RESUMEN

The challenges of sodium metal anodes, including formation of an unstable solid-electrolyte interphase (SEI) and uncontrolled growth of sodium dendrites during charge-discharge cycles, impact the stability and safety of sodium metal batteries. Motivated by the promising commercialization potential of sodium metal batteries, it becomes imperative to systematically explore innovative protective interlayers specifically tailored for sodium metal anodes. In this work, a NaBix/NaVyOz hybrid and porous interfacial layer on sodium anode is successfully fabricated via pretreating sodium with bismuth vanadate. The hybrid interlayer effectively combines the advantages of sodium vanadates and alloys, raising a synergistic effect in facilitating sodium deposition kinetics and inhibiting the growth of sodium dendrites. As a result, the modified sodium electrodes (BVO-Na) can stably cycle for 2000 h at 0.5 mA cm-2 with a fixed capacity of 1 mAh cm-2, and the BVO-Na||Na3V2(PO4)3 full cell sustains a high capacity of 94 mAh g-1 after 600 cycles at 5 C. This work demonstrates that constructing an artificial hybrid interlayer is a practical solution to obtain high performance anodes in sodium metal batteries.

RESUMEN

Manganese (Mn)-based Prussian blue analogs (PBAs) are of great interest as a prospective cathode material for sodium-ion batteries (SIBs) due to their high redox potential, easy synthesis, and low cost. However, the Jahn-Teller effect and low electrical conductivity of Mn-based PBA cause poor structure stability and unsatisfactory performance during the cycling. Herein, a novel nickel- and copper-codoped K2Mn[Fe(CN)6] cathode is developed via a simple coprecipitation strategy. The doping elements improve the electrical conductivity of Mn-based PBA by reducing the bandgap, as well as suppress the Jahn-Teller effect by stabilizing the framework, as verified by the density functional theory calculations. Simultaneously, the substitution of sodium with potassium in the lattice is beneficial for filling vacancies in the PBA framework, leading to higher average operating voltages and superior structural stability. As a result, the as-prepared Mn-based cathode exhibits excellent reversible capacity (116.0 mAh g-1 at 0.01 A g-1) and superior cycling stability (81.8% capacity retention over 500 cycles at 0.1 A g-1). This work provides a profitable doping strategy to inhibit the Jahn-Teller structural deformation for designing stable cathode material of SIBs.

RESUMEN

Designing three-dimensional (3D) porous carbonaceous skeletons for K metal is one of the most promising strategies to inhibit dendrite growth and enhance the cycle life of potassium metal batteries. However, the nucleation and growth mechanism of K metal on 3D skeletons remains ambiguous, and the rational design of suitable K hosts still presents a significant challenge. In this study, the relationships between the binding energy of skeletons toward K and the nucleation and growth of K are systematically studied. It is found that a high binding energy can effectively decrease the nucleation barrier, reduce nucleation volume, and prevent dendrite growth, which is applied to guide the design of 3D current collectors. Density functional theory calculations show that P-doped carbon (P-carbon) exhibits the highest binding energy toward K compared to other elements (e.g., N, O). As a result, the K@P-PMCFs (P-binding porous multichannel carbon nanofibers) symmetric cell demonstrates an excellent cycle stability of 2100 h with an overpotential of 85 mV in carbonate electrolytes. Similarly, the perylene-3,4,9,10-tetracarboxylic dianhydride || K@P-PMCFs cell achieves ultralong cycle stability (85% capacity retention after 1000 cycles). This work provides a valuable reference for the rational design of 3D current collectors.

RESUMEN

Room-temperature sodium-sulfur (RT Na-S) batteries are promising for low-cost and large-scale energy storage applications. However, these batteries are plagued by safety concerns due to the highly flammable nature of conventional electrolytes. Although non-flammable electrolytes eliminate the risk of fire, they often result in compromised battery performance due to poor compatibility with sodium metal anode and sulfur cathode. Herein, we develop an additive of tin trifluoromethanesulfonate (Sn(OTf)2 ) in non-flammable phosphate electrolytes to improve the cycling stability of RT Na-S batteries via modulating the Na+ solvation environment and interface chemistry. The additive reduces the Na+ desolvation energy and enhances the electrolyte stability. Moreover, it facilitates the construction of Na-Sn alloy-based anode solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI). These interphases help to suppress the growth of Na dendrites and the dissolution/shuttling of sodium polysulfides (NaPSs), resulting in improved reversible capacity. Specifically, the Na-S battery with the designed electrolyte boosts the capacity from 322 to 906 mAh g-1 at 0.5 A g-1 . This study provides valuable insights for the development of safe and high-performance electrolytes in RT Na-S batteries.

