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Solid‐state lithium–air batteries (SSLABs) have become the focus of next‐generation advanced batteries due to their safety and high energy densities. Current research on SSLABs is mainly centered on solid‐state electrolytes (SSEs). Although SSEs exhibit excellent properties, such as good stability, high safety, and great mechanical strength, they also display several distinct weaknesses of low ionic conductivities, poor stabilities in air, and high interfacial impedances, which will require sustained attentions for further investigations. This review first overviews the development history of SSEs achieved in terms of Li–air batteries. Subsequently, the fundamental properties, preparation methods, merits and drawbacks of different SSEs, along with their use in SSLABs, and the optimization strategy, especially for the inorganic solid electrolytes, polymer electrolytes, and hybrid electrolytes are comprehensively summarized. Finally, the research progresses made with SSEs are outlined, and critical insights and approaches for the remaining challenges of electrolytes and commercial application of SSLABs are proposed, which include advanced characterization, combining experiments and artificial intelligence such as theoretical calculations, and constructing selective permeability membranes. It is expected that this timely review will provide researchers with an integrated, systematic, and in‐depth understanding of SSEs and guidelines for future research, thus further promoting the commercial application of SSLABs. [ABSTRACT FROM AUTHOR]

Sodium‐ion batteries (NIBs) have emerged as a promising alternative to commercial lithium‐ion batteries (LIBs) due to the similar properties of the Li and Na elements as well as the abundance and accessibility of Na resources. Most of the current research has been focused on the half‐cell system (using Na metal as the counter electrode) to evaluate the performance of the cathode/anode/electrolyte. The relationship between the performance achieved in half cells and that obtained in full cells, however, has been neglected in much of this research. Additionally, the trade‐off in the relationship between electrochemical performance and cost needs to be given more consideration. Therefore, systematic and comprehensive insights into the research status and key issues for the full‐cell system need to be gained to advance its commercialization. Consequently, this review evaluates the recent progress based on various cathodes and highlights the most significant challenges for full cells. Several strategies have also been proposed to enhance the electrochemical performance of NIBs, including designing electrode materials, optimizing electrolytes, sodium compensation, and so forth. Finally, perspectives and outlooks are provided to guide future research on sodium‐ion full cells. [ABSTRACT FROM AUTHOR]

Hydrogen‐bonded organic frameworks (HOFs) are considered as potential choice for future energy storage systems due to their adjustable chemistry, environment friendliness, and cost‐effectiveness. In this study, structurally stabilized and aldehyde‐tuned hydrogen‐bonded organic frameworks (HOFs‐8) are designed and prepared to contain arrayed electronegative sites for sodium‐ion storage. Benefitting from the flexible hydrogen bond and unique structural symmetry, HOFs‐8 can achieve efficient utilization of the active sites and fast transport of sodium ions and electrons. The HOFs‐8 electrode exhibits an impressive lifespan of 5000 cycles at 3.66 A g−1 (20 C). In situ Fourier Transform infrared spectroscopy (in situ FT‐IR) and ex situ X‐ray Photoelectron Spectroscopy (ex situ XPS) analyses are performed to illustrate the mechanism of sodium‐ion storage involving aldehyde‐tuned C═O. Additionally, flexible hydrogen bonds in HOFs materials with unique structural symmetries are investigated to elucidate the mechanism of hydrogen bonding for improving their electrochemical properties. Density functional theory (DFT) simulations verified that HOFs‐8 has excellent Na+ diffusion kinetics, enabling it to demonstrate outstanding rate capability. This work offers insight into the design of new electrodes and improved HOFs, which are expected to have tremendous potential in energy storage systems. [ABSTRACT FROM AUTHOR]

Zn deposition with a surface‐preferred (002) crystal plane has attracted extensive attention due to its inhibited dendrite growth and side reactions. However, the nucleation and growth of the Zn(002) crystal plane are closely related to the interfacial properties. Herein, oriented growth of Zn(002) crystal plane is realized on Ag‐modified surface that is directly visualized by in situ atomic force microscopy. A solid solution HCP‐Zn (~1.10 at. % solubility of Ag, 30 °C) is formed on the Ag coated Zn foil (Zn@Ag) and possesses the same crystal structure as Zn to reduce its nucleation barrier caused by their lattice mismatch. It merits oriented Zn deposition and corrosion‐resistant surface, and presents long cycling stability in symmetric cells and full cells coupled with V2O5 cathode. This work provides insights into interfacial regulation of Zn anodes for high‐performance aqueous zinc metal batteries. [ABSTRACT FROM AUTHOR]

Alloying‐type antimony (Sb) with high theoretical capacity is a promising anode candidate for both lithium‐ion batteries (LIBs) and sodium‐ion batteries (SIBs). Given the larger radius of Na+ (1.02 Å) than Li+ (0.76 Å), it was generally believed that the Sb anode would experience even worse capacity degradation in SIBs due to more substantial volumetric variations during cycling when compared to LIBs. However, the Sb anode in SIBs unexpectedly exhibited both better electrochemical and structural stability than in LIBs, and the mechanistic reasons that underlie this performance discrepancy remain undiscovered. Here, using substantial in situ transmission electron microscopy, X‐ray diffraction, and Raman techniques complemented by theoretical simulations, we explicitly reveal that compared to the lithiation/delithiation process, sodiation/desodiation process of Sb anode displays a previously unexplored two‐stage alloying/dealloying mechanism with polycrystalline and amorphous phases as the intermediates featuring improved resilience to mechanical damage, contributing to superior cycling stability in SIBs. Additionally, the better mechanical properties and weaker atomic interaction of Na−Sb alloys than Li−Sb alloys favor enabling mitigated mechanical stress, accounting for enhanced structural stability as unveiled by theoretical simulations. Our finding delineates the mechanistic origins of enhanced cycling stability of Sb anode in SIBs with potential implications for other large‐volume‐change electrode materials. [ABSTRACT FROM AUTHOR]

