Swelling Effects on the Conductivity of Graphene/PSS/PAH Composites

Graphene/poly-(sodium-4-styrene sulfonate)(PSS)/poly-(allylamine hydrochloride) (PAH) composite is a frequently adopted system for fabricating polyelectrolyte multilayer films. Swelling is the bottleneck limiting its applications, and its effects on the conductivity is still controversial. Herein, we report successful swelling of a graphene/PSS/PAH composite in a vapor atmosphere, and the relation with the mass fraction of water is uncovered. The composite was prepared via a layer-by-layer assembly technique and systematically characterized. The results indicated that the average thickness for each bilayer was about 0.95 nm. The hardness and modulus were 2.5 ± 0.2 and 68 ± 5 GPa, respectively, and both were independent of thickness. The sheet resistance decreased slightly with the prolongation of immersion time, but was distinct from that of the water mass fraction. It reduced from 2.44 × 10⁵ to 2.34 × 10⁵ ohm/sq, and the change accelerated as the water mass fraction rose, especially when it was larger than 5%. This could be attributing to the lubrication effect of the water molecules, which sped up the migration of charged groups in the polyelectrolytes. Moreover, molecular dynamics simulations confirmed that a microphase separation occurred when the fraction reached an extreme value owing to the dominated interaction between PSS and PAH. These results provide support for the structural stability of this composite material and its applications in devices.