Rechargeable Seawater-Based Chloride-Ion Batteries Enabled by Covalent Surface Chemistry in MXenes.

Rechargeable aqueous chloride-ion batteries (ACIBs) using Cl- ions as charge carriers represent a promising energy-storage technology, especially when natural seawater is introduced as the electrolyte, which can bring remarkable advantages in terms of cost-effectiveness, safety, and environmental sustainability. However, the implementation of this technology is hindered by the scarcity of electrodes capable of reversible chloride-anion storage. Here, we show that a Ti3C2Clx MXene with Cl surface terminations enables reversible Cl- ion storage in aqueous electrolytes. Further, we developed seawater-based ACIBs that show a high specific capacity and an exceptionally long lifespan (40000 cycles, more than 1 year) in natural seawater electrolyte. The pouch-type cells achieve a high energy density (50 Wh Lcell-1) and maintain stable performance across a broad temperature range (-20 to 50 °C). Our investigations reveal that the covalent interaction between Cl- ions and Cl-terminated MXene facilitates Cl- ion intercalation into the MXene interlayer, promoting rapid ion migration with a low energy barrier (0.10 eV). Moreover, this MXene variant also enables the reversible storage of Br- ions in an aqueous electrolyte with a long cycle life. This study may advance the design of anion storage electrodes and enable the development of sustainable aqueous batteries.

Interlayer Engineering of Layered Materials for Efficient Ion Separation and Storage.

Layered materials are characterized by strong in-plane covalent chemical bonds within each atomic layer and weak out-of-plane van der Waals (vdW) interactions between adjacent layers. The non-bonding nature between neighboring layers naturally results in a vdW gap, which enables the insertion of guest species into the interlayer gap. Rational design and regulation of interlayer nanochannels are crucial for converting these layered materials and their 2D derivatives into ion separation membranes or battery electrodes. Herein, based on the latest progress in layered materials and their derivative nanosheets, various interlayer engineering methods are briefly introduced, along with the effects of intercalated species on the crystal structure and interlayer coupling of the host layered materials. Their applications in the ion separation and energy storage fields are then summarized, with a focus on interlayer engineering to improve selective ion transport and ion storage performance. Finally, future research opportunities and challenges in this emerging field are comprehensively discussed.