Optimization of an Artificial Solid Electrolyte Interphase Formed on an Aluminum Anode and Its Application in Rechargeable Aqueous Aluminum Batteries.

Electrochemical cells that incorporate aluminum (Al) as the active material have become increasingly popular due to the advantages of high energy density, cost-effectiveness, and superior safety features. Despite the progress made by research groups in developing rechargeable Al//MxOy (M = Mn, V, etc.) cells using an aqueous Al trifluoromethanesulfonate-based electrolyte, the reactions occurring at the Al anode are still not fully understood. In this study, we explore the artificial solid electrolyte interphase (ASEI) on the Al anode by soaking it in AlCl3/urea ionic liquid. Surprisingly, our findings reveal that the ASEI actually promotes the corrosion of Al by providing chloride anions rather than facilitating the transport of Al3+ ions during charge/discharge cycles. Importantly, the ASEI significantly enhances the cycling stability and activity of Al cells. The primary reactions occurring at the Al anode during the charge/discharge cycle were determined to be irreversible oxidation and gas evolution. Furthermore, we demonstrate the successful realization of urea-treated Al (UTAl)//AlxMnO2 cells (discharge operating voltage of ∼1.45 V and specific capacity of 280 mAh/g), providing a platform to investigate the underlying mechanisms of these cells further. Overall, our work highlights the importance of ASEI in controlling the corrosion of Al in aqueous electrolytes, emphasizing the need for the further development of electrolytic materials that facilitate the transport of Al3+ ions in rechargeable Al batteries.

Understanding the Oxidation and Reduction Reactions of Sulfur in Rechargeable Aluminum-Sulfur Batteries with Deep Eutectic Solvent and Ionic Liquid Electrolytes.

Al-based batteries are promising next-generation rechargeable batteries owing to the abundance of raw materials and their high potential energy density. The Al-S system has attracted considerable attention because of its high energy density and low cost. However, its low discharge voltage plateau (0.6-1.2 V) hampers its practical application. Herein, eight ionic liquids or deep eutectic solvents were studied as electrolyte candidates for an Al-S cell. This was the first study to demonstrate that an Al-S cell based on an AlCl3 /acetamide electrolyte (1.3 molar ratio) showed high discharge voltage plateaus (1.65-1.95 V) and a charging cut-off voltage of 2.5 V in Al-S cells. An Al-S cell of 0.33 mAh capacity with the AlCl3 /acetamide electrolyte successfully lit up a red LED (forward voltage 1.6-2.0 V) for around 2 h. This work may help in promoting the development of high-performance and low-cost Al-S cells.

Aqueous Aluminum Cells: Mechanisms of Aluminum Anode Reactions and Role of the Artificial Solid Electrolyte Interphase.

Electrochemical cells with aluminum (Al) as the active material offer the benefits of high energy density, low cost, and high safety. Although several research groups have assembled rechargeable Al//MxOy (M = Mn, V, etc) cells with 2 m aqueous Al trifluoromethanesulfonate as an electrolyte and demonstrated the importance of the artificial solid electrolyte interphase (ASEI) on the Al anode for realizing high rechargeable capacity, the reactions of the Al anode in such cells remain underexplored. Herein, we investigate the effects of the ASEI on the charge/discharge cycling stability and activity of Al cells with the abovementioned aqueous electrolyte and reveal that this interphase provides chloride anions to induce the corrosion of Al rather than to support the transportation of Al3+ ions during charge/discharge. Regardless of the ASEI presence/absence, the main reactions at the Al anode during charge/discharge cycling are identified as oxidation and gas evolution, which suggests that the reduction of Al in the employed electrolyte is irreversible. The simple introduction of chloride anions (e.g., 0.15 m NaCl) into the electrolyte is shown to allow the realization of an Al//MnO2 cell with superior performance (discharge working voltage ≈ 1.5 V and specific capacity = 250 mA h/g). Thus, the present work unveils the mechanisms of reactions occurring at the Al anode of aqueous electrolyte Al cells to support their further development.

Low-Cost Gel Polymer Electrolyte for High-Performance Aluminum-Ion Batteries.

The classical AlCl3/imidazole-chloride-salt ionic liquid electrolytes are expensive, corrosive, and environmentally sensitive, which limit the large-scale application of aluminum-ion batteries. Herein, a gel polymer electrolyte is prepared through a facile process using a low-cost AlCl3/Et3NHCl ionic liquid as the plasticizer and polyamide as the polymer matrix. The gel polymer electrolyte achieves a decent ionic conductivity of 3.86 × 10-3 S cm-1, a wide electrochemical stability window of 2.6 V (vs Al), and long-term interfacial stability at room temperature. The assembled Al//graphite battery delivers considerable rate capability and excellent cycling performance. Besides, the gel polymer electrolyte can alleviate both moisture sensitivity and leakage corrosion issues owing to the full encapsulation of the ionic liquid by polyamide polymeric matrix. The gel polymer electrolyte should offer great potential for aluminum-ion battery applications.

Electrochemical Performance of Graphitic Multi-walled Carbon Nanotubes with Different Aspect Ratios as Cathode Materials for Aluminum-ion Batteries.

Graphitic multi-walled carbon nanotubes (MWCNTs) can function as high-performance cathode materials for rechargeable Al-ion batteries with well-defined discharging plateaus and reasonable charge/discharge C-rates. However, the main intercalation/deintercalation or adsorption/desorption path of AlCl4- anions into or onto G-MWCNTs has not been elucidated. Herein, we used battery cells comprised of G-MWCNTs with different aspect ratios, Al metal, and AlCl3/1-ethyl-3-methylimidazolium chloride ionic liquid as the cathode, anode, and electrolyte, respectively. The electrochemical performance of the Al||G-MWCNT cell increased as the aspect ratio of the G-MWCNT cathode increased (i. e., longer and thinner). The degree of defects of the G-MWCNTs was similar (0.15-0.22); hence, the results confirm that the main and alternate paths for the AlCl4- intercalation/de-intercalation or adsorption/desorption into/from or onto/from the G-MWCNT are the basal and edge planes, respectively. The step-like structures of defects on the basal plane provide the main reaction site for AlCl4- anions.