Sodium‐ion batteries (SIBs) with wide operating temperature are regarded as promising candidates for large‐scale energy storage systems. However, SIBs operating under elevated temperature aggravate the electrolyte decomposition with unstable cathode‐electrolyte interphase (CEI), causing a rapid capacity degradation. Herein, anion receptor tris(pentafluorophenyl)borane (TPFPB) is selected as electrolyte additive to construct robust NaF‐rich CEI. The strong interactions between anion and TPFPB via the electron‐deficient boron atoms weaken ClO4− solvation and promote the coordination capability between solvents and Na+ cations, demonstrating greatly improved oxidative stability. Na3V2(PO4)3 cathode in TPFPB‐containing electrolyte delivers long‐term stability with a capacity retention of 86.9% after 100 cycles at a high cut‐off voltage of 4.2 V (vs. Na+/Na) and a high temperature of 60 °C. Besides, TPFPB also works well with enhanced performance over a temperature range from −30 to 60 °C. This study proposes a prospective method by manipulating the solvation chemistry for constructing high‐temperature rechargeable SIBs. [ABSTRACT FROM AUTHOR]

Given the merits of affordable cost, superior low‐temperature performance, and advanced safe properties, sodium‐ion batteries (SIBs) have exhibited great development potential in large scale energy storage applications. Among various emerging carbonaceous anode materials applied for SIBs, hard carbon (HC) has recently gained significant attention regarding their relatively low cost, wide availability, and optimal overall performance. However, the insufficient initial Coulombic efficiency (ICE) of HC is the main bottlenecks, which is inevitably hindering their further commercial applications. Herein, an in‐depth holistic exposition about the reasons causing the unsatisfied ICE and the recent advances on effective improvement strategies are comprehensively summarized in this review, which have been divided into two aspects including the intrinsic property (degree of graphitization, pore structure, defect, et al.) and the extrinsic factor (electrolyte, electrode materials, et al.). In addition, future prospects and perspectives on HC to enable practical application in SIBs are also briefly outlined. [ABSTRACT FROM AUTHOR]

Sodium (Na) metal anodes are promising candidates for various batteries with high energy density and high‐power density, however, the dendrite growth of Na metal is impeding their practical applications. The binary alloy Na–K is in the liquid state at room temperature with a wide composition range, which renders it inherently free from solid dendrite growth. Whereas the application of Na–K alloy is plagued by the lack of a wettable matrix to immobilize the liquid metal. Herein, a facile method is reported to introduce oxygen‐rich functional groups into carbon fiber cloth (O‐CFC), which is initially Na–K phobic yet turns into superwetting after the treatment. The superwetting behavior of the O‐CFC can be attributed to the favorable enthalpy changes as a result of the introduction of O‐rich functional groups. The superwetting property of the O‐CFC exhibits good universality, which can be extended to melting Na and K metals. By adopting the superwetting O‐CFC as a host for liquid Na–K alloy, the liquid metal can be well retained in the matrix and deliver a stable cycling for >1600 h. The concept of enthalpy‐driven wettability regulation can be enlightening for the host material design of other liquid metals and alloys. [ABSTRACT FROM AUTHOR]

Sodium dual‐ion batteries (Na‐DIBs) have attracted increasing attention due to their high operative voltages and low‐cost raw materials. However, the practical applications of Na‐DIBs are still hindered by the issues, such as low capacity and poor Coulombic efficiency, which is highly correlated with the compatibility between electrode and electrolyte but rarely investigated. Herein, fluoroethylene carbonate (FEC) is introduced into the electrolyte to regulate cation/anion solvation structure and the stability of cathode/anode‐electrolyte interphase of Na‐DIBs. The FEC modulates the environment of PF6− solvation sheath and facilitates the interaction of PF6− on graphite. In addition, the NaF‐rich interphase caused by the preferential decomposition of FEC effectively inhibits side reactions and pulverization of anodes with the electrolyte. Consequently, Sb||graphite full cells in FEC‐containing electrolyte achieve an improved capacity, cycling stability and Coulombic efficiency. This work elucidates the underlying mechanism of bifunctional FEC and provides an alternative strategy of building high‐performance dual ion batteries. [ABSTRACT FROM AUTHOR]

