RESUMEN
Interfacial Na+ behaviors of sodium (Na) anode severely threaten the stability of sodium-metal batteries (SMBs). This review systematically and in-depth discusses the current fundamental understanding of interfacial Na+ behaviors in SMBs including Na+ migration, desolvation, diffusion, nucleation, and deposition. The key influencing factors and optimization strategies of these behaviors are further summarized and discussed. More importantly, the high-energy-density anode-free sodium metal batteries (AFSMBs) are highlighted by addressing key issues in the areas of limited Na sources and irreversible Na loss. Simultaneously, recent advanced characterization techniques for deeper insights into interfacial Na+ deposition behavior and composition information of SEI film are spotlighted to provide guidance for the advancement of SMBs and AFSMBs. Finally, the prominent perspectives are presented to guide and promote the development of SMBs and AFSMBs.
RESUMEN
Sodium metal batteries (SMBs) have received increasing attention due to the abundant sodium resources and high energy density, but suffered from the sluggish interfacial kinetic and unstable plating/stripping of sodium anode at low temperature, especially when matched with ester electrolytes. Here, we develop a stable ultra-low-temperature SMBs with high-capacity retention at -50°C in a weak solvated carbonate ester-based electrolyte, combined with an electrodeposited Na (Cu/Na) anode. The Cu/Na anode with electrochemically activated "deposited sodium" and stable inorganic-rich solid electrolyte interphase (SEI) was favor for the fast Na+ migration, therefore accelerating the interfacial kinetic process. As a result, the Cu/Na || NaCrO2 battery exhibited the highest capacity retention (compared to room-temperature capacity) in carbonate ester-based SMBs (98.05% at -25°C, 91.3% at -40°C, 87.9% at -50°C, respectively). The cyclic stability of 350 cycles at -25°C with a high energy efficiency of 96.15% and 70 cycles at -50°C can be achieved. Even in chill atmospheric environment with the fluctuant temperature, the battery can still operate over one month. This work provides a new opportunity for the development of low-temperature carbonate ester-based SMBs.
RESUMEN
Irreversible interfacial reactions at the anodes pose a significant challenge to the long-term stability and lifespan of zinc (Zn) metal batteries, impeding their practical application as energy storage devices. The plating and stripping behavior of Zn ions on polycrystalline surfaces is inherently influenced by the microscopic structure of Zn anodes, a comprehensive understanding of which is crucial but often overlooked. Herein, commercial Zn foils were remodeled through the incorporation of cerium (Ce) elements via the 'pinning effect' during the electrodeposition process. By leveraging the electron-donating effect of Ce atoms segregated at grain boundaries (GBs), the electronic configuration of Zn is restructured to increase active sites for Zn nucleation. This facilitates continuous nucleation throughout the growth stage, leading to a high-rate instantaneous-progressive composite nucleation model that achieves a spatially uniform distribution of Zn nuclei and induces spontaneous grain refinement. Moreover, the incorporation of Ce elements elevates the site energy of GBs, mitigating detrimental parasitic reactions by enhancing the GB stability. Consequently, the remodeled ZnCe electrode exhibits highly reversible Zn plating/stripping with an accumulated capacity of up to 4.0 Ah cm-2 in a Zn symmetric cell over 4000 h without short-circuit behavior. Notably, a â¼0.4 Ah Zn||NH4V4O10 pouch cell runs over 110 cycles with 83% capacity retention with the high-areal-loading cathode (≈20 mg cm-2). This refining-grains strategy offers new insights into designing dendrite-free metal anodes in rechargeable batteries.
RESUMEN
Interfacial instability within aqueous zinc batteries (AZBs) spurs technical obstacles including parasitic side reactions and dendrite failure to reach the practical application standards. Here, an interfacial engineering is showcased by employing a bio- derived zincophilic macromolecule as the electrolyte additive (0.037 wt%), which features a long-chain configuration with laterally distributed hydroxyl and sulfate anion groups, and has the propensity to remodel the electric double layer of Zn anodes. Tailored Zn2+-rich compact layer is the result of their adaptive adsorption that effectively homogenizes the interfacial concentration field, while enabling a hybrid nucleation and growth mode characterized as nuclei-rich and space-confined dense plating. Further resonated with curbed corrosion and by-products, a dendrite-free deposition morphology is achieved. Consequently, the macromolecule-modified zinc anode delivers over 1250 times of reversible plating/stripping at a practical area capacity of 5 mAh cm-2, as well as a high zinc utilization rate of 85%. The Zn//NH4V4O10 pouch cell with the maximum capacity of 1.02 Ah can be steadily operated at 71.4 mA g-1 (0.25 C) with 98.7% capacity retained after 50 cycles, which demonstrates the scale-up capability and highlights a "low input and high return" interfacial strategy toward practical AZBs.
