In Situ Insight into the Interfacial Dynamics in "Water-in-Salt" Electrolyte-Based Aqueous Zinc Batteries.

Water-in-salt (WIS) electrolyte is considered as one of most promising systems for aqueous zinc batteries (AZBs) due to its dendrite-free plating/stripping with nearly 100% Coulombic efficiency. However, the understanding of the interfacial mechanisms remains elusive, which is crucial for further improvements in battery performance. Herein, the interfacial processes of solid electrolyte interphase (SEI) formation and subsequent Zn plating/stripping are monitored by in situ atomic force microscopy and in situ optical microscopy. The live formation of uniform and compact LiF-rich SEI in WIS systems could induce the uniform hexagonal Zn deposition with preferential orientation growth in the (002) crystal plane, showing excellent plating/stripping reversibility. In contrast, the SEI formed in 1 m zinc bis(trifluoromethylsulfonyl)imide (Zn(TFSI)2 ) is uneven and rich in inert ZnO, adversely triggering the dendrite propagation and successive "dead" Zn accumulation in repeated deposition/dissolution cycles. This work provides an in-depth understanding of the relationship between SEI evolution and Zn-deposited behaviors in AZBs, possibly stimulating more research on rational composition design and structural optimization of solid/liquid interface for advanced rechargeable aqueous multivalent-ion batteries.

Designing and Demystifying the Lithium Metal Interface toward Highly Reversible Batteries.

Reversible lithium (Li) plating/stripping is essential for building practical high-energy-density batteries based on Li metal chemistry, which unfortunately remains a severe challenge. In this contribution, it is demonstrated that through the rational regulation of strong Li+ -anion coordination structures in a highly compatible low-polarity solvent, 2-methyl tetrahydrofuran, the Li plating/stripping assisted by a nucleation modulation procedure delivers a remarkably high average Coulombic efficiency under rather demanding conditions (99.7% and 99.5% under 1.0 mA cm-2 , 3.0 mAh cm-2 and 3.0 mA cm-2 , 3.0 mAh cm-2 , respectively). The exceedingly reversible cycling obtained herein is fundamentally correlated with the flattened Li deposition and minimized solid electrolyte interphase (SEI) generation/reconstruction in the customized condition, which notably restrains the growth rates of both dead Li0 (0.0120 mAh per cycle) and SEI-Li+ (0.0191 mAh per cycle) during consecutive cycles. Benefiting from the efficient Li plating/stripping manner, the assembled anode-free Cu|LiFePO4 (2.7 mAh cm-2 ) coin and pouch cells exhibit impressive capacity retention of 43.8% and 41.6% after 150 cycles, respectively, albeit with no optimization on the test conditions. This work provides guidelines into the targeted interfacial design of high-efficiency working Li anodes, aiming to pave the way for the practical deployment of high-energy-density Li metal batteries.