In alkaline seawater electrolysis, the oxygen evolution reaction (OER) is greatly suppressed by the occurrence of electrode corrosion due to the formation of hypochlorite. Herein, a catalyst consisting of MoC nanowires modified with NiFe alloy nanoparticles (NiFe/MoC) on nickel foam (NF) is prepared. The optimized catalyst can deliver a large current density of 500 mA cm−2 at a very low overpotential of 366 mV in alkaline seawater, respectively, outperforming commercial IrO2. Remarkably, an electrolyzer assembled with NiFe/MoC/NF as the anode and NiMoN/NF as the cathode only requires 1.77 V to drive a current density of 500 mA cm−2 for alkaline seawater electrolysis, as well as excellent stability. Theory calculation indicates that the initial activity of NiFe/MoC is attributed to increased electrical conductivity and decreased energy barrier for OER due to the introduction of Fe. We find that the change of the catalyst in the composition occurred after the stability test; however, the reconstructed catalyst has an energy barrier close to that of the pristine one, which is responsible for its excellent long‐term stability. Our findings provide an efficient way to construct high‐performance OER catalysts for alkaline seawater splitting. [ABSTRACT FROM AUTHOR]

Sodium‐ion batteries (SIBs) present great appeal in various energy storage systems, especifically for stationary grid storage, on account of the abundance of sources and low cost. Unfortunately, the commercialization of SIBs is mainly limited by available electrode materials, especially for the cathodes. Prussian blue analogs (PBAs), emerge as a promising alternative for their structural feasibility in the application of SIBs. Decreasing the defects (vacancies and coordinated water) is an effective strategy to achieve superior electrochemical performance during the synthetic processes. Herein, we summarize crystal structures, synthetic methods, electrochemical mechanisms, and the influences of synthesis conditions of PBAs in detail. This comprehensive overview on the current research progresses of PBAs will give guides and directions to solve the existing problems for their application in SIBs. [ABSTRACT FROM AUTHOR]

The pursuit of high energy density while achieving long cycle life remains a challenge in developing transition metal (TM) oxide cathode materials for sodium‐ion batteries (SIBs). Here, we present a concept of precisely manipulating structural evolution via local coordination chemistry regulation to design high‐performance composite cathode materials. The controllable structural evolution process is realized by tuning magnesium content in Na0.6Mn1−xMgxO2, which is elucidated by a combination of experimental analysis and theoretical calculations. The substitution of Mg into Mn sites not only induces a unique structural evolution from layered–tunnel structure to layered structure but also mitigates the Jahn–Teller distortion of Mn3+. Meanwhile, benefiting from the strong ionic interaction between Mg2+ and O2−, local environments around O2− coordinated with electrochemically inactive Mg2+ are anchored in the TM layer, providing a pinning effect to stabilize crystal structure and smooth electrochemical profile. The layered–tunnel Na0.6Mn0.95Mg0.05O2 cathode material delivers 188.9 mAh g−1 of specific capacity, equivalent to 508.0 Wh kg−1 of energy density at 0.5C, and exhibits 71.3% of capacity retention after 1000 cycles at 5C as well as excellent compatibility with hard carbon anode. This work may provide new insights of manipulating structural evolution in composite cathode materials via local coordination chemistry regulation and inspire more novel design of high‐performance SIB cathode materials. [ABSTRACT FROM AUTHOR]

High‐voltage lithium‐ion batteries (LIBs) have attracted great attention due to their promising high energy density. However, severe capacity degradation is witnessed, which originated from the incompatible and unstable electrolyte‐electrode interphase at high voltage. Herein, a robust additive‐induced sulfur‐rich interphase is constructed by introducing an additive with ultrahigh S‐content (34.04 %, methylene methyl disulfonate, MMDS) in 4.6 V LiNi0.5Co0.2Mn0.3O2 (NCM523)||graphite pouch cell. The MMDS does not directly participate the inner Li+ sheath, but the strong interactions between MMDS and PF6− anions promote the preferential decomposition of MMDS and broaden the oxidation stability, facilitating the formation of an ultrathin but robust sulfur‐rich interfacial layer. The electrolyte consumption, gas production, phase transformation and dissolution of transition metal ions were effectively inhibited. As expected, the 4.6 V NCM523||graphite pouch cell delivers a high capacity retention of 87.99 % even after 800 cycles. This work shares new insight into the sulfur‐rich additive‐induced electrolyte‐electrode interphase for stable high‐voltage LIBs. [ABSTRACT FROM AUTHOR]

Prussian blue analogues (PBAs) have been regarded as promising cathode materials for alkali‐ion batteries owing to their high theoretical energy density and low cost. However, the high water and vacancy content of PBAs lower their energy density and bring safety issues, impeding their large‐scale application. Herein, a facile "potassium‐ions assisted" strategy is proposed to synthesize highly crystallized PBAs. By manipulating the dominant crystal plane and suppressing vacancies, the as‐prepared PBAs exhibit increased redox potential resulting in high energy density up to ≈450 Wh kg−1, which is at the same level of the well‐known LiFePO4 cathodes for lithium‐ion batteries. Remarkably, unconventional highly‐reversible phase evolution and redox‐active pairs were identified by multiple in situ techniques for the first time. The preferred guest‐ion storage sites and migration mechanism were systematically analysed through theoretical calculations. We believe these results could inspire the design of safe with high energy density. [ABSTRACT FROM AUTHOR]

