Search

Aqueous rechargeable batteries based on aluminum chemistry have become the focus of immense research interest owing to their earth abundance, low cost, and the higher theoretical volumetric energy density of this element compared to lithium-ion batteries. Efforts to harness this huge potential have been hindered by the narrow potential window of water and by passivating effects of the high-electrical band-gap aluminum oxide film. Herein, we report a high-performing aqueous aluminum-ion battery (AIB), which is constructed using a Zn-supported Al alloy, an aluminum bis(trifluoromethanesulfonyl)imide (Al[TFSI] 3 ) electrolyte, and a MnO 2 cathode. The use of Al[TFSI] 3 significantly extends the voltage window of the electrolyte and enables the cell to access Al 3+ /Al electrochemistry, while the use of Zn-Al alloy mitigates the issue of surface passivation. The Zn-Al alloy, which is produced by in situ electrochemical deposition, obtained from Al[TFSI] 3 showed excellent long-term reversibility for Al electrochemistry and displays the highest performance in AIB when compared to the response obtained in Al 2 (SO 4 ) 3 or aluminum trifluoromethanesulfonate electrolyte. AIB cells constructed using the Zn-Al|Al[TFSI] 3 |MnO 2 combination achieved a record discharge voltage plateau of 1.75 V and a specific capacity of 450 mAh g -1 without significant capacity fade after 400 cycles. These findings will promote the development of energy-dense aqueous AIBs.

The development of rechargeable Zinc-ion batteries (ZIBs) has been hindered by the lack of efficient cathode materials due to the strong binding of divalent zinc ions with the host lattice. Herein, we report a strategy that eliminates the participation of Zn 2+ within the cathode chemistry. The approach involves the use of composite cathode materials that contain Zn halides (ZnCl 2 , ZnBr 2 , and ZnI 2 ) and carbon (graphite or activated carbon), where the halide ions act both as charge carriers and redox centers while using a Zn 2+ -conducting water-in-salt gel electrolyte. The use of graphite in the composite electrode produced batterylike behavior, where the voltage plateau was related to the standard potential of the halogen species. When activated carbon was used in the composite, however, the cell acted as a hybrid Zn-ion capacitor due to the fast, reversible halide ion electrosorption/desorption in the carbon pores. The ZnX 2 -activated carbon composite delivers a capacity of over 400 mAh g -1 and cell energy density of 140 Wh kg -1 while retaining over 95% of its capacity after 500 cycles. The halogen reaction mechanism has been elucidated using combinations of electrochemical and in situ spectroscopic techniques.

The current state-of-the-art positive electrode material for chloroaluminate ion batteries (AIBs) or dual-ion batteries (DIBs) is highly crystalline graphite; however, the rate capability of this material at high discharge currents is significantly reduced by the modest conductivity of graphite. This limitation is addressed through the use of graphene-based positive electrodes, which can improve the rate capability of these batteries due to their higher conductivity. However, conventional methods of graphene production induce a significant number of defects, which impair the performance of AIBs and DIBs. Herein, we report the use of a defect-free graphene positive electrode, which was produced using the electrochemical exfoliation of graphite in an aqueous solution with the aid of Co 2+ as an antioxidant. The Co-treated graphene electrode achieved high capacities of 150 mAh g -1 in DIBs and 130 mAh g -1 in AIBs with high rate capability for both batteries. The charge-discharge mechanism of the batteries is examined using in situ Raman spectroscopy, and the results revealed that the intercalation density of [AlCl 4 ] - or [PF 6 ] - increased from a dilute staging index graphite intercalation compound (GIC) to a stage 1 GIC within the operating voltage window. The simple production method of high-quality graphene in conjunction with its high performance in DIBs should enable the use of graphene for DIB technologies.