Intriguing properties of graphite/polysiloxane composite-based pencil electrodes

• Published in: Electrochimica acta 2024-01, Vol.475, p.143615, Article 143615
• Main Authors: Li, Xiaochun, Čechal, Jan, Spanhel, Lubomir, Toscani, Siro, Martinik, Jakub, Oborilova, Radka, Trnkova, Libuse
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Composites; DSC; EIS; Elimination voltammetry with linear scan (EVLS); GC-MS/MS; Other; Pencil graphite electrode; Polymers; Polysiloxanes; SEM; XPS
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2023.143615

Pencil leads can be considered well-defined and cheap graphite electrodes for a wide range of electrochemistry applications. These electrodes display many intriguing properties; however, the origin of these properties is not clear. Using various analytical approaches applied to two different commercially available Tombow (TO) and Staedtler (ST) pencils we reveal a causal relationship between the unique properties of pencils and their graphite/polysiloxane composite. We explore the impact of chloroform etching on chemical composition changes, thermal stability and electrochemical parameters of pencils. Using a combination of X-ray photoelectron spectroscopy (XPS) and gas chromatography-mass spectrometry (GC-MS/MS) various polydimethylsiloxanes in composites are revealed. The polysiloxane species leave into the chloroform solvent during the etching resulting in a significant decrease of their content within the electrodes. Differential scanning calorimetry (DSC) data, corroborated by gravimetric measurements, provide additional proof of the presence of composite structures in ST and TO pencils, showing glass transition temperatures at around 76 °C and 81 °C. The main difference between the TO and ST electrodes is the content and composition of the polysiloxanes within the graphite matrix. ST composites have significantly higher polymer content (∼ 30 %) with traces of Na and S impurities compared to TO ones (∼ 14 %) free of contaminations. Furthermore, mainly cyclic nanostructures appear in chloroform extracts of ST composites whereas rather chain-like clusters are liberated out of the TO counterparts. Complementary electrochemical experiments using cyclic voltammetry (CV), impedance spectroscopy (EIS) and the less known elimination voltammetry with linear scan (EVLS) reflect the performance superiority of TO electrodes with much lower polysiloxane content and free of impurities. High conductivity, low capacitive current along with favoured charge carrier transfer all promise a wide range of technological applications for the TO pencil material. [Display omitted]