The development of large‐scale energy storage systems (ESSs) aimed at application in renewable electricity sources and in smart grids is expected to address energy shortage and environmental issues. Sodium‐ion batteries (SIBs) exhibit remarkable potential for large‐scale ESSs because of the high richness and accessibility of sodium reserves. Using low‐cost and abundant elements in cathodes with long cycling stability is preferable for lowering expenses on cathodes. Many investigated cathodes for SIBs are dogged by structural and morphology changes, unstable interphases between the cathode and the electrolyte, and air sensitivity, causing unsatisfactory cycling performance. Therefore, understanding the mechanism of capacity degeneration in depth and developing precise solutions are critical for designing low‐cost cathodes that are highly stable under cycling. Herein, recent progress in long‐cycle‐life and low‐cost cathodes for SIBs is focused on, and a comprehensive discussion of the key points in SIBs toward large‐scale applications is provided. The roots of the unstable cycling performance of low‐cost cathodes are discussed. Also, effective strategies are summarized from the recent progress on long‐cycle‐life and low‐cost cathodes. This review is expected to encourage deeper investigation of long‐lifespan cathodes for SIBs, particularly for potential large‐scale industrialization. [ABSTRACT FROM AUTHOR]

Sodium‐ion batteries (SIBs) are considered as a low‐cost complementary or alternative system to prestigious lithium‐ion batteries (LIBs) because of their similar working principle to LIBs, cost‐effectiveness, and sustainable availability of sodium resources, especially in large‐scale energy storage systems (EESs). Among various cathode candidates for SIBs, Na‐based layered transition metal oxides have received extensive attention for their relatively large specific capacity, high operating potential, facile synthesis, and environmental benignity. However, there are a series of fatal issues in terms of poor air stability, unstable cathode/electrolyte interphase, and irreversible phase transition that lead to unsatisfactory battery performance from the perspective of preparation to application, outside to inside of layered oxide cathodes, which severely limit their practical application. This work is meant to review these critical problems associated with layered oxide cathodes to understand their fundamental roots and degradation mechanisms, and to provide a comprehensive summary of mainstream modification strategies including chemical substitution, surface modification, structure modulation, and so forth, concentrating on how to improve air stability, reduce interfacial side reaction, and suppress phase transition for realizing high structural reversibility, fast Na+ kinetics, and superior comprehensive electrochemical performance. The advantages and disadvantages of different strategies are discussed, and insights into future challenges and opportunities for layered oxide cathodes are also presented. [ABSTRACT FROM AUTHOR]

Hard carbon (HC) anodes have shown extraordinary promise for sodium‐ion batteries, but are limited to their poor initial coulombic efficiency (ICE) and low practical specific capacity due to the large amount of defects. These defects with oxygen containing groups cause irreversible sites for Na+ ions. Highly graphited carbon decreases defects, while potentially blocking diffusion paths of Na+ ions. Therefore, molecular‐level control of graphitization of hard carbon with open accessible channels for Na+ ions is key to achieve high‐performance hard carbon. Moreover, it is challenging to design a conventional method to obtain HCs with both high ICE and capacity. Herein, a universal strategy is developed as manganese ions‐assisted catalytic carbonization to precisely tune graphitization degree, eliminate defects, and maintain effective Na+ ions paths. The as‐prepared hard carbon has a high ICE of 92.05% and excellent cycling performance. Simultaneously, a sodium storage mechanism of "adsorption‐intercalation‐pore filling‐sodium cluster formation" is proposed, and a clear description given of the boundaries of the pore structure and the specific dynamic process of pore filling. [ABSTRACT FROM AUTHOR]

Layered transition metal oxide (NaxTMO2), being one of the most promising cathode candidates for sodium‐ion batteries (SIBs), have attracted intensive interest because of their nontoxicity, high theoretical capacities, and easy manufacturability. However, their physical and electrochemical properties of water sensitivity, sluggish Na+ transport kinetics, and irreversible multiple‐phase translations hinder the practical application. Here, a concept of surface lattice‐matched engineering is proposed based on in situ spinel interfacial reconstruction to design a spinel coating P2/P3 heterostructure cathode material with enhanced air stability, rate, and cycle performance. The novel structure and its formation process are verified by transmission electron microscopy and in situ high‐temperature X‐ray diffraction. The electrode exhibits an excellent rate performance with the highly reversible phase transformation demonstrated by in situ charging/discharging X‐ray diffraction. Additionally, even after a rigorous water sensitivity test, the electrode materials still retain almost the same superior electrochemical performance as the fresh sample. The results show that the surface spinel phase can play a vital role in preventing the ingress of water molecules, improving transport kinetics, and enhancing structural integrity for NaxTMO2 cathodes. The concept of surface lattice‐matched engineering based on in situ spinel interfacial reconstruction will be helpful for designing new ultra‐stable cathode materials for high‐performance SIBs. [ABSTRACT FROM AUTHOR]

Sodium‐ion batteries (SIBs) show tremendous potential for large‐scale energy storage systems due to the high abundance of sodium resources and potentially low cost. Among the discovered anode materials for SIBs, metal selenides with large theoretical capacities are considered as a promising candidate. Nevertheless, metal selenide‐based anodes are trapped by poor ionic/electronic conductivity, low initial Coulombic efficiency, and drastic volume changes during the (de)sodiation process. Herein, the differences in sodium‐storage mechanisms of different metal selenides are first analyzed. Subsequently, the specific challenges and corresponding modification strategies (such as nanostructure design, carbon modification, potential window regulation, electrolyte optimization, and constructing heterostructures) for metal selenides as SIB anodes are discussed in detail, and recent advances are also presented. Finally, the potential research directions of metal selenides in SIBs are comprehensively reviewed. It is believed that this review can provide constructive comments on the optimization and large‐scale application of high‐performance metal selenide‐based anode for SIBs. [ABSTRACT FROM AUTHOR]

