Yunus Karatas

Salt-in-Polymer Electrolytes for Lithium Ion Batteries Based on Organo-Functionalized Polyphosphazenes and Polysiloxanes

Abstract An overview is given on polymer electrolytes based on organo-functionalized polyphosphazenes and polysiloxanes. Chemical and electrochemical properties are discussed with respect to the synthesis, the choice of side groups and the goal of obtaining membranes and thin films that combine high ionic conductivity and mechanical stability. Electrochemical stability, concentration polarization and the role of transference numbers are discussed with respect to possible applications in lithium batteries. It is shown that the ionic conductivities of salt-in-polymer membranes without additives and plasticizers are limited to maximum conductivities around 10-4S/cm. Nevertheless, a straightforward strategy based on additives can increase the conductivities to at least 10-3S/cm and maybe further. In this context, the future role of polymers for safe, alternative electrolytes in lithium batteries will benefit from concepts based on polymeric gels, composites and hybrid materials. Presently developed polymer electrolytes with oligoether sidechains are electrochemically stable in the potential range 0–4.5V (vs. Li/Li+ reference).

Nanocomposites based on borate esters as improved lithium-ion electrolytes

Borate esters with different lengths of ethyleneoxy units were investigated as electrolyte solvents for lithium salts such as lithium triflate, perchlorate, bis(trifluoromethanesulfonyl)imide, bis(pentafluoroethanesulfonyl)imide and bis(oxalato)borate. The ionic conductivity of the salt solutions was measured to be of the order of 10−3 to 10−4 S cm−1 at room temperature. Transference number measurements for the borate ester–lithium perchlorate system indicated roughly equal contributions of cations and anions to the total conductivity, while the borate ester–lithium bis(oxalato)borate showed predominant anionic conductivity. Nanocomposite electrolytes were prepared by heterogeneous doping of the borate esters with silica. Composites with 10 nm silica particles exhibited low-viscous electrolyte behavior with a clear but modest conductivity enhancement at very low volume fractions of silica and a depression of the conductivity value at higher volume fractions. In the case of fumed silica (7 nm) the nanocomposites had at a sufficiently high volume fraction and a jelly, transparent appearance with the favorable mechanical properties of a high-viscous semi-solid without noteworthy decrease in the Li ion conductivity. In particular the last material with its combination of favourable electrical, mechanical and optical properties, promises to be a viable candidate for various applications (Li-based batteries, solar cells).