High transference number (t +) electrolytes have attracted recent interest as a means to improve the energy density and rate capabilities of current lithium ion batteries. Here the viscosity and transport properties of a sulfonated polysulfone/polyethylene glycol copolymer that displays both high t + and high conductivity when dissolved in dimethylsulfoxide (DMSO) are investigated for the first time in a battery-relevant solvent of nearly equivalent dielectric constant: mixed ethylene carbonate (EC) / dimethyl carbonate (DMC). The addition of a binary salt to each solution is investigated as a means to improve conductivity, and the diffusion coefficient of each species is tracked by pulse field gradient nuclear magnetic resonance (PFG-NMR). Through the 7 Li NMR peak width and quantum chemistry calculations of the dissociation constant, it is shown that although the two solvent systems have nearly equivalent dielectric constants, the conductivity and transference number of the EC/DMC solutions are significantly lower as a result of poor dissociation of the sulfonate group on the polymer backbone. These results are the first study of polyelectrolyte properties in a battery-relevant solvent, and clearly demonstrate the need to consider solvent properties other than the dielectric constant in the design of these electrolytes.

Nonaqueous polyelectrolyte solutions have recently been proposed as potential battery electrolytes due to their unique ability to tune the mobility of the anion relative to that of the electrochemically active lithium ion. This could potentially be used to study the effect of concentration polarization during battery charge, a major limiting factor in achieving fast charge rates that is caused by high anion mobility. An important consideration in the design of polyelectrolyte solutions for battery applications is the solubility of the polymer in battery-relevant carbonate blend solvents. Little is understood from a transport perspective, however, about the importance of designing the polymer to be solvophillic or if it is sufficient to obtain solubility through the incorporation of appended ions alone (as with polystyrene sulfonate in water). Using a model polysulfone-based system without added salt, we investigate the conductivity, viscosity, and diffusion of polyelectrolyte solutions over a range of concentrations and molecular weights in dimethyl sulfoxide (DMSO) and water. In both solvents, sulfonated polysulfone is readily soluble and the charged group is known to dissociate, but the neutral backbone polymer is only soluble in DMSO. We find marked differences in the transport behavior of polymer solutions prepared from the two solvents, particularly at high concentrations. Comparing this transport behavior to that of the monomer in solution demonstrates a larger decrease in lithium motion in DMSO than in water, even though the bulk viscosity in water increases far more rapidly. This study sheds light on the important parameters for optimizing polyelectrolyte solution transport in different solvents.

In this work, evidence for ligand formation between Sn and Bi is provided utilizing time-resolved X-ray Absorption and 119Sn Mӧssbauer spectroscopy during the colloidal synthesis of Bi metal nanoparticles (NP)...