Room‐temperature sodium–sulfur (RT‐Na/S) batteries are emerging as promising candidates for stationary energy‐storage systems, due to their high energy density, resource abundance, and environmental benignity. A better understanding of RT‐Na/S batteries in the view of the whole battery components is of essential importance for fundamental research and practical applications. In particular, the components other than sulfur cathodes in preventing the migration of polysulfides and accelerating the reaction kinetics have been greatly overlooked. Such a biased research trend is also adverse to the broader applications for RT‐Na/S batteries, which have long been ignored in previous reviews. Herein, approaches to the historical progress toward practical RT‐Na/S batteries through a "teamwork" perspective are comprehensively summarized, and balanced research trends are encouraged to enable practical RT‐Na/S batteries. In the meantime, the persisting issues, promising solutions, and practical applications of advanced sulfur host design, Na metal anode protection, electrolyte optimization, separator modification, and binder engineering are clearly emphasized. Finally, the device‐scale evaluation in practical parameters and advanced characterization tools are thoroughly provided. This review aims to provide the "teamwork" perspective on the whole‐cell design and fundamental guidelines that can shed light on research directions for practical RT‐Na/S batteries. [ABSTRACT FROM AUTHOR]

Sodium‐ion oxide cathodes with triphase heterostructures have attracted intensive attention, since the sodium‐storage performance can be enhanced by utilizing the synergistic effect of different phases. However, the composite structures generally suffer from multiple irreversible phase transitions and high lattice strain because of interlayer‐gliding during the charge/discharge process. Here, the concept of strain engineering via manipulating the local chemistry of heterostructured oxide cathode is proposed to regulate the relevant physical and chemical properties, resulting in highly reversible structural evolution (P2/P3/spinel → P2/P3″/spinel) and low intrinsic stress in the potential window of 1.5–4.0 V. Also, the simple structural evolution at a relatively high cut‐off potential of 4.3 V can be detected by in situ X‐ray diffraction and other electrochemical characterization techniques during Na+ extraction/insertion. Meanwhile, the electrode exhibits a high reversible capacity (169.4 mAh g−1 at 0.2 C) and excellent rate performance from 1.5 to 4.3 V. Overall, this study reveals the mechanisms of regulating local chemistry to realize strain engineering of the cathode materials and paves the way for the further improvement of high‐performance sodium‐ion batteries. [ABSTRACT FROM AUTHOR]

Sodium metal batteries are recognized as promising candidates for next‐generation energy storage devices, as a result of their high energy density, low redox potential, and cheap material price. Na metal anodes, however, generally exhibit notorious problems, including progressively thickened interfaces with active Na loss and Na metal dendrite growth with safety hazards. Herein, a lightweight aerogel consisting of MgF2 nanocrystals grown on a reduced graphene oxide (RGO) aerogel matrix (MgF2@RGO) is rationally designed as a multifunctional host material for Na metal anodes. The MgF2 nanocrystals can be electrochemically converted in situ into Mg and NaF nanograins during the first Na plating process, in which the Mg works as sodiophilic nucleation seeds for Na plating and NaF plays a key role in suppressing Na dendrite growth. Significantly, the Na metal anodes with the MgF2@RGO aerogel host deliver significantly enhanced Coulombic efficiency and dramatically improved cycling stability for more than 1600 h. The morphology evolution confirms the advantages of the Na metal anode with the MgF2@RGO host, which exhibits dense and flat interfaces. By pairing with the Na3V2(PO4)3 cathode, the Na metal batteries achieve stable cycling and good rate capability, suggesting the potential of the Na/MgF2@RGO anode for practical applications. [ABSTRACT FROM AUTHOR]

Prussian blue analogues (PBAs) have attracted extensive attention as cathode materials in sodium‐ion batteries (SIBs) due to their low cost, high theoretical capacity, and facile synthesis process. However, it is of great challenge to control the crystal vacancies and interstitial water formed during the aqueous co‐precipitation method, which are also the key factors in determining the electrochemical performance. Herein, an antioxidant and chelating agent co‐assisted non‐aqueous ball‐milling method to generate highly‐crystallized Na2‐xFe[Fe(CN)6]y with hollow structure is proposed by suppressing the speed and space of crystal growth. The as‐prepared Na2‐xFe[Fe(CN)6]y hollow nanospheres show low vacancies and interstitial water content, leading to a high sodium content. As a result, the Na‐rich Na1.51Fe[Fe(CN)6]0.87·1.83H2O hollow nanospheres exhibit a high initial Coulombic efficiency, excellent cycling stability, and rate performance via a highly reversible two‐phase transition reaction confirmed by in situ X‐ray diffraction. It delivers a specific capacity of 124.2 mAh g−1 at 17 mA g−1, presenting ultra‐high rate capability (84.1 mAh g−1 at 3400 mA g−1) and cycling stability (65.3% capacity retention after 1000 cycles at 170 mA g−1). Furthermore, the as‐reported non‐aqueous ball‐milling method could be regarded as a promising method for the scalable production of PBAs as cathode materials for high‐performance SIBs. [ABSTRACT FROM AUTHOR]

