Binding Energy and Work Function of Organic Electrode Materials Phenanthraquinone, Pyromellitic Dianhydride and Their Derivatives Adsorbed on Graphene

Abstract

Electroactive organic compounds are a novel group of green cathode materials for rechargeable metal-ion batteries. However, the organic battery life is short because the organic compounds can be dissolved by nonaqueous electrolytes. Here a comparative investigation of phenanthraquinone (PQ), pyromellitic dianhydride (PMDA) and their derivatives, i.e., benzo[1,2-b:4,3-b']difuran-4,5-dione (BDFD), benzo[1,2-b:4,3-b']dithiophene-4,5-quinone (BDTQ), 3,8-phenanthroline-5,6-dione (PAD), pyromellitic dithioanhydride (PMDT), pyromellitic diimide (PMDI) and 1,4,5,8-anthracenetetrone (ATO), adsorbed on graphene is performed using a density functional theory (DFT) with a van der Waals (vdW) dispersion-correction. The computed results show a strong physisorption with the binding energies between 1.10 and 1.56 eV. A sequence of the calculated binding energies from weak to strong is found to be BDFD < BDTQ < PMDA ≤ PMDI < PMDT < PQ < PAD < ATO. The formation of stable organic molecule-graphene nanocomposites can prevent the dissolution of the eight organic compounds in nonaqueous electrolyte and hence improve cycling performance of batteries. In addition, the work functions for the nanocomposites are found to be strongly affected by the work function of each organic compound. To understand the DFT results, a novel simple expression is proposed to predict the work function of the nanocomposites from the interfacial dipole and the work functions of the isolated graphene nanosheet and organic molecules. The predicted work functions for the nanocomposites from the new equation agree quite well with the values calculated from the vdW dispersion-corrected DFT.

A rechargeable lithium/quinone battery using a commercial polymer electrolyte

“…Finally, improvements of this technology are expected thanks to a better confinement of molecules within the cathode compartment. For instance, addition of graphene nanosheets during the processing of the composite electrode could be an option to further prevent the diffusion phenomenon because strong π-π stacking interactions (physisorption) are expected with aromatic structures such as quinones [17].…”

Review—Advanced Carbon-Supported Organic Electrode Materials for Lithium (Sodium)-Ion Batteries

“…This could be ascribed to higher electron affinities of the former two molecules, which would lead to stronger interaction with the graphene support (Figure 7b). In fact, the interaction between organic molecules and graphene could be predicted by the calculations based on density functional theory (DFT), 109,110 implying that some of the electrochemical properties of organic electrode materials could be predictably engineered with delicate molecular modification.…”

Removal of Cr(VI) by 3D TiO 2 -graphene hydrogel via adsorption enriched with photocatalytic reduction

“…It is carcinogenic and thus is a threat to human healthy [1] . An rich array of physical and chemical approaches including ion exchange [2], chemical precipitation [3], electro-reduction [4] , and membrane separation [5] have been developed for removing chromium from industrial waste. However, most of these methods suffer from drawbacks such as low efficiency, high cost, generation of secondary pollution, and incapability of removing trace contaminants, thereby limiting practical applications.…”