Combining Deep Eutectic Solvents with TEMPO‐based Polymer Electrodes: Influence of Molar Ratio on Electrode Performance

For sustainable energy storage, all-organic batteries based on redox-active polymers promise to become an alternative to lithium ion batteries. Yet, polymers contribute to the goal of an all-organic cell as electrodes or as solid electrolytes. Here, we replace the electrolyte with a deep eutectic solvent (DES) composed of sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) and N-methylacetamide (NMA), while using poly(2,2,6,6-tetramethylpiperidin-1-yl-oxyl methacrylate) (PTMA) as cathode. The successful combination of a DES with a polymer electrode is reported here for the first time. The electrochemical stability of PTMA electrodes in the DES at the eutectic molar ratio of 1 : 6 is comparable to conventional battery electrolytes. More viscous electrolytes with higher salt concentration can hinder cycling at high rates. Lower salt concentration leads to decreasing capacities and faster decomposition. The eutectic mixture of 1 : 6 is best suited uniting high stability and moderate viscosity

Melting of a colloidal crystal

A melting transition for a system of hard spheres interacting by a repulsive Yukawa potential of DLVO form is studied. To find the location of the phase boundary, we propose a simple theory to calculate the free energies for the coexisting liquid and solid. The free energy for the liquid phase is approximated by a virial expansion. The free energy of the crystalline phase is calculated in the spirit of the Lenard-Jonnes and Devonshire (LJD) theory. The phase boundary is found by equating the pressures and chemical potentials of the coexisting phases. When the approximation leading to the equation of state for the liquid breakes down, the first order transition line is also obtained by applying the Lindemann criterion to the solid phase. Our results are then compared with the Monte Carlo simulations.Comment: 7 pages, Revtex (using twocolumn style), four figures and postscript file. Submitted to Physica

Effective charge versus bare charge for colloids in the infinite dilution limit

We propose an analytical approximation for the dependence of the effective charge on the bare charge for spherical and cylindrical macro-ions as a function of the size of the colloid and salt content, for the situation of a unique colloid immersed in a sea of electrolyte (where the definition of an effective charge is non ambiguous). Our approach is based on the Poisson-Boltzmann (PB) mean-field theory. Mathematically speaking, our estimate is asymptotically exact in the limit $\kappa a\gg 1$, where $a$ is the radius of the colloid and $\kappa$ the inverse screening length. In practice, a careful comparison with effective charges parameters obtained by numerically solving the full non-linear PB theory proves that it is good down to $\kappa a\sim 1$. This is precisely the limit appropriate to treat colloidal suspensions. A particular emphasis is put on the range of parameters suitable to describe both single and double strand DNA molecules under physiological conditions.Comment: Proceedings of the International Conference on Strongly Coupled Coulomb Systems, Santa Fe (2002

Diffusion and conduction in a salt-free colloidal suspension via molecular dynamics simulations

Molecular dynamics (MD) simulations are used to determine the diffusion coefficients, electrophoretic mobilities and electrical conductivity of a charged colloidal suspension in the salt-free regime as a function of the colloid charge. The behavior of the colloidal particles' diffusion constant can be well understood in terms of two coupled effects: counterion 'condensation' and slowdown due to the relaxation effect. We find that the conductivity exhibits a maximum which approximately separates the regimes of counterion-dominated and colloid-dominated conduction. We analyze the electrophoretic mobilities and the conductivity in terms of commonly employed assumptions about the role of "free" and "condensed" counterions, and discuss different interpretations of this approach.Comment: 10 pages, 4 figure

Combining Deep Eutectic Solvents with TEMPO-based Polymer Electrodes: Influence of Molar Ratio on Electrode Performance

For sustainable storage of electrical energy, all-organic batteries based on redox-active polymers promise to become an alternative to conventional lithium ion batteries. Yet, polymers can only contribute to the goal of an all-organic cell as electrodes or as solid electrolytes. Here, we replace the electrolyte with a sustainable deep eutectic solvent (DES) composed of sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) and N-methylacetamide (NMA), while using poly(2,2,6,6-tetramethylpiperidin-1-yl-oxyl methacrylate) (PTMA) as cathode. The successful combination of a DES with a polymer electrode is reported here for the first time. The electrochemical stability of PTMA electrodes in the DES at the eutectic molar ratio of 1:6 is comparable to conventional battery electrolytes. More viscous electrolytes with higher salt concentrations can hinder charging and discharging at high rates. Lower salt concentrations on the other hand lead to decreasing capacities and faster decomposition. The used eutectic mixture of 1:6 is best suited uniting high stability and moderate viscosity