Boosting Ion Diffusion and Charge Transfer by Zincophilic Accordion Arrays to Achieve Ultrafast Aqueous Zinc Metal Batteries

A key challenge to apply aqueous zinc metal batteries (AZMBs) as next-generation energy storage device is to improve the rechargeability at high current densities, which is needed to circumvent slowly ion diffusion in anode and sluggish charge transfer of Zn²⁺. Herein, a zincophilic accordion array derived from MOF is developed as zinc host for simultaneously boosted ion diffusion and charge transfer. The designed host is prepared by etching and disproportionation reactions, the abundant zincophilic Sn sites with nano-size uniform disperse on accordion arrays nanosheets (Sn-AA). Then a composite Zn anode (Sn-AA@Zn) is obtained by compacting Sn-AA host with zinc power (Zn-P). The Sn-AA@Zn anode has an ultra-low activation energy (37.1 kJ mol⁻¹) and nucleation overpotential (10 mV), achieving fast charge transfer of Zinc deposition. In addition, the cycle life of the symmetric cell with Sn-AA@Zn anode exceeds 13 000 cycles at 50 mA cm⁻², which is 32 times than that of the Zn-P anode. And the full cell with Sn-AA@Zn anode and MnO₂ cathode maintains a capacity of 122 mAh g⁻¹ after 5000 cycles at 5 Ag⁻¹. Hopefully, the 3D anode based on Sn-AA@Zn accordion array and Zn-P has significantly improved the rechargeability of AZMB at high current density.     

Single Nanostructure Electrochemical Devices for Studying Electronic Properties and Structural Changes in Lithiated Si Nanowires

Nanostructured Si is a promising anode material for the next generation of Li‐ion batteries, but few studies have focused on the electrical properties of the Li‐Si alloy phase, which are important for determining power capabilities and ensuring sufficient electrical conduction in the electrode structure. Here, we demonstrate an electrochemical device framework suitable for testing the electrical properties of single Si nanowires (NWs) at different lithiation states and correlating these properties with structural changes via transmission electron microscopy (TEM). We find that single Si NWs usually exhibit Ohmic I–V response in the lithiated state, with conductivities two to three orders of magnitude higher than in the delithiated state. After a number of sequential lithiation/delithiation cycles, the single NWs show similar conductivity after each lithiation step but show large variations in conductivity in the delithiated state. Finally, devices with groups of NWs in physical contact were fabricated, and structural changes in the NWs were observed after lithiation to investigate how the electrical resistance of NW junctions and the NWs themselves affect the lithiation behavior. The results suggest that electrical resistance of NW junctions can limit lithiation. Overall, this study shows the importance of investigating the electronic properties of individual components of a battery electrode (single nanostructures in this case) along with studying the nature of interactions within a collection of these component structures.     

Observation of Electrochemically Driven Elemental Segregation in a Si Alloy Thin‐Film Anode and its Effects on Cyclic Stability for Li‐Ion Batteries

The results of employing (Ti, Fe)‐alloyed Si thin‐film anode for Li‐ion batteries are reported. The material demonstrates an impressive cyclic stability with stable operation for more than 500 cycles at a capacity higher than 1400 mAh g^?1. Materials characterization using scanning electron microscopy and transmission electron microscopy illuminates an intriguing materials process behind the performance: ripple‐like pattern formation via electrochemically driven segregation of the inactive elements (Ti and Fe). The ripple structure plays a buffer role by suppressing loss of the active material upon further cycling, allowing the anode to gradually transform into an array of microbumps. The morphological evolution helps the anode endure long cycles (even up to 1000 cycles) without catastrophic failure as the bumps shrank slowly and steadily, consistent with the electrochemical data.     

Diffusion Limitation of Lithium Metal and Li–Mg Alloy Anodes on LLZO Type Solid Electrolytes as a Function of Temperature and Pressure

The morphological instability of the lithium metal anode is the key factor restricting the rate capability of lithium metal solid state batteries. During lithium stripping, pore formation takes place at the interface due to the slow diffusion kinetics of vacancies in the lithium metal. The resulting current focusing increases the internal cell resistance and promotes fast lithium penetration. In this work, galvanostatic electrochemical impedance spectroscopy is used to investigate operando the morphological changes at the interface by analysis of the interface capacitances. Therewith, the effect of temperature, stack pressure, and chemical modification is investigated. The work demonstrates that introducing 10 at% Mg into the lithium metal anode can effectively prevent contact loss. Nevertheless, a fundamental kinetic limitation is also observed for the Li‐rich alloy, namely the diffusion controlled decrease of the lithium metal concentration at the interface. An analytical diffusion model is used to describe the temperature‐dependent delithiation kinetics of Li–Mg alloys. Overall, it is shown that different electrode design concepts should be considered. Mg alloying can increase lithium utilization, when no external pressure is applied while pure lithium metal is superior for setups that allow stack pressures in the MPa range.     

Recent Progress in the Development of Anode Materials for Solid Oxide Fuel Cells

The field of research into solid oxide fuel cell (SOFC) anode materials has been rapidly moving forward. In the four years since the last in‐depth review significant advancements have been made in the reduction of the operating temperature and improvement of the performance of SOFCs. This progress report examines the developments in the field and looks to draw conclusions and inspiration from this research. A brief introduction is given to the field, followed by an overview of the principal previous materials. A detailed analysis of the developments of the last 4 years is given using a selection of the available literature, concentrating on metal‐fluorite cermets and perovskite‐based materials. This is followed by a consideration of alternate fuels for use in SOFCs and their associated problems and a short discussion on the effect of synthesis method on anode performance. The concluding remarks compile the significant developments in the field along with a consideration of the promise of future research. The recent progress in the development of anode materials for SOFCs based on oxygen ion conducting electrolytes is reviewed.