Exploration of novel Li-Sn compounds at ambient and moderately high pressure for high-performance Li-ion batteries, Dr Priya Johari, Assistant Professor

Dr Priya Johari, Assistant Professor, Department of Physics and her Ph.D. student, Mr. Raja Sen, have recently published a paper in ACS Applied Materials & Interfaces, titled: “Understanding the Lithiation of the Sn Anode for High-Performance Li-ion Batteries with Exploration of Novel Li-Sn Compounds at Ambient and Moderately High Pressure”. Besides having higher gravimetric capacity (990 mAhg-1 for Li17Sn4) than the conventionally used graphite anode (372 mAhg-1) and other advantages over its neighbors in group IV, Sn is still far from being used as an anode in commercial Li-ion batteries because of huge irreversible capacity loss, particle fracture, and electrochemical pulverization due to drastic volume expansion and elastic softening of the Sn anode on lithiation. It can, however, be overcome with the help of void space engineering by using a LixSn phase as the pre-lithiated anode, where an optimal value for x is desired. Currently, Li4.25Sn is known as the most lithiated Li−Sn compound, but recent studies have shown that at high pressure, several exotic and unusual stoichiometries can be obtained that may even survive decompression from high-to-ambient pressure with improved mechanical properties. With a belief that hydrostatic pressure may help in realizing Li-richer (x > 4.25) Li−Sn compounds as well, Dr. Johari and her student performed extensive calculations using an evolutionary algorithm and density functional theory to explore all stable and low-energy metastable Li−Sn compositions at pressures ranging from 1 atm to 20 GPa. Besides the experimentally known Li−Sn compounds, their study reveals the existence of five unreported stoichiometries (Li8Sn3, Li3Sn1, Li4Sn1, Li5Sn1, and Li7Sn1) and their associated crystal structures at ambient and high pressure. Although Li8Sn3 has been identified as one of the most stable Li−Sn compound in the entire pressure range (1 atm− 20 GPa) with R3̅m symmetry, the Li-rich compounds like Li3Sn1-P2/m, Li4Sn1-R3̅m, Li5Sn1-C2/m, and Li7Sn1-C2/m are predicted to be metastable at ambient pressure and found to get thermodynamically stable at high pressure. The discovery of Li5Sn1 and Li7Sn1 opens up the possibility to integrate them as a pre-lithiated anode for efficiently preventing electrochemical pulverization, as compared to the experimentally known highest lithiated compound, Li17Sn4. The study by Dr. Johari and her student has not only enriched the Li−Sn chemistry, in general, but it also helps in improving the understanding of the reaction mechanism in Li−Sn batteries, in particular, and guiding a route to improve the performance of Li-ion batteries through synthesis of Li-rich phases.