Organic materials have attracted much attention in sodium ion batteries (SIBs) because of their advantages such as being environmentally benign and having high designability. Capacities and cycle life of organic materials are the most important parameters in most research which has been paid much effort to obtain an impressive electrochemical performance on the material level, and the sodium‐detachable ability of these materials to directly match with the sodium‐free anode is neglected. In this work, one organic sodium salt (C6H2Na2O6) exhibits the unique ability (charging first in half cell) unlike other reported organic cathode materials (normally discharging first) for SIBs. The redox mechanism and structure change are investigated by in situ and ex situ tests to give a better understanding for C6H2Na2O6. Satisfying electrochemical performance (74% capacity retention after 600 cycles at 0.05 A g−1 and 63% capacity retention at 5 A g−1 when compared with capacity at 0.05 A g−1) is achieved by the C6H2Na2O6 electrode. In addition, matched with hard carbon, full cells are assembled successfully like other transition metal containing cathode materials because C6H2Na2O6 electrode can deliver its sodium ions to a sodium‐free anode directly without any presodiation. [ABSTRACT FROM AUTHOR]

The shell structure design has been recognized as a highly efficient strategy to buffer the severe volume expansion and consecutive pulverization of conversion‐type anodes. Nevertheless, construction of a functional shell with a stabilized structure that meets the demands of both high electronic conductivity and feasible pathways for Na+ ions has been a challenge so far. Herein, we design a two‐in‐one shell configuration for bimetal selenides to achieve fast sodium storage within broadened voltage windows. The hybridized shell, which benefits from the combination of titanium dioxide quantum dots and amorphous carbon, can not only effectively buffer the strain and maintain structural integrity but also allow facile and reversible transport of electrons and Na+ uptake for electrode materials during sodiation/desodiation processes, resulting in increased reaction kinetics and diffusion of sodium ions, conferring many benefits to the functionality of conversion‐type electrode materials. As a representative material, Ni‐CoSe2 with such structural engineering shows a reversible capacity of 515 mAh g−1 at 0.1 A g−1 and a stable capacity of 416 mAh g−1 even at 6.4 A g−1; more than 80% of the capacity at 0.1 A g−1 could be preserved, so that this strategy holds great promise for designing fast‐charging conversion‐type anodes in the future. [ABSTRACT FROM AUTHOR]

Carbonaceous materials are considered strong candidates as anode materials for sodium‐ion batteries (SIBs), which are expected to play an indispensable role in the carbon‐neutral era. Herein, novel braided porous carbon fibres (BPCFs) are prepared using the chemical vapour deposition (CVD) method. The BPCFs possess interwoven porous structures and abundant vacancies. The growth mechanism of the BPCFs can be attributed to the polycrystalline transformation of the nanoporous copper catalyst in the early stage of CVD process. Density functional theory calculations suggest that the Na+ adsorption energies of the mono‐vacancy edges of the BPCFs (−1.22 and −1.09 eV) are lower than that of an ideal graphene layer (−0.68 eV), clarifying in detail the adsorption‐dominated sodium storage mechanism. Hence, the BPCFs as an anode material present an outstanding discharge capacity of 401 mAh g−1 at 0.1 A g−1 after 500 cycles. Remarkably, this BPCFs anode, under high‐mass‐loading of 5 mg cm−2, shows excellent long‐term cycling ability with a reversible capacity of 201 mAh g−1 at 10 A g−1 over 1000 cycles. This study provided a novel strategy for the development of high‐performance carbonaceous materials for SIBs. [ABSTRACT FROM AUTHOR]

The shuttling behavior and sluggish conversion kinetics of intermediate lithium polysulfides (LiPS) represent the main obstacles to the practical application of lithium–sulfur batteries (LSBs). Herein, an innovative sulfur host is proposed, based on an iodine‐doped bismuth selenide (I‐Bi2Se3), able to solve these limitations by immobilizing the LiPS and catalytically activating the redox conversion at the cathode. The synthesis of I‐Bi2Se3 nanosheets is detailed here and their morphology, crystal structure, and composition are thoroughly. Density‐functional theory and experimental tools are used to demonstrate that I‐Bi2Se3 nanosheets are characterized by a proper composition and micro‐ and nano‐structure to facilitate Li+ diffusion and fast electron transportation, and to provide numerous surface sites with strong LiPS adsorbability and extraordinary catalytic activity. Overall, I‐Bi2Se3/S electrodes exhibit outstanding initial capacities up to 1500 mAh g−1 at 0.1 C and cycling stability over 1000 cycles, with an average capacity decay rate of only 0.012% per cycle at 1 C. Besides, at a sulfur loading of 5.2 mg cm−2, a high areal capacity of 5.70 mAh cm−2 at 0.1 C is obtained with an electrolyte/sulfur ratio of 12 µL mg−1. This work demonstrated that doping is an effective way to optimize the metal selenide catalysts in LSBs. [ABSTRACT FROM AUTHOR]

