Lithium Bis(oxalate)borate Additive for Self‐repairing Zincophilic Solid Electrolyte Interphases towards Ultrahigh‐rate and Ultra‐stable Zinc Anodes

Abstract

The artificial solid electrolyte interphase (SEI) plays a pivotal role in Zn anode stabilization but its long‐term effectiveness at high rates is still challenged. Herein, to achieve superior long‐life and high‐rate Zn anode, an exquisite electrolyte additive, lithium bis(oxalate)borate (LiBOB), is proposed to in situ derive a highly Zn2+‐conductive SEI and to dynamically patrol its cycling‐initiated defects. Profiting from the as‐constructed real‐time, automatic SEI repairing mechanism, the Zn anode can be cycled with distinct reversibility over 1800 h at an ultrahigh current density of 50 mA cm−2, presenting a record‐high cumulative capacity up to 45 Ah cm−2. The superiority of the formulated electrolyte is further demonstrated in the Zn||MnO2 and Zn||NaV3O8 full batteries, even when tested under harsh conditions (limited Zn supply (N/P≈3), 2500 cycles). This work brings inspiration for developing fast‐charging Zn batteries toward grid‐scale storage of renewable energy sources.

Biomimetic Superstructured Interphase for Aqueous Zinc-Ion Batteries

“…The failure of 2D-mPDA@Zn after long-term cycles can be ascribed to emerging cracks and protuberances in the interphase resulting from severe volume change accumulation during zinc deposition and stripping (Figure S15). Conversely, the 2D-mPDA@GO@Zn and bare Zn electrodes experience short circuits after 327 and 100 h, respectively, further highlighting the enhanced lifespan afforded by the 2D-mPDA interphase layer . Additionally, the 2D-mPDA@Zn symmetric cells show stable and stepwise increasing voltage hysteresis with a rising current density from 1 to 20 mA cm –2 , reflecting the impressive rate performance (Figure S13c).…”

Multifunctional Cellulose Nanocrystals Electrolyte Additive Enable Ultrahigh‐Rate and Dendrite‐Free Zn Anodes for Rechargeable Aqueous Zinc Batteries

“…The average number of H 2 O and SO 4 2− in the solvation shell surrounding Zn 2+ is approximately 5.0 and 0.9, respectively. Hence, the solvation structure in ZnSO 4 electrolyte is marked as [Zn(H 2 O) 5 SO 4 ] [21b] . In CNCs‐ZnSO 4 electrolyte, the peak corresponding to Zn 2+ ‐CNCs manifests at a comparable position, indicating that CNCs infiltrate the solvation structure of Zn 2+ (Figure 2k).…”

“…The Zn anode in CNCs‐ZnSO 4 electrolyte exhibits a reduced activation energy (35.17 kJ mol −1 ) than that of in ZnSO 4 electrolyte (45.89 kJ mol −1 ), reflecting the accelerated de‐solvation process and Zn 2+ ion transport by CNCs (Figure S24c) [23b] . This is attributed to the reconfiguration of the solvation structure and the hydrophilic Zn interface, resulting in a reduction of water molecules and the provision of abundant nucleation sites, respectively [21b,31a] . Due to efficient electron/Zn 2+ transport, the reduction of Zn 2+ rapidly occurs at the interface, thereby expedites the Zn plating process with diminished polarization and interface resistance.…”

Effective Orientation Control of the Zinc Anode for High-Performance Aqueous Zinc-Ion Batteries: A Key Approach To Address Dendrite Growth and Side Reactions

“…Aqueous zinc-ion batteries (AZIBs) pose significant potential in large-scale grid energy storage as a result of their high theoretical capacity (820 mAh g –1 or 5855 mAh cm –3 ), low redox potential [−0.76 V versus standard hydrogen electrode (SHE)], minimal toxicity, and abundant Zn reserves. − Nevertheless, commercialization of AZIBs is normally hampered by the inherent instability and short cycle life of the Zn metal anode. − These limitations are primarily attributed to the uncontrollable Zn dendrites and side reactions [inevitable hydrogen evolution reaction (HER), corrosion, and passivation] during the Zn plating/stripping process. − Specifically, inhomogeneous distribution of the electric field will occur as a result of the “tip effect”, − which leads to inhomogeneous distribution of Zn 2+ . Therefore, Zn 2+ tends to accumulate and deposit on the tip, eventually leading to the formation of Zn dendrites, which can puncture the separator, trigger “dead Zn”, − and short circuit AZIBs.…”