storage, namely, Faradaic and capacitive one. In result, the quite good proportion of working potentials between positive and negative electrodes (772 mV vs. 628 mV, respectively) can be seen. The intercalation of lithium ions into graphite material occurs relatively slowly, hence the difference in power between the electrochemical capacitors and lithium-ion batteries. The electrode with the slowest sweep of potential will determine the power of the device. In this case chemically reduced graphite oxide seems to be promising material as an anode in lithium ion capacitors due to the merged lithium insertion movement, that’s why the energy storage can take place comparatively fast, as in the positive electrode. Financial support from the project DEC-2013/09/D/ST5/03886 is gratefully acknowledged. Fig. 1. Comparison of working potentials positive and negative electrodes in hybrid systems AC/G(Li) and AC/CRGO(Li), obtained from cyclic voltammetry measurements. [i] A. Burke, J. Power Sources 91 (2000) 37 [ii] P. Simon, Y. Gogotsi, Nat. Mater. 7 (2008) 845 [iii] G.C. Amatucci, F. Badway, A.D. Pasquier, T. Zheng, J. Electrochem. Soc. 148 (2001) A930 [iv] D. Cericola, R. Kötz, Electrochimica Acta 72 (2012) 1 [v] W.J. Cao, J. Shih, J.P. Zheng, T. Doung, J. Power Sources 257 (2014) 388 [vi] S.R. Sivakkumar, A.G. Pandolfo, J. Appl. Electrochem. 44 (2014) 105 [vii] X. Sun, X. Zhang, H. Zhang, N. Xu, K. Wang, Y. Ma, J. Power Sources 270 (2014) 318 [viii] S. Dsoke, B. Fuchs, E. Gucciardi, M. Wohlfahrt-Mehrens, J. Power Sources 282 (2015) 385 [ix] J. Zhang, Z. Shi, J. Wang, J. Shi, J. Electroana. Chem. 747 (2015) 20 [x] K. Naoi, P.Simon, Electrochem. Soc. Interface 17 (1) (2008) 34 [xi] J.W. Long, D. Belanger, T. Brousse, W. Sugimoto, M.B. Sassin, O. Crosnier, MRS Bull. 36 (2011) 513 [xii] Z.J. Fan, J. Yan, T. Wei, L.J. Zhi, G.Q. Ning, T.Y. Li, F. Wei, Adv. Funct. Mater. 21 (2011) 2366 Figure 1