Synthesis of Carbide Derived Carbon (CDC) By Electrolysis of Molten Chloride Salts
Authors: McNallan Michael , Mika Mariusz , Cheng Kai-yuan 
Published: February 2020

Synthesis of Carbide Derived Carbon (CDC) by Electrolysis of Molten Chloride Salts
Mariusz Mika, Michael McNallan, Kai-yuan Cheng, Department of Civil and Materials Engineering, University of Illinois at Chicago, 842 w. Taylor St., Chicago, IL 60607
Carbide Derived Carbon (CDC) is a nanostructured porous carbon that is produced by extraction of the metal component from a ceramic carbide by a high temperature reaction. CDC materials are useful in a number of advanced devices, including supercapacators, lithium ion batteries, and tribological systems. [1-3] Carbide derived carbons have been produced by exposing carbide ceramics to vacuum at very high temperatures, by hydrothermal reactions, and by electrochemical processing in room temperature electrolytes,[4,5] but the largest quantities of these materials have been produced by exposing the ceramics to halogen gases, mainly chlorine, at temperatures between 800 and 1200oC, where the high vapor pressures of metal halide species, such as SiCl4, and TiCl4 leads to rapid removal of the metal component. Because this temperature is not sufficiently high to facilitate the crystallization of the carbon into the equilibrium graphite structure, the product is amorphous and nanocrystalline carbon containing nanoscale porosity.
The use of chlorine gas to synthesize CDC presents many practical problems due to its corrosive and toxic nature. The system requires close monitoring for safety, and equipment tends to deteriorate rapidly because of exposure to the chlorine. If an application requires synthesis of CDC only on specific locations on the carbide, it is difficult to mask the surface of the carbide from the aggressive gas.
As an alternative method to produce CDC, we have prepared CDC on several carbides by electrolysis of molten chloride salts. The apparatus used to produce CDC is shown schematically in Figure 1. The electrolyte was a KCl-NaCl eutectic at temperatures between 750oC and 900oC. Several carbides, including SiC and Ti2AlC have been processed, all resulting in carbide derived carbon synthesis as identified by Raman spectroscopy. The effects of process parameters including precursor carbide, temperature, cell voltage, and temperature will be discussed.
References:
1. Y.G.Gogotsi, I.D. Jeon, M.J. McNallan, “Carbon Coatings on Silicon Carbide by Reaction with Chlorine Containing Gases,” Journal of Materials Chemistry, 7, 1997, pp 1841-1848.
2. Y. Gogotsi, “Not just Graphene, The Wonderful World of Carbon and Related Nanomaterials,” MRS Bulletin, 40, 2015, pp.1110-1120.
3. V. Presser, M. Heon, Y. Gogotsi, “Carbide Derived Carbons – From Porous Networks to Nanotubes and Graphene,” Advanced Functional Materials, 21, 2011, pp 810-833.
4. J. Senthilnathan, C.C. Weng, W.T. Tsai, Y. Gogotsi, M. Yoshimura, “Synthesis of Carbon Films by Electrochemical Etching of SiC with Hydrofluoric Acid in Non-aqueous Solvents,” Carbon, 71, 2014, pp 181-189.
5. M.R. Lukatskaya, J. Halim, B. Dyatkin, M. Naguib, Y.S. Buranova, M. Barsoum, Y. Gogotsi, “Room Temperature Carbide Derived Carbon Synthesis by Electrochemical Etching of MAX Phases,” Angewandte Chemie, International Edition, 53, 2014, pp 4877-4880.
Figure 1. Schematic diagram of apparatus for electrolytic production of CDC from metal carbides in a molten chloride electrolyte.

Figure 1