Understanding Electrochemical Reaction Mechanisms and Properties of Rechargeable Aluminum-Sulfur and Aluminum-Selenium Batteries
Authors: Jay Rahul , Jadhav Ankur , Messinger Robert J. 
Published: December 2020

The continual rise in global energy demands coupled with recent incremental advances in the cost and energy density of lithium-ion batteries have given researchers an impetus to investigate high-energy-density batteries such as those that use multivalent-ions. Rechargeable Al metal batteries have recently garnered significant interest due to its low cost, earth abundance, inherent safety, and high volumetric (8040 mAh cm -3) and gravimetric (2980 mAh g -1) capacities due to the trivalent nature of Al3+ ions (3-electron redox). Commercialization of rechargeable aluminum battery systems has been limited, however, due to the small number of (i) electrolytes that enable reversible electrodeposition of Al metal at room temperature and (ii) positive electrode materials that are compatible with the electrolytes while providing high capacity and cycle life. Sulfur (S) and selenium (Se) are promising positive electrode materials for rechargeable battery systems as they exhibit very high specific capacities during electrochemical conversion reactions.
Sulfur is a very low-cost material due to its earth abundance and generation as a byproduct of the petroleum industry, while it can provide a very high specific capacity up to 1675 mAh g-1. Commercialization of battery systems with sulfur electrodes has been hindered due to its low electrical conductivity, high volume expansion during galvanostatic cycling, and deleterious polysulfide shuttle reactions during charge and discharge1-3. Selenium, like sulfur, is also a chalcogen and is expected to exhibit similar electrochemical reactions. Although Se is a heavier element and consequently exhibits lower specific capacity (675 mAh g-1), it possesses significantly higher electronic conductivity compared to sulfur4 that would be beneficial in mitigating key challenges that faces sulfur electrodes, such as low active material utilization and high charge transfer overpotentials during galvanostatic cycling. To date, there are few reports of Al-S2,3, and Al-Se4,5 systems. There is no clear consensus on the electrochemical reaction mechanism during the charge/discharge process, while capacity fade plagues both systems during galvanostatic cycling.
Here, aluminum-sulfur (Al-S) and aluminum-selenium (Al-Se) cells were investigated with a chloroaluminate ionic liquid electrolyte, AlCl3:[EMIm][Cl] (molar ratio of 1.5:1), whose electrochemical reaction mechanisms and ensuing reaction products were analyzed via a combination of bulk (XRD, NMR) and surface (XPS) analyzation techniques. Electrochemical experiments for Al-S batteries showed high initial capacities close to 1200 mAh g-1, which exhibited a inverse correlation with galvanostatic cycling rate. For Al-S batteries a higher capacity was observed upon charge, compared to discharge, pointing towards either an unwanted side reaction or polysulfide-shuttle-like behavior. This behavior occurred predominately at low current densities and affected the reversibility of the system. For the Al-Se batteries, the two different reaction mechanisms that have been previously reported were found to be dependent on (i) the applied current density and (ii) the crystallinity of the active material, as shown by XRD. We demonstrate that, with appropriate cycling conditions, both reaction mechanisms can occur during a single charge/discharge step, thus significantly increasing the capacity and the electrochemical window of the Al-Se cell. A significant capacity fade was also observed over a course of multiple cycles showing similar behavior compared to Al-S cells.
To understand the reaction mechanisms of Al-S and Al-Se batteries at a molecular level, solid-state and liquid-state 27Al NMR and 77Se NMR measurements (on Al-Se systems) were acquired on the electrodes and electrolyte at different states-of-charge, respectively. XPS was also performed on cycled chalcogen electrodes to understand surface compositions. The combination of electrochemical, spectroscopic, and X-ray diffraction data yield insights into the reaction mechanisms and products, including the aluminum coordination environments and relative populations in these environments. This work establishes the potential of conversion-type aluminum-chalcogen batteries as high-energy-density energy storage systems and highlights the importance that molecular-level analytical tools like NMR spectroscopy can have in clarifying electrochemical mechanisms in emerging electrochemical systems.
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