(Invited) Challenges in Reversible Electrodeposition and Stripping of Lithium Peroxide for Li-Air Batteries (2020)

Thanks to a high theoretical energy density combined to a relatively high operation voltage around 3 Volts versus Li + /Li, the non-aqueous Li-Air battery is a good candidate for future electric cars with an increased driving range. In principle, this battery relies on the reversible electrochemical reaction between the metallic Li and the gaseous O 2 in presence of a non-aqueous electrolyte where Li + ions and dissolved O 2 molecules diffuse and react to form the ideal discharge product lithium peroxide Li 2 O 2 . However, this apparently simple reaction process appears to be more complicated when put into practice. Considering the Li-O 2 discharge process, there are two main models proposed in the literature to explain the Oxygen Reduction Reaction which were unified in a single mechanism process where Li 2 O 2 formation goes through a surface reaction or/and a solution reaction 1 , depending on system parameters such as the applied potential or the solvent properties. Using an electrochemical quartz crystal microbalance (EQCM) we studied the products formed in discharge as well as the reversibility of the reactions from a mass point of view during cycling. 2 Regarding the Li-O 2 charge process, the Li 2 O 2 decomposition occurring is a rather sluggish and incomplete process. A lot of efforts was made in this area by the research community, and several approaches were proposed to facilitate and fasten the Li 2 O 2 decomposition: the use of solid state catalyst of several kind (doped carbon, non-precious materials...) or soluble catalysts also called redox mediators, such as for example TTF 3 (tetrathiafulvalene), TEMPO 4 (2,2,6,6-tetramethylpiperidinyloxyl), Cobalt Bis(terpyridine) 5 , lithium iodide 6 (LiI). The mobile redox mediators, electron-hole transfer agents, aid the oxidation of Li 2 O 2 as has been reported previously. In our EQCM study we activated in situ the TTF and confirms its usefulness on the mass reversibility of the deposition/dissolution of Li 2 O 2 during cycling 2 . Later on, we performed a detailed study of the effect of LiI redox mediator on the formation and decomposition of Li 2 O 2 . 7 We showed that the solvent could drastically change the mechanism of decomposition during charge 8 . Finally, we will discuss the parameters able to influence the most the deposition and stripping of Li 2 O 2 in a non-aqueous medium. Reference s : 1 L. Johnson, C. Li, Z. Liu, Y. Chen, S. A. Freunberger, J. M. Tarascon, P. C. Ashok, B. B. Praveen, K. Dholakia, P. G. Bruce, Nature Chemistry , 6 , 1091 – 1099 (2014). 2 S. Schaltin, G. Vanhoutte, M. Wu, F. Bardé, J. Fransaer, Phys. Chem. Chem. Phys. , 17 , 12575 – 12586 (2015). 3 Y. Chen, S. A. Freunberger, Z. Peng, O. Fontaine, and P. G. Bruce, Nature Chemistry , 5 , 489 – 494 (2013). 4 Y. Hase, J. Seki, T. Shiga, F. Mizuno, H. Nishikoori, H. Iba, K. Takechi, Chem. Commun., 52 , 12151 – 12154 (2016). 5 Koffi P.C. Yao, J. T. Frith, S. Youssef Sayed, F. Bardé, J. R. Owen, Y. Shao-Horn, N. Garcia-Araez, J. Phys. Chem. C, 120 (30), 16290 – 16297 (2016). 6 Y. Qiao, S. Wu, Y. Sun, S. Guo, J. Yi, P. He, H. Zhou, ACS Energy Letters, 2, 8 , 1869 – 1878 (2017). 7 M. Tulodziecki, G.M. Leverick, C.V; Amanchukwu, Y. Katayama, D.G. Kwabi, F. Bardé, P. Hammond, Y. Shao-Horn, Energy Environ. Sci., 10 , 1828, (2017). 8 G. Leverick, M. Tułodziecki, R. Tatara, F. Bardé, Y. Shao-Horn, Joule , Vol. 3, Issue 4, 1106-1126, (2019).