Tailoring Pseudo-Graphitic Domain by Molybdenum Modification to Boost Sodium Storage Capacity and Durability for Hard Carbon.

Hard carbon (HC) stands out as the most prospective anode for sodium-ion batteries (SIBs) with significant potential for commercial applications. However, some long-standing and intractable obstacles, like low first coulombic efficiency (ICE), poor rate capability, storage capacity, and cycling stability, have severely hindered the conversion process from laboratory to commercialization. The above-mentioned issues are closely related to Na+ transfer kinetics, surface chemistry, and internal pseudo-graphitic carbon content. Herein, constructing molybdenum-modified hard carbon solid spheres (Mo2C/HC-5.0), both the ion transfer kinetics, surface chemistry, and internal pseudo-graphitic carbon content are comprehensively improved. Specifically, Mo2C/HC-5.0 with higher pseudo-graphitic carbon content provides a large number of active sites and a more stable layer structure, resulting in improved sodium storage capacity, rate performance, and cycling stability. Moreover, the lower defect density and specific surface area of Mo2C/HC-5.0 further enhance ICE and sodium storage capacity. Consequently, the Mo2C/HC-5.0 anode achieves a high capacity of 410.7 mA h g-1 and an ICE of 83.9% at 50 mA g-1. Furthermore, the material exhibits exceptional rate capability and cycling stability, maintaining a capacity of 202.8 mA h g-1 at 2 A g-1 and 214.9 mA h g-1 after 800 cycles at 1 A g-1.

Carbonate Ester-Based Sodium Metal Battery with High-Capacity Retention at -50 °C Enabled by Weak Solvents and Electrodeposited Anode.

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) is 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.

Aligned Dipoles Induced Electric-Field Promoting Zinc-Ion De-Solvation toward Highly Stable Dendrite-Free Zinc-Metal Batteries.

Water-induced parasitic reactions and uncontrolled dendritic Zn growth are long-lasting tricky problems that severely hinder the development of aqueous zinc-metal batteries. Those notorious issues are closely related to electrolyte configuration and zinc-ion transport behavior. Herein, through constructing aligned dipoles induced electric-field on Zn surface, both the solvation structure and transport behavior of zinc-ions are fundamentally changed. The vertically ordered zinc-ion migration trajectory and gradually concentrated zinc-ion achieved inside the polarized electric-field remarkably eliminate water related side-reactions and Zn dendrites. Zn-metal under the polarized electric-field demonstrated significantly improve reversibility and a dendrite-free surface with strong (002) Zn deposition texturing. Zn||Zn symmetric cell delivers greatly prolonged lifespan up to 1400 h (17 times longer than that of the cell based on bare Zn) while the Zn||Cu half-cell demonstrate ultrahigh 99.9% coulombic efficiency. NH4 V4 O10 ||Zn half-cell delivered exceptional-high 132 mAh g-1 capacity after ultralong 2000 cycles (≈100% capacity retention). In addition, MnO2 ||Zn pouch-cell under aligned dipoles induced electric-field maintains 87.9% capacity retention after 150 cycles under practical condition of high MnO2 mass loading (≈10 mg cm-2 ) and limited N/P ratio. It is considered that this new strategy can also be implemented to other metallic batteries and spur the development of batteries with long-lifespan and high-energy-density.

Zincophilic Electrode Interphase with Appended Proton Reservoir Ability Stabilizes Zn Metal Anodes.

The rampant dendrites and hydrogen evolution reaction (HER) resulting from the turbulent interfacial evolution at the anode/electrolyte are the main culprits of short lifespan and low Coulombic efficiency of Zn metal batteries. In this work, a versatile protective coating with excellent zincophilic and amphoteric features is constructed on the surface of Zn metal (ZP@Zn) as dendrite-free anodes. This kind of protective coating possesses the advantages of reversible proton storage and rapid desolvation kinetics, thereby mitigating the HER and facilitating homogeneous nucleation concomitantly. Furthermore, the space charge polarization effect promotes charge redistribution to achieve uniform Zn deposition. Accordingly, the ZP@Zn symmetric cell manifests excellent reversibility at an ultrahigh cumulative plating capacity of 4700 mAh cm-2 and stable cycling at 80 % depth of discharge (DOD). The ZP@Zn//V6 O13 pouch cell also reveals superior cycling stability with a high capacity of 326.6 mAh g-1 .

Multichannel Ca2+ Generator for Synergistic Tumor Therapy via Intracellular Ca2+ Overload and Chemotherapy.

