Electrolyte contact changes nano-Li4Ti5O12 bulk properties – surface polarons enable Li+ equilibrium between bulk and electrolyte

Autor: Philipp Schleker, Cristina Grosu, Marc Paulus, Peter Jakes, Robert Schlögl, Rüdiger-A. Eichel, Christoph Scheurer, Josef Granwehr
Rok vydání: 2022
DOI: 10.26434/chemrxiv-2022-z7pnt
Popis: It is of general interest to combine the faradaic processes based high energy density of a battery with the non-faradaic processes based high power density of a capacitor in one cell. Surface area and functional groups of electrode materials strongly affect these properties, but a mechanistic explanation for the interplay between such process and how to balance them is largely missing. For the anode material Li4Ti5O12 (LTO), we suggest a polaron based mechanism that influences Li ion uptake and mobility. Electrolytes containing a lithium salt induce an observable change in the bulk NMR relaxation properties of LTO nano particles. The longitudinal 7Li NMR relaxation time of bulk LTO can change by almost an order of magnitude and, therefore, reacts very sensitively to the cation and its concentration in the surrounding electrolyte. The reversible effect is largely independent of the used anions and of potential anion decomposition products. It is concluded that lithium salt containing electrolytes increase the mobility of surface polarons. These polarons and additional lithium cations from the electrolyte can now diffuse through the bulk, induce the observed enhanced relaxation rate and enable the non-faradaic process. This picture of a Li+ ion equilibrium between electrolyte and solid may help with improving the charging properties of electrode materials.
Databáze: OpenAIRE