Journalartikel

Jahr der Veröffentlichung: 2014

Seiten: 15054-15064

Zeitschrift: Journal of the American Chemical Society

Bandnummer: 136

Heftnummer: 42

ISSN: 0002-7863

eISSN: 1520-5126

DOI Link: https://doi.org/10.1021/ja508400m

Verlag: American Chemical Society

Abstract: 
Nonaqueous Li-O-2 batteries are an intensively studied future energy storage technology because of their high theoretical energy density. However, a number of barriers prevent a practical application, and one of the major challenges is the reduction of the high charge overpotential: Whereas lithium peroxide (Li2O2) is formed during discharge at around 2.7 V (vs Li+/Li), its electrochemical decomposition during the charge process requires potentials up to 4.5 V. This high potential gap leads to a low round-trip efficiency of the cell, and more importantly, the high charge potential causes electrochemical decomposition of other cell constituents. Dissolved oxidation catalysts can act as mobile redox mediators (RM), which enable the oxidation of Li2O2 particles even without a direct electric contact to the positive electrode. Herein we show that the addition of 10 mM TEMPO (2,2,6,6-tetramethylpiperidinyloxyl), homogeneously dissolved in the electrolyte, provides a distinct reduction of the charging potentials by 500 mV. Moreover, TEMPO enables a significant enhancement of the cycling stability leading to a doubling of the cycle life. The efficiency of the TEMPO mediated catalysis was further investigated by a parallel monitoring of the cell pressure, which excludes a considerable contribution of a parasitic shuttle (i.e., internal ionic short circuit) to the anode during cycling. We prove the suitability of TEMPO by a systematic study of the relevant physical and chemical properties, i.e., its (electro)chemical stability, redox potential, diffusion coefficient and the influence on the oxygen solubility. Furthermore, the charging mechanisms of Li-O-2 cells with and without TEMPO were compared by combining different electrochemical and analytical techniques.

Harvard-Zitierstil: Bergner, B., Schürmann, A., Peppler, K., Garsuch, A. and Janek, J. (2014) TEMPO: A Mobile Catalyst for Rechargeable Li-O-2 Batteries, Journal of the American Chemical Society, 136(42), pp. 15054-15064. https://doi.org/10.1021/ja508400m

APA-Zitierstil: Bergner, B., Schürmann, A., Peppler, K., Garsuch, A., & Janek, J. (2014). TEMPO: A Mobile Catalyst for Rechargeable Li-O-2 Batteries. Journal of the American Chemical Society. 136(42), 15054-15064. https://doi.org/10.1021/ja508400m