Effects of sulfuric acid treatment on the microstructure and electrochemical performance of a polyacrylonitrile (PAN)-based carbon anode

Abstract

To examine whether acid treatment of a non-graphitizing hard carbon influences positively or negatively its electrochemical anodic performance, this study reports the effects of sulfuric acid treatment on the microstructural changes and electrochemical performance of PAN-based hard carbons prepared at various temperatures. It was found that PAN-based hard carbons heat treated at 900degreesC (TAN9) exhibit an increased reversible capacity by up to similar to20% and a decreased irreversible capacity by up to similar to8% following the sulfuric acid treatment (TAN9S series). Since small changes in microstructure, except for slight reductions in surface area and crystallite size (L-a) value, were observed after sulfuric acid treatment, it was speculated that the capacity responses of samples in series TAN9S were due to the introduction of new functional groups such as -SO3H and -SO4H. As the newly introduced functional groups are strong acids but their conjugates (-SO3 and -SPO4) are weak bases, those conjugates were thus considered to be able to react with Li+ ion relatively weakly and reversibly. For PAN-based hard carbons heat treated at 1100degreesC (TANI 1), there were much smaller changes, as compared with series TAN9S samples, in surface chemistry and microstructure by sulfuric acid treatment. Consequently, we observed an analogous but smaller influence of sulfuric acid oxidation on electrochemical performance. The samples from series TANIIS exhibited very stable cycling behavior. It was suggested that the acidity/basicity of surface functional groups may be an influential factor for improving the electrochemical performance of hard carbon-based anodic materials for lithium ion batteries. (C) 2004 Elsevier Ltd. All rights reserved.