RESUMEN

Graphene-based materials (GBMs) possess a unique set of properties including tunable interlayer channels, high specific surface area, and good electrical conductivity characteristics, making it a promising material of choice for making electrode in rechargeable batteries. Lithium-ion batteries (LIBs) currently dominate the commercial rechargeable battery market, but their further development has been hampered by limited lithium resources, high lithium costs, and organic electrolyte safety concerns. From the performance, safety, and cost aspects, zinc-based rechargeable batteries have become a promising alternative of rechargeable batteries. This review highlights recent advancements and development of a variety of graphene derivative-based materials and its composites, with a focus on their potential applications in rechargeable batteries such as LIBs, zinc-air batteries (ZABs), zinc-ion batteries (ZIBs), and zinc-iodine batteries (Zn-I2 Bs). Finally, there is an outlook on the challenges and future directions of this great potential research field.

RESUMEN

Inorganic all-solid-state sodium batteries (IASSSBs) are emerged as promising candidates to replace commercial lithium-ion batteries in large-scale energy storage systems due to their potential advantages, such as abundant raw materials, robust safety, low price, high-energy density, favorable reliability and stability. Inorganic sodium solid electrolytes (ISSEs) are an indispensable component of IASSSBs, gaining significant attention. Herein, this review begins by discussing the fundamentals of ISSEs, including their ionic conductivity, mechanical property, chemical and electrochemical stabilities. It then presents the crystal structures of advanced ISSEs (e.g., ß/ß''-alumina, NASICON, sulfides, complex hydride and halide electrolytes) and the related issues, along with corresponding modification strategies. The review also outlines effective approaches for forming intimate interfaces between ISSEs and working electrodes. Finally, current challenges and critical perspectives for the potential developments and possible directions to improve interfacial contacts for future practical applications of ISSEs are highlighted. This comprehensive review aims to advance the understanding and development of next-generation rechargeable IASSSBs.

RESUMEN

Sodium-ion batteries (SIBs) are seen as an emerging force for future large-scale energy storage due to their cost-effective nature and high safety. Compared with lithium-ion batteries (LIBs), the energy density of SIBs is insufficient at present. Thus, the development of high-energy SIBs for realizing large-scale energy storage is extremely vital. The key factor determining the energy density in SIBs is the selection of cathodic materials, and the mainstream cathodic materials nowadays include transition metal oxides, polyanionic compounds, and Prussian blue analogs (PBAs). The cathodic materials would greatly improve after targeted modulations that eliminate their shortcomings and step from the laboratory to practical applications. Before that, some remaining challenges in the application of cathode materials for large-scale energy storage SIBs need to be addressed, which are summarized at the end of this Outlook.

RESUMEN

Prussian blue analogues (PBAs) used as sodium ion battery (SIB) cathodes are usually the focus of attention due to their three-dimensional open frame and high theoretical capacity. Nonetheless, the disadvantages of a low working voltage and inferior structural stability of PBAs prevent their further applications. Herein, we propose constructing the Kx(MnFeCoNiCu)[Fe(CN)6] (HE-K-PBA) cathode by high-entropy and potassium incorporation strategy to simultaneously realize high working voltage and cycling stability. The reaction mechanism of metal cations in HE-K-PBA are revealed by synchrotron radiation X-ray absorption spectroscopy (XAS), ex situ X-ray photoelectron spectroscopy (XPS), and in situ Raman spectra. We also investigate the entropy stabilization mechanism via finite element simulation, demonstrating that HE-K-PBA with small von Mises stress and weak structure strain can significantly mitigate the structural distortion. Benefit from the stable structure and everlasting K+ (de)intercalation, the HE-K-PBA delivers high output voltage (3.46 V), good reversible capacity (120.5 mAh g-1 at 0.01 A g-1), and capacity retention of 90.4% after 1700 cycles at 1.0 A g-1. Moreover, the assembled full cell and all-solid-state batteries with a stable median voltage of 3.29 V over 3000 cycles further demonstrate the application prospects of the HE-K-PBA cathode.