Ca2+ overload has attracted an increasing attention due to its benefit of precise cancer therapy, but its efficacy is limited by the strong Ca2+ excretion of cancer cells. Moreover, monotherapy of Ca2+ overload usually fails to treat tumors satisfactorily. Herein, we develop a multifunctional nanosystem that could induce Ca2+ overload by multipathway and simultaneously produce chemotherapy for synergistic tumor therapy. The nanosystem (CaMSN@CUR) is prepared by synthesizing a Ca-doped mesoporous silica nanoparticle (CaMSN) followed by loading the anticancer drug curcumin (CUR). CaMSN serves as the basis Ca2+ generator to induce Ca2+ overload directly in the intracellular environment by acid-triggered Ca2+ release, while CUR could not only exhibit chemotherapy but also facilitate Ca2+ release from the endoplasmic reticulum to the cytoplasm and inhibit Ca2+ efflux out of cells to further enhance Ca2+ overload. The in vitro and in vivo results show that CaMSN@CUR could exhibit a remarkable cytotoxicity against 4T1 cells and significantly inhibit tumor growth in 4T1 tumor-bearing mice via the synergy of Ca2+ overload and CUR-mediated chemotherapy. It is expected that the designed CaMSN@CUR has a great potential for effective tumor therapy.

Design Strategies for High-Energy-Density Aqueous Zinc Batteries.

In recent years, the increasing demand for high-capacity and safe energy storage has focused attention on zinc batteries featuring high voltage, high capacity, or both. Despite extensive research progress, achieving high-energy-density zinc batteries remains challenging and requires the synergistic regulation of multiple factors including reaction mechanisms, electrodes, and electrolytes. In this Review, we comprehensively summarize the rational design strategies of high-energy-density zinc batteries and critically analyze the positive effects and potential issues of these strategies in optimizing the electrochemistry, cathode materials, electrolytes, and device architecture. Finally, the challenges and perspectives for the further development of high-energy-density zinc batteries are outlined to guide research towards new-generation batteries for household appliances, low-speed electric vehicles, and large-scale energy storage systems.

In Situ Defect Induction in Close-Packed Lattice Plane for the Efficient Zinc Ion Storage.

In situ electrochemical activation brings unexpected electrochemical performance improvements to electrode materials, but the mechanism behind it still needs further study. Herein, an electrochemically in situ defect induction in close-packed lattice plane of vanadium nitride oxide (VNx Oy ) in aqueous zinc-ion battery is reported. It is verified by theoretical calculation and experiment that the original compact structure is not suitable for the insert of Zn2+ ion, while a highly active one after the initial electrochemical activization accompanied by the in situ defect induction in close-packed lattice plane of VNx Oy exhibits efficient zinc ion storage. As expected, activated VNx Oy can achieve very high reversible capacity of 231.4 mA h g-1 at 1 A g-1 and cycle stability upto 6000 cycles at 10 A g-1 with a capacity retention of 94.3%. This work proposes a new insight for understanding the electrochemically in situ transformation to obtain highly active cathode materials for the aqueous zinc-ion batteries.

Facilitating Phase Evolution for a High-Energy-Efficiency, Low-Cost O3-Type NaxCu0.18Fe0.3Mn0.52O2 Sodium Ion Battery Cathode.

The phase transition and lattice parameter evolution of O3 structure commonly occurs in O3-type sodium ion battery (SIB) cathodes, which might enlarge the voltage hysteresis and lower the energy efficiency. Given that the cost is one of the issues discouraging the application of SIBs in large-scale energy storage, here we focus on Co/Ni-free NaxCu0.18Fe0.3Mn0.52O2 (x = 0.8, 0.85, 0.9) and propose a convenient strategy to reduce the voltage hysteresis. It is found that when the Na content is 0.8, the highest energy efficiency of 95.4% after activation is achieved (2.5-4.0 V, 50 mA g-1, the 50th cycle), in addition to a satisfactory capacity retention (about 0.056% decay per cycle). The further characterizations reveal that Na0.8Cu0.18Fe0.3Mn0.52O2 owns a gentle O3-P3 phase transition process and does not undergo O3 phase lattice parameter evolution. The key point lies in the attainability of the O3/P3 composite of the material. This work will provide a simple strategy for the rational design of O3-type cathodes with a high energy efficiency and might offer inspiration to search for layered oxides with a higher O3/P3 critical Na content through element adjustments.

Solvent Molecule Cooperation Enhancing Lithium Metal Battery Performance at Both Electrodes.

Developing electrolytes compatible with efficient and reversible cycling of electrodes is critical to the success of rechargeable Li metal batteries (LMBs). The Coulombic efficiencies and cycle lives of LMBs with ethylene carbonate (EC), dimethyl carbonate, ethylene sulfite (ES), and their combinations as electrolyte solvents show that in a binary-solvent electrolyte the extent of electrolyte decomposition on the electrode surface is dependent on the solvent component that dominates the solvation sheath of Li+ . This knowledge led to the development of an EC-ES electrolyte exhibiting high performance for Li||LiFePO4 batteries. Carbonate molecules occupy the solvation sheath and improve the Coulombic efficiencies of both the anode and cathode. Sulfite molecules lead to desirable morphology and composition of the solid electrolyte interphase and extend the cycle life of the Li metal anode. The cooperation between these components provides a new example of electrolyte optimization for improved LMBs.

