Poly(vinylferrocene) as an Ionomer and Sulfur-Confining Additive for Lithium-Sulfur Batteries.

Abstract

Lithium-sulfur (Li-S) batteries are promising owing to their high energy density, environmental benignity, and low cost. Most of the commonly used binders in Li-S battery cathodes are inert and have no significant effect on the challenges of sulfur as a cathode material, such as the polysulfide shuttle effect, low ionic/electronic conductivity, and a sluggish redox reaction. In this work, we demonstrate the use of poly(vinylferrocene) (PvFc) as a binder additive that can effectively increase the ionic conductivity of the cathode and act as a sulfide-confining agent. Electrochemical tests performed with PvFc as part of the binder mixture used to cast the cathodes demonstrate an increase in rate capability and cycle life when compared to the baseline samples. Ionic conductivity measurements and X-ray photoelectron spectroscopy suggest that the π-cation molecular interaction between the cyclopentadienyl rings from ferrocene and Li+ behaves like an ion couple with ferrocene acting as a static, covalently bound acceptor of Li+ ions that enhances their mobility through the cathode. This coupled with the affinity between the ferrocenyl cations and the Li salt anions, which provides more distribution of counterions for Li+ movement and improves accessibility to the cathode S reservoir, make PvFc a promising ionomer for Li-S batteries. In addition, the π-cation bonds between cyclopentadienyl and lithium polysulfides produce a sulfide-confining effect that mitigates capacity fade through polysulfide dissolution. This work demonstrates an expansion in the utility of PvFc as a component in Li-ion batteries, which so far is mostly limited to use as an active material in organometallic batteries.