RESUMEN

Vanadium selenium has gained attention as a potential anode for sodium-ion batteries (SIBs) due to the tunable crystal structure, effective channels for Na+ diffusion, and high theoretical specific capacity. However, the pursuit of vanadium selenium remains an enormous challenge. Herein, we demonstrated that V2Se9 nanosheets could be fabricated facilely and efficiently via a one-pot synthesis method with the careful selection of the solvent/surfactant. The V2Se9 anode have demonstrated excellent electrochemical performance for SIBs. An intercalation and conversion mechanism of Na-storage in V2Se9 were clarified by ex situ X-ray diffraction. This work develops an effective strategy to fabricate transition metal chalcogenides for high-performance sodium storage.

RESUMEN

Potassium-ion batteries (KIBs) are promising candidates for large-scale energy storage devices due to their high energy density and low cost. However, the large potassium-ion radius leads to its sluggish diffusion kinetics during intercalation into the lattice of the electrode material, resulting in electrode pulverization and poor cycle stability. Herein, vanadium trioxide anodes with different oxygen vacancy concentrations (V2O2.9, V2O2.8, and V2O2.7 determined by the neutron diffraction) are developed for KIBs. The V2O2.8 anode is optimal and exhibits excellent potassium storage performance due to the realization of expanded interlayer spacing and efficient ion/electron transport. In situ X-ray diffraction indicates that V2O2.8 is a zero-strain anode with a volumetric strain of 0.28% during the charge/discharge process. Density functional theory calculations show that the impacts of oxygen defects are embodied in reducing the band gap, increasing electron transfer ability, and lowering the diffusion energy barriers for potassium ions. As a result, the electrode of nanosized V2O2.8 embedded in porous reticular carbon (V2O2.8@PRC) delivers high reversible capacity (362 mAh g-1 at 0.05 A g-1), ultralong cycling stability (98.8% capacity retention after 3000 cycles at 2 A g-1), and superior pouch-type full-cell performance (221 mAh g-1 at 0.05 A g-1). This work presents an oxygen defect engineering strategy for ultrastable KIBs.

RESUMEN

Development of high-performance sodium metal batteries (SMBs) with a wide operating temperature range (from -40 to 55 °C) is highly challenging. Herein, an artificial hybrid interlayer composed of sodium phosphide (Na3 P) and metal vanadium (V) is constructed for wide-temperature-range SMBs via vanadium phosphide pretreatment. As evidenced by simulation, the VP-Na interlayer can regulate redistribution of Na+ flux, which is beneficial for homogeneous Na deposition. Moreover, the experimental results confirm that the artificial hybrid interlayer possesses a high Young's modulus and a compact structure, which can effectively suppress Na dendrite growth and alleviate the parasitic reaction even at 55 °C. In addition, the VP-Na interlayer exhibits the capability to knock down the kinetic barriers for fast Na+ transportation, realizing a 30-fold decrease in impedance at -40 °C. Symmetrical VP-Na cells present a prolonged lifespan reaching 1200, 500, and 500 h at room temperature, 55 °C and -40 °C, respectively. In Na3 V2 (PO4 )3 ||VP-Na full cells, a high reversible capacity of 88, 89.8, and 50.3 mAh g-1 can be sustained after 1600, 1000, and 600 cycles at room temperature, 55 °C and -40 °C, respectively. The pretreatment formed artificial hybrid interlayer proves to be an effective strategy to achieve wide-temperature-range SMBs.

RESUMEN

Sodium metal battery is supposed to be a propitious technology for high-energy storage application owing to the advantages of natural abundance and low cost. Unfortunately, the uncontrollable dendrite growth critically hampers its practical implementation. Herein, an inorganic/organic hybrid layer of NaF/CF/CC on the surface of Na foil (IOHL-Na) is designed and synthesized through the in situ reaction of polyvinylidene fluoride (PVDF) and metallic sodium. This protective layer possesses satisfactory Young's modulus, good kinetic property, and sodiophilicity, which can distinctly stabilize Na metal anode. As a result, the symmetric IOHL-Na cell achieves a lifespan of 770 h at 1 mAh cm-2 /1 mA cm-2 in carbonate electrolyte. The assembled full battery of IOHL-Na||Na3 V2 (PO4 )3 delivers a high discharge capacity of 85 mAh g-1 at 10 C after 600 cycles under ambient temperature. Furthermore, the IOHL-Na||Na3 V2 (PO4 )3 cell still can steadily operate at 10 C for 600 cycles at 55 °C. And when testing at an ultralow temperature of -40 °C, the full cell achieves 40 mAh g-1 at 0.5 C with a prolonged lifespan of 450 cycles. This work offers a new approach to protect the metal sodium anode without dendrite growth under wide temperatures.

