Several measures for mitigating manganese dissolution or its consequences have been reported over the years in the literature,1,2 including elemental substitutions (doping) in the lattice of the positive electrode active material,3 surface coatings4 and the application an inorganic barrier coatings onto electrodes by atomic layer deposition (ALD),5 passivating additives in the electrolyte solution,6 and the reduction of the state-of-charge swing during battery operation. Unfortunately, no single mitigation measure turned out 100% successfully so far, i.e., without negatively affecting other properties of the LIB such as energy density and internal resistance.
A different approach, that of using a separator containing multifunctional (manganese ion chelating, HF scavenging and alkali metal dispensing) material, may avoid the above described previously mentioned drawbacks.7-9 Herein we review recent progress on our understanding of Mn species in electrolyte solutions and on a mitigation measure first proposed by Tarascon and coworkers in 1999,7 namely chelation of TM cations. Our focus is a practicable, drop-in technical solution, based on multi-functional materials placed in the inter-electrode space. Such materials can trap Mn cations, scavenge HF and dispense sacrificial Li+ ions,8-10 with significant benefits for LIBs performance: increased capacity retention during operation at room and above-ambient temperatures, robust (more electronically insulating) solid-electrolyte interfaces, as well as reduced charge transfer and film resistances at both negative and positive electrode surfaces.
1. G. Amatucci, A. Du Pasquier, A. Blyr, T. Zheng, and J.-M. Tarascon, Electrochim. Acta 45 (1999) 255-271.
2. Y. Xia and M. Yoshio, Ch. 12 in Lithium Batteries: Science and Technology, G. A. Nazri and G. Pistoia (editors), Springer Verlag US, 2003, ISBN 978-1-4020-7628-2, DOI: 10.1007/978-0-387-92675-9.
3. M. Choi and A. Manthiram, J. Electrochem. Soc. 153 (2006) A1760-A1764.
4. C. Li, H. P. Zhang, L. J. Fu, H. Liu, Y. P. Wu, E. Rahm, R. Holze, and H. Q. Wu, Electrochim. Acta 51 (2006) 3872-2883.
5. Y. S. Jung, A. S. Cavanagh, A. C. Dillon, M. D. Groner, S. M. George, and S.-H. Lee, J. Electrochem. Soc. 157 (2010) A75-A81.
6. Y. S. Jung, A. S. Cavanagh, R. A. Leah, S. H. Kang, A. C. Dillon, M. D. Groner, S. M. George, and Y.-H. Lee, Adv. Mater. 22 (2010) 2172-2176.
7. G. Amatucci, A. Du Pasquier, A. Blyr, T. Zheng, and J. Tarascon, Electrochim. Acta, 45, (1999) 255-271.
8. A. Banerjee, B. Ziv, Y. Shilina, S. Luski, D. Aurbach, and I. C. Halalay, J. Electrochem. Soc. 163 (2016) A1083-A1094.
9. A. Banerjee, B. Ziv, Y. Shilina, S. Luski, D. Aurbach, and I. C. Halalay, Adv. Energy Mat. article 1601556 (2016)
10. A. Banerjee, B. Ziv, S. Luski, D. Aurbach, and I. C. Halalay, J. Power Sources, 2017, (accepted for publication.)