Serpentine Ni3 Ge2 O5 (OH)4 Nanosheets with Tailored Layers and Size for Efficient Oxygen Evolution Reactions.

Layered serpentine Ni3 Ge2 O5 (OH)4 is compositionally active and structurally favorable for adsorption and diffusion of reactants in oxygen evolution reactions (OER). However, one of the major problems for these materials is limited active sites and low efficiency for OER. In this regard, a new catalyst consisting of layered serpentine Ni3 Ge2 O5 (OH)4 nanosheets is introduced via a controlled one-step synthetic process where the morphology, size, and layers are well tailored. The theoretical calculations indicate that decreased layers and increased exposure of (100) facets in serpentine Ni3 Ge2 O5 (OH)4 lead to much lower Gibbs free energy in adsorption of reactive intermediates. Experimentally, it is found that the reduction in number of layers with minimized particle size exhibits plenty of highly surface-active sites of (100) facets and demonstrates a much enhanced performance in OER than the corresponding multilayered nanosheets. Such a strategy of tailoring active sites of serpentine Ni3 Ge2 O5 (OH)4 nanosheets offers an effective method to design highly efficient electrocatalysts.

Nb2O5 microstructures: a high-performance anode for lithium ion batteries.

We report the synthesis of three-dimensional (3D) urchin-like Nb2O5 microstructures by a facile hydrothermal approach with subsequent annealing treatment. As anode materials for lithium-ion batteries, the 3D urchin-like Nb2O5 microstructures exhibit superior electrochemical performance with excellent rate capability as well as long-term cycling stability. The electrode delivers high capacity of 131 mA h g-1 after 1000 cycles at a high current density of 1 A g-1. The excellent electrochemical performance suggests the 3D urchin-like Nb2O5 microstructures may be a promising anode candidate for high-power lithium ion batteries.

Template-free synthesis of highly porous V2O5 cuboids with enhanced performance for lithium ion batteries.

Highly porous hierarchical V2O5 cuboids have been synthesized by a template-free PVP-assisted polyxol method and the formation mechanism is studied. The cuboids are assembled from numerous mesoporous nanoplates and the preferred orientation of each single nanoplate exposes the 〈110〉 facets, facilitating lithium-ion diffusion by offering a prior channel. This material exhibits a high capacity of 143 mA h g(-1), high rate capacity of 10 C and long life cycling performance up to 1000 cycles. The excellent electrochemical performance of V2O5 cuboid electrodes is due to its unique porous cuboid morphology and optimized structural stability upon cycling. This research provides an effective route to the construction of complex porous architectures assembled from nanocrystals through a surfactant-assisted synthesis method.

Low-current-density stability of vanadium-based cathodes for aqueous zinc-ion batteries.

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.

In-Depth Understanding of Interfacial Na+ Behaviors in Sodium Metal Anode: Migration, Desolvation, and Deposition.

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.

Single [0001]-oriented zinc metal anode enables sustainable zinc batteries.

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.

From Natural Fibers to High-Performance Anodes: Sisal Hemp Derived Hard Carbon for Na-/K-Ion Batteries and Mechanism Exploration.

Hard carbon (HC) is a promising anode material in alkali metal ion batteries owing to its cost-effectiveness, abundant sources, and low working voltage. However, challenges persist in achiving prolonged cycling stability and consistent capacity, and the sodium storage mechanism in HC is still debated. Herein, an unreported biomass precursor, "sisal," for deriving hard carbon is developed. A series of sisal hemp-derived hard carbon with natural 3D porous channels are prepared. Through phase characterization and electrochemical testing, the relationship between microstructure and sodium storage capacity is elucidated, further confirming the suitability of the "adsorption-insertion-filling" mechanism for sodium storage properties in hard carbon materials. Without the need for any additional modification strategies, this biomass-derived hard carbon demonstrates excellent electrochemical performance in both sodium-ion and potassium-ion batteries (SIBs and PIBs). The as-prepared HC-1300 demonstrates excellent ion storage capability, delivering a high reversible capacity of 345.2 mAh g-1 in SIBs and 310 mAh g-1 in PIBs at 0.1 C. Moreover, it maintains a specific capacity of 237.3 mAh g-1 over 1200 cycles at 1 C when used in SIBs. The excellent cycling stability and superior rate performance are also presented in full cells, highlighting its potential for practical applications.

Conversion-type anode chemistry with interfacial compatibility toward Ah-level near-neutral high-voltage zinc ion batteries.

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.

Validating Operating Stability and Biocompatibility Toward Safer Zinc-Based Batteries.

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.

Cations-Pillared and Polyaniline-Encapsulated Vanadate Cathode for High-Performance Aqueous Zinc-Ion Batteries.

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 492 mAh g-1 at 0.1 A g-1 and exceptional capacity retention up to 89.2 % after 1000 cycles at a current density of 5 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.

Interfacial Biomacromolecular Engineering Toward Stable Ah-Level Aqueous Zinc Batteries.

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.