Prussian blue analogs (PBAs) are promising cathode materials for sodium‐ion batteries (SIBs) due to their low‐cost, similar energy density comparable with that of LiFePO4 in lithium‐ion batteries, and long cycle life. Nevertheless, crystal water (≈10 wt%) in PBAs from aqueous synthesis environments can bring significant side effects in real SIBs, especially for calendar life and high temperature storage performance. Therefore, it is of great importance to eliminate crystal water in PBAs for future commercial applications. Herein, a facile heat‐treatment method is reported in order to remove water from Fe‐based PBAs. Although the heat‐treated sample can be easily rehydrated in air, it still exhibits a stable cycling performance over 2000 times under controlled charge cut‐off voltage. In situ synchrotron high‐temperature powder X‐ray diffraction demonstrates that the as‐prepared sample is maintained at a new trigonal phase after dehydration. Moreover, the redox reaction of low‐spin Fe2+/Fe3+ is activated and the high‐temperature storage performance of as‐prepared sample is significantly improved after removal of water. [ABSTRACT FROM AUTHOR]

High energy density and long‐term cycling stability are crucial factors for the commercialization of sodium batteries in large scale. In this regard, cathode materials that can operate at high voltage have attracted great interest owing to their high energy density. However, traditional electrolytes cannot be used in high‐voltage sodium batteries due to their limited oxidative stability. Therefore, there is a great challenge to develop appropriate electrolytes for high‐voltage cathode materials. Herein, a diluted fluoroethylene carbonate (FEC)‐based electrolyte (1 m NaPF6 in FEC/DMC = 2/8 by volume) is designed for Na4Co3(PO4)2P2O7 (NCPP) cathode with a high operation voltage of 4.7 V to achieve superior electrochemical performance with a capacity retention of 90.10% after 500 cycles at 0.5 C and capacity retention of 89.99% after 1000 cycles at 1 C. The excellent electrochemical performance of the NCPP||Na cells can be attributed to the formation of inorganic and robust NaF‐rich cathode electrolyte interphase and F‐rich solid electrolyte interface on high voltage NCPP cathode and Na metal anode, respectively. This work points out a very promising strategy to develop high‐voltage sodium batteries toward practical applications. [ABSTRACT FROM AUTHOR]

The exploration of facile, low‐cost, and universal synthetic strategies for high‐performance aqueous energy storage is extremely urgent. The electrochemical activation tactic is an emerging synthetic technique that can turn inert or weakly active substances into highly active materials for aqueous energy storage via in situ or ex situ electrochemical treatment, which is receiving increasing attention due to its advantages of facile operation, variable control, high efficiency, flexibility, and wide applicability. This review first discusses the definition and general implementing methods of the electrochemical activation tactic, as well as the fundamental activation mechanisms, and then summarizes its applications in various aqueous systems, including rechargeable batteries and electrochemical capacitors with different charge carriers. The remaining challenges, potential solutions, and further perspectives are discussed finally. It is believed that this review will provide a timely summary and new inspiration for cutting‐edge research on advanced aqueous energy storage devices. [ABSTRACT FROM AUTHOR]

It is vital to dynamically regulate S activity to achieve efficient and stable room‐temperature sodium–sulfur (RT/Na−S) batteries. Herein, we report using cobalt sulfide as an electron reservoir to enhance the activity of sulfur cathodes, and simultaneously combining with cobalt single atoms as double‐end binding sites for a stable S conversion process. The rationally constructed CoS2 electron reservoir enables the straight reduction of S to short‐chain sodium polysulfides (Na2S4) via a streamlined redox path through electron transfer. Meanwhile, cobalt single atoms synergistically work with the electron reservoir to reinforce the streamlined redox path, which immobilize in situ formed long‐chain products and catalyze their conversion, thus realizing high S utilization and sustainable cycling stability. The as‐developed sulfur cathodes exhibit a superior rate performance of 443 mAh g−1 at 5 A g−1 with a high cycling capacity retention of 80 % after 5000 cycles at 5 A g−1. [ABSTRACT FROM AUTHOR]

Prussian blue analogs (PBAs), as promising cathode materials for sodium‐ion batteries (SIBs), have received extensive research interest due to their appealing characteristics, e.g., the low cost of their raw materials, easy manufacturing, open frameworks, and high theoretical specific capacity. There are some challenges for PBAs cathodes, however, hindering their performance output, making them currently unacceptable for practical applications. To improve the performance and cycling stability of PBAs, a clear in‐depth understanding of the relationship of their electrochemical reaction process to their ion insertion/extraction mechanisms and structural evolution is extremely important. Nowadays, advanced characterization techniques have become an important tool to guide the construction of high‐performance PBAs cathodes. In this review, the various advances by using advanced characterization techniques to reveal the reaction mechanisms for PBAs cathodes are summarized and discussed. By appreciating how the advanced characterization techniques to guide fabrication of high‐performance PBAs or reveal their detailed reaction mechanisms, it is hoped that this review can assist readers to find more valuable and advanced technologies to help to resolve some key problems and enhance their performance so as to accelerate the practical application of PBAs cathode for SIBs. [ABSTRACT FROM AUTHOR]