RESUMEN

Suppressing the severe water-induced side reactions and uncontrolled dendrite growth of zinc (Zn) metal anodes is crucial for aqueous Zn-metal batteries to achieve ultra-long cyclic lifespans and promote their practical applications. Herein, a concept of multi-scale (electronic-crystal-geometric) structure design is proposed to precisely construct the hollow amorphous ZnSnO3 cubes (HZTO) for optimizing Zn metal anodes. In situ gas chromatography demonstrates that Zn anodes modified by HZTO (HZTO@Zn) can effectively inhibit the undesired hydrogen evolution. The pH stabilization and corrosion suppression mechanisms are revealed via operando pH detection and in situ Raman analysis. Moreover, comprehensive experimental and theoretical results prove that the amorphous structure and hollow architecture endow the protective HZTO layer with strong Zn affinity and rapid Zn2+ diffusion, which are beneficial for achieving the ideal dendrite-free Zn anode. Accordingly, excellent electrochemical performances for the HZTO@Zn symmetric battery (6900 h at 2 mA cm-2 , 100 times longer than that of bare Zn), HZTO@Zn||V2 O5 full battery (99.3% capacity retention after 1100 cycles), and HZTO@Zn||V2 O5 pouch cell (120.6 Wh kg-1 at 1 A g-1 ) are achieved. This work with multi-scale structure design provides significant guidance to rationally develop advanced protective layers for other ultra-long-life metal batteries.

RESUMEN

Next-generation secondary batteries including sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) are considered the most promising candidates for application to large-scale energy storage systems due to their abundant, evenly distributed and cost-effective sodium/potassium raw materials. The electrochemical performance of SIBs (PIBs) significantly depends on the inherent characteristics of the cathode material. Among the wide variety of cathode materials, sodium/potassium vanadium fluorophosphate (denoted as MVPF, M = Na and K) composites are widely investigated due to their fast ion transportation and robust structure. However, their poor electron conductivity leads to low specific capacity and poor rate capacity, limiting the further application of MVPF cathodes in large-scale energy storage. Accordingly, several modification strategies have been proposed to improve the performance of MVPF such as conductive coating, morphological regulation, and heteroatomic doping, which boost the electronic conductivity of these cathodes and enhance Na (K) ion transportation. Furthermore, the development and application of MVPF cathodes in SIBs at low temperatures are also outlined. Finally, we present a brief summary of the remaining challenges and corresponding strategies for the future development of MVPF cathodes.

RESUMEN

Due to the high theoretical energy density, low cost, and rich abundance of sodium and sulfur, room-temperature sodium-sulfur (RT Na-S) batteries are investigated as the promising energy storage system. However, the inherent insulation of the S8 , the dissolution and shuttle of the intermediate sodium polysulfides (NaPSs), and especially the sluggish conversion kinetics, restrict the commercial application of the RT Na-S batteries. To address these issues, various catalysts are developed to immobilize the soluble NaPSs and accelerate the conversion kinetics. Among them, the polar catalysts display impressive performance. Polar catalysts not only can significantly accelerate (or alter) the redox process, but also can adsorb polar NaPSs through polar-polar interaction because of their intrinsic polarity, thus inhibiting the notorious shuttle effect. Herein, the recent advances in the electrocatalytic effect of polar catalysts on the manipulation of S speciation pathways in RT Na-S batteries are reviewed. Furthermore, challenges and research directions to realize rapid and reversible sulfur conversion are put forward to promote the practical application of RT Na-S batteries.

RESUMEN

Carbonate electrolytes have excellent chemical stability and high salt solubility, which are ideally practical choice for achieving high-energy-density sodium (Na) metal battery at room temperature. However, their application at ultra-low temperature (-40 °C) is adversely affected by the instability of solid electrolyte interphase (SEI) formed by electrolyte decomposition and the difficulty of desolvation. Here, we designed a novel low-temperature carbonate electrolyte by molecular engineering on solvation structure. The calculations and experimental results demonstrate that ethylene sulfate (ES) reduces the sodium ion desolvation energy and promotes the forming of more inorganic substances on the Na surface, which promote ion migration and inhibit dendrite growth. At -40 °C, the Na||Na symmetric battery exhibits a stable cycle of 1500 hours, and the Na||Na3 V2 (PO4 )3 (NVP) battery achieves 88.2 % capacity retention after 200 cycles.

RESUMEN

Room temperature sodium-sulfur (RT Na-S) batteries are highly competitive as potential energy storage devices. Nevertheless, their actually achieved reversible capacities are far below the theoretical value due to incomplete transformation of polysulfides. Herein, atomically dispersed Fe-N/S active center by regulating the second-shell coordinating environment of Fe single atom is proposed. The Fe-N4 S2 coordination structure with enhanced local electronic concentration around the Fermi level is revealed via synchrotron radiation X-ray absorption spectroscopy (XAS) and theoretical calculations, which can not only significantly promote the transformation kinetics of polysulfides, but induce uniform Na deposition for dendrite-free Na anode. As a result, the obtained S cathode delivers a high initial reversible capacity of 1590 mAh g-1 , nearly the theoretical value. This work opens up a new avenue to facilitate the complete transformation of polysulfides for RT Na-S batteries.

Asunto(s)

RESUMEN

Na3V2(PO4)2O2F (NVPOF) is considered a promising cathode material for sodium-ion batteries (SIBs) on account of its attractive electrochemical properties such as high theoretical capacity, stable structure, and high working platform. Nevertheless, the inevitable interface problems like sluggish interfacial electrochemical reaction kinetics and poor interfacial ion storage capacity seriously hinder its application. Construction of chemical bonding is a highly effective way to solve interface problems. Herein, NVPOF with interfacial V-F-C bonding (CB-NVPOF) is developed. The CB-NVPOF cathode exhibits high rate capability (65 mA h g-1 at 40C) and long-term cycling stability (a capacity retention of 77% after 2000 cycles at 20C). Furthermore, it shows impressive electrochemical performance at temperatures as low as -40 °C, delivering a capacity of 56 mA h g-1 at 10C and a capacity retention of ∼80% after 500 cycles at 2C. The interfacial V-F-C bond engineering significantly advances the electronic conductivity, Na+ diffusion, as well as interface compatibility at -40 °C. This study provides a novel idea for improving the electrochemical performance of NVPOF-based cathodes for SIBs aiming for low-temperature applications.

RESUMEN

The practical application of the room-temperature sodium-sulfur (RT Na-S) batteries is hindered by the insulated sulfur, the severe shuttle effect of sodium polysulfides, and insufficient polysulfide conversion. Herein, on the basis of first principles calculations, single-atom vanadium anchored on a 3D nitrogen-doped hierarchical porous carbon matrix (denoted as 3D-PNCV) is designed and fabricated to enhance sulfur reactivity, and adsorption and catalytic conversion performance of sodium polysulfide. The 3D-PNCV host with abundant and active V sites, hierarchical porous structure, high electrical conductivity, and strong chemical adsorption/conversion ability of V-N bonding can immobilize the polysulfides and promote reversibly catalytic conversion of polysulfides toward Na2 S. Therefore, as-fabricated RT Na-S batteries can achieve a high reversible capacity (445 mAh g-1 over 800 cycles at 5 A g-1 ) and excellent rate capability (224 mAh g-1 at 10 A g-1 ). The electrocatalysis mechanism of sodium polysulfides is further experimentally and theoretically revealed, which provides a new strategy to develop the highly stable RT Na-S batteries.

RESUMEN

The sodium (Na)-metal anode with high theoretical capacity and low cost is promising for construction of high-energy-density metal batteries. However, the unsatisfactory interface between Na and the liquid electrolyte induces tardy ion transfer kinetics and dendritic Na growth, especially at ultralow temperature (-40 °C). Herein, an artificial heterogeneous interphase consisting of disodium selenide (Na2 Se) and metal vanadium (V) is produced on the surface of Na (Na@Na2 Se/V) via an in situ spontaneous chemical reaction. Such interphase layer possesses high sodiophilicity, excellent ionic conductivity, and high Young's modulus, which can promote Na-ion adsorption and transport, realizing homogenous Na deposition without dendrites. The symmetric Na@Na2 Se/V cell exhibits outstanding cycling life span of over 1790 h (0.5 mA cm-2 /1 mAh cm-2 ) in carbonate-based electrolyte. More remarkably, ab initio molecular dynamics simulations reveal that the artificial Na2 Se/V hybrid interphase can accelerate the desolvation of solvated Na+ at -40 °C. The Na@Na2 Se/V electrode thus exhibits exceptional electrochemical performance in symmetric cell (over 1500 h at 0.5 mA cm-2 /0.5 mAh cm-2 ) and full cell (over 700 cycles at 0.5 C) at -40 °C. This work provides an avenue to design artificial heterogeneous interphase layers for superior high-energy-density metal batteries at ambient and ultralow temperatures.