Preparation of a Homologous Series of Tetraalkylammonium Graphite Intercalation Compounds

Abstract

Graphite intercalation compounds (GICs) of a series of symmetric or asymmetric tetraalkylammonium (TAA) intercalates are obtained from stage-1 [Na(en)1.0]C15 via cation exchange. The prepared dull-black TAA-GICs contain either flattened monolayer or bilayer galleries, with significant cointercalation of the dimethylsulfoxide (DMSO) solvent in the bilayer galleries. The TAA-GIC products obtained are characterized by X-ray diffraction and related structural modeling, compositional analyses, and Raman spectroscopy. [(C4H9)4N]C43 is obtained as a pure stage-1 GIC with the flattened monolayer structure. The larger symmetric TAA cations, (C6H13)4N, (C7H15)4N, (C8H17)4N, and the asymmetric TAA cations, (C12H25)(CH3)3N, (C18H37)(CH3)3N, (C18H37)2(CH3)2N, all form pure stage-1 GICs with flattened bilayer conformations. Thermogravimetric analyses combined with mass spectrometry and elemental analyses indicate the presence of ∼1-2 DMSO cointercalates per bilayer cation. The intercalate layers in these TAA-GICs have expansions along the stacking direction of ∼0.40 nm. Raman data confirm the low graphene sheet charge densities in the obtained TAA-GICs.