Organic electroactive compounds hold great potential to act as cathode material for organic sodium‐ion batteries (OSIBs) because of their environmental friendliness, sustainability, and high theoretical capacity. Although some organic electrodes have been developed with good performance, their practical application is still obstructed by some inherent drawbacks such as low conductivity and solubility in organic electrolytes. In addition, research on OSIBs has been mainly focused on the performance of electrodes on the material level and neglected the trade‐off relationship between the high redox potentials and specific capacities. Almost all organic cathodes used in OSIBs lack the ability to be charged first in half‐cells because of the absence of detachable sodium ions, resulting in low attractiveness when assembling full cells with hard carbon as anode. Here, this review presents several existing reaction mechanisms in OSIBs and designs of organic cathode materials. Furthermore, strategies are proposed in order to provide guidelines for improving their performance according to some critical parameters (output voltage, specific capacity, and cycle life) in potential practical OSIBs, and some accounts of organic materials assembled in full cells are summarized. Finally, the challenges and prospects of organic electrodes for OSIBs are also discussed in this review. [ABSTRACT FROM AUTHOR]

The practical application of lithium–sulfur batteries is hampered by the sluggish redox reaction kinetics and severe lithium polysulfide (LiPS) migration, especially under high sulfur loading and lean electrolyte scenarios. Strategies to catalyze the sulfur liquid/solid conversion within a "hermetic" nano‐container have been proposed, where the LiPS migration and sluggish reaction kinetics can be simultaneously addressed. Herein, to realize rapid LiPS conversion and slow LiPS migration, the sulfur species are packed by a hermetic catalytic interface, constructed by the phosphorene/graphene heterostructure. The 2D phosphorene/graphene stacking has two unique benefits: 1) a direct electron transfer avoiding any insulating media, resulting in an exceptional catalytic effect on LiPS conversion; ii) favorable charge rearrangement that enhances chemisorption toward LiPS and limits LiPS crossover. The proposed highly flexible hermetic interface with strong van der Waals serves as a bifunctional nano‐container to pack sulfur species and promote sulfur redox reactions, which gives rise to excellent battery performances: a high areal capacity of 5.57 mAh cm−2 under a low electrolyte/sulfur ratio of 5.7 mL g−1. This work affords a coupling strategy that embraces interfacial and structural engineering to promote kinetic reactions of sulfur conversions under electrolyte‐lean conditions. [ABSTRACT FROM AUTHOR]

Highly efficient electrocatalysts for the oxygen evolution reaction (OER) are very important for various energy storage and conversion systems such as water splitting devices and metal‐air batteries. However, developing OER electrocatalysts with high activity and excellent stability at a high current density remains a considerable challenge. Herein, a facile room‐temperature‐stirring strategy is described to obtain FeCoNi layered double hydroxide nanocages (FeCoNi‐LDHs) using a metal–organic framework as a precursor. The FeCoNi‐LDHs have hollow features, while their walls are assembled with ultrathin layered hydroxide nanosheets. By designing a unique structure and tuning the composition, high activity and robust long‐term stability of the FeCoNi‐LDHs for the OER outperform IrO2, used as the reference catalyst. The as‐obtained high electrochemically active surface area and the decreased transfer resistance are ascribed to the significantly improved activity. Density functional theory calculations suggest that the introduction of Fe can fine‐tune the electronic structure and decrease the Gibbs free energy difference of the rate‐determining step (ΔG3), improving the intrinsic activity of FeCoNi‐LDHs toward the OER. Furthermore, the proposed room‐temperature‐stirring strategy can be easily scaled up to more than 10 grams of nanocages through a single batch reaction process, demonstrating the large‐scale applicability of the catalysts. [ABSTRACT FROM AUTHOR]

The safety of energy storage equipment has always been a stumbling block to the development of battery, and sodium ion battery is no exception. However, as an ultimate solution, the use of non‐flammable electrolyte is susceptible to the side effects, and its poor compatibility with electrode, causing failure of batteries. Here, we report a non‐flammable electrolyte design to achieve high‐performance sodium ion battery, which resolves the dilemma via regulating the solvation structure of electrolyte by hydrogen bonds and optimizing the electrode–electrolyte interphase. The reported non‐flammable electrolyte allows stable charge‐discharge cycling of both sodium vanadium phosphate@hard carbon and Prussian blue@hard carbon full pouch cell for more than 120 cycles with a capacity retention of >85 % and high cycling Coulombic efficiency (99.7 %). [ABSTRACT FROM AUTHOR]

Recently, environmental degradation along with the energy crisis has led to an urgent necessity to develop renewable and clean energy storage devices. The sodium ion batteries (SIBs) have become promising candidates in the whole energy storage system, due to its rich and low‐cost sodium resources. To accelerate the commercialization of SIBs, the energy density of SIBs needs to be further improved. Increasing the operating voltage of SIBs is considered to be an effective method, which requires stable and high‐voltage cathode materials. Comparatively, polyanionic sulfate materials (PSMs) with stable skeletons, adjustable structures, operational safety, and the high electronegativity of SO42− are believed to be the most promising high‐energy‐cathodes. In this review, recent progresses on several typical sulfates for SIBs are summarized. What's more, based on their intrinsic characteristics, the structures and kinetic behaviors of PSMs are also discussed. Reported measures to optimize their electrochemical performances and structural stability are summarized and reviewed. The key challenges and corresponding opportunities for PSMs are also discussed. The insights presented in this review may be a guide for designing and developing stable and practical PSMs for room‐temperature SIBs, which is conducive to promoting their industrialization. [ABSTRACT FROM AUTHOR]

The shuttle effect and sluggish conversion kinetