Electrochemical and spectroscopic studies of carbon electrodes in lithium battery electrolyte systems

In this work we studied several parameters that influence the intercalation of lithium ions into carbons (e.g. carbon type, binder and solution composition). The carbons investigated included carbon blacks (e.g. acetylene black, Ketjen black), graphite and carbon fibers. The solvents used in this study include methyl formate, propylene and ethylene carbonate, ethers (e.g. tetrahydrofuran) and their mixtures. The salts included LiClO₄, LiAsF₆ and LiBF₄. CO₂ was tested as an additive. The electrochemical behavior of the electrodes in solutions was followed by chronopotentiometry in galvanostatic charge/discharge cycling and their surface chemistry in solutions was investigated using surface sensitive Fourier-transform infrared spectroscopy (FT-IR) in transmittance, attenuated total reflectance and diffuse reflectance modes. It was found that the solvents and salts are reduced on the carbon electrodes at low potentials to form surface films. In general, their surface chemistry is quite similar to that of lithium or noble metal electrodes at low potential (in the same solutions). The electrochemical behavior of the carbon electrodes in terms of degree of intercalation and its reversibility is strongly affected by their surface chemistry. Reversible intercalation was obtained with graphite in methyl formate solutions containing CO₂. Some degree of reversible intercalation was also obtained with graphite in ethers. The presence of propylene carbonate in solution is detrimental for lithium intercalation in graphite. Reversible lithium-carbon intercalation was also obtained with acetylene black and carbonized polyacrylonitrile. The binder types have a strong impact on the electrode's performance. Preliminary guidelines for optimizing the performance of carbon electrodes as anodes in rechargeable lithium battery are discussed.