Constructing a 3D Zinc Anode Exposing the Zn(002) Plane for Ultralong Life Zinc-Ion Batteries.

The limited lifespan of aqueous Zn-ion batteries (ZIBs) is primarily attributed to the irreversible issues associated with the Zn anode, including dendrite growth, hydrogen evolution, and side reactions. Herein, a 3D Zn anode exposing Zn(002) crystal planes (3D-Zn(002) anode) is first constructed by an electrostripping method in KNO3 solution. Experiments and theoretical calculations indicate that the priority adsorption of KNO3 on Zn(100) and Zn(101) planes decreases the dissolution energy of Zn atoms, thereby exposing more Zn(002) planes. The 3D-Zn(002) anode effectively regulates ion flux to realize the uniform nucleation of Zn2+. Moreover, it can inhibit water-induced formation of side-products and hydrogen evolution reaction. Consequently, the 3D-Zn(002) symmetrical cell exhibits an exceptionally long lifespan surpassing 6000 h at 5.0 mA cm-2 with a capacity of 1.0 mAh cm-2, and enduring 8500 cycles at 30 mA cm-2 with a capacity of 1.0 mAh cm-2. Besides, when NH4V4O10 is used as the cathode, the 3D-Zn(002)//NH4V4O10 full cell shows stable cycling performance with a capacity retention rate of 75.7% after 4000 cycles at 5.0 A g-1. This study proposes a feasible method employing a 3D-Zn(002) anode for enhancing the cycling durability of ZIBs.

Constructing Built-In Electric Field in NiCo2O4-CeO2 Heterostructures to Regulate Li2O2 Formation Routes at High Current Densities.

Developing catalysts with suitable adsorption energy for oxygen-containing intermediates and elucidating their internal structure-performance relationships are essential for the commercialization of Li-O2 batteries (LOBs), especially under high current densities. Herein, NiCo2O4-CeO2 heterostructure with a spontaneous built-in electric field (BIEF) is designed and utilized as a cathode catalyst for LOBs at high current density. The driving mechanism of electron pumping/accumulation at heterointerface is studied via experiments and density functional theory (DFT) calculations, elucidating the growth mechanism of discharge products. The results show that BIEF induced by work function difference optimizes the affinity for LiO2 and promotes the formation of nano-flocculent Li2O2, thus improving LOBs performance at high current density. Specifically, NiCo2O4-CeO2 cathode exhibits a large discharge capacity (9546 mAh g-1 at 4000 mA g-1) and high stability (>430 cycles at 4000 mA g-1), which are better than the majority of previously reported metal-based catalysts. This work provides a new method for tuning the nucleation and decomposition of Li2O2 and inspires the design of ideal catalysts for LOBs to operate at high current density.