RESUMEN
High-voltage aqueous zinc ion batteries (AZIBs) with a high-safety near-neutral electrolyte is of great significance for practical sustainable application; however, they suffer from anode and electrode/electrolyte interfacial incompatibility. Herein, a conversion-type anode chemistry with a low anodic potential, which is guided by the Gibbs free energy change of conversion reaction, was designed for high-voltage near-neutral AZIBs. A reversible conversion reaction between ZnC2O4·2H2O particles and three-dimensional Zn metal networks well-matched in CH3COOLi-based electrolyte was revealed. This mechanism can be universally validated in the battery systems with sodium or iodine ions. More importantly, a cathodic crowded micellar electrolyte with a water confinement effect was proposed in which lies the core for the stability and reversibility of the cathode under an operating platform voltage beyond 2.0 V, obtaining a capacity retention of 95% after 100 cycles. Remarkably, the scientific and technological challenges from the coin cell to Ah-scale battery, sluggish kinetics of the solid-solid electrode reaction, capacity excitation under high loading of active material, and preparation complexities associated with large-area quasi-solid electrolytes, were explored, successfully achieving an 88% capacity retention under high loading of more than 20 mg cm-2 and particularly a practical 1.1 Ah-level pouch cell. This work provides a path for designing low-cost, eco-friendly and high-voltage aqueous batteries.
RESUMEN
Layered vanadium-based oxides have emerged as highly promising candidates for aqueous zinc-ion batteries (AZIBs) due to their open-framework layer structure and high theoretical capacity among the diverse cathode materials investigated. However, the susceptibility to structural collapse during charge-discharge cycling severely hampers their advancement. Herein, we propose an effective strategy to enhance the cycling stability of vanadium oxides. Initially, the structural integrity of the host material is significantly reinforced by incorporating bi-cations Na+ and NH4 + as "pillars" between the V2O5 layers (NaNVO). Subsequently, surface coating with polyaniline (PA) is employed to further improve the conductivity of the active material. As anticipated, the assembled Zn//NaNVO@PA cell exhibits a remarkable discharge capacity of 492â mAh g-1 at 0.1â A g-1 and exceptional capacity retention up to 89.2 % after 1000 cycles at a current density of 5â A g-1. Moreover, a series of in-situ and ex-situ characterization techniques were utilized to investigate both Zn ions insertion/extraction storage mechanism and the contribution of polyaniline protonation process towards enhancing capacity.
RESUMEN
The optimization of crystalline orientation of a Zn metal substrate to expose more Zn(0002) planes has been recognized as an effective strategy in pursuit of highly reversible Zn metal anodes. However, the lattice mismatch between substrate and overgrowth crystals has hampered the epitaxial sustainability of Zn metal. Herein, we discover that the presence of crystal grains deviating from [0001] orientation within a Zn(0002) metal anode leads to the failure of epitaxial mechanism. The electrodeposited [0001]-uniaxial oriented Zn metal anodes with a single (0002) texture fundamentally eliminate the lattice mismatch and achieve ultra-sustainable homoepitaxial growth. Using high-angle angular dark-filed scanning transmission electron microscopy, we elucidate the homoepitaxial growth of the deposited Zn following the "~ABABAB~" arrangement on the Zn(0002) metal from an atomic-level perspective. Such consistently epitaxial behavior of Zn metal retards dendrite formation and enables improved cycling, even in Zn||NH4V4O10 pouch cells, with a high capacity of 220 mAh g-1 for over 450 cycles. The insights gained from this work on the [0001]-oriented Zn metal anode and its persistently homoepitaxial mechanism pave the way for other metal electrodes with high reversibility.
RESUMEN
Vanadium-based cathodes have received widespread attention in the field of aqueous zinc-ion batteries, presenting a promising prospect for stationary energy storage applications. However, the rapid capacity decay at low current densities has hampered their development. In particular, capacity stability at low current densities is a requisite in numerous practical applications, typically encompassing peak load regulation of the electricity grid, household energy storage systems, and uninterrupted power supplies. Despite possessing notably high specific capacities, vanadium-based materials exhibit severe instability at low current densities. Moreover, the issue of stabilizing electrode reactions at these densities for vanadium-based materials has been explored insufficiently in existing research. This review aims to investigate the matter of stability in vanadium-based materials at low current densities by concentrating on the mechanisms of capacity fading and optimization strategies. It proposes a comprehensive approach that includes electrolyte optimization, electrode modulation, and electrochemical operational conditions. Finally, we presented several crucial prospects for advancing the practical development of vanadium-based aqueous zinc-ion batteries.
RESUMEN
Wearable and implantable electronics are standing at the frontiers of science and technology, driven by the increasing demands from modernized lifestyles. Zinc-based batteries (ZBs) are regarded as ideal energy suppliers for these biocompatible electronics, but the corresponding biocompatibility validation is still in the initial stage. Meanwhile, complicated working conditions and some extreme electrolyte environments raise strict challenges, leaving less choices for safe ZBs. Toward higher operating stability and biocompatibility, this work proposes a hydrogel electrolyte featuring the moisture maintaining ability and a robust interface, which could further provide a milder environment for Zn-MnO2 batteries and Zn-air batteries. The cytotoxicity and tissue injury of batteries are evaluated with human cell lines and battery implantations on the animal models, which demonstrate the high biocompatibility of ZBs, while preliminary wearable devices implementation further verifies their operating stability. This work may provide a pathway for developing and validating biocompatible ZBs, contributing to their future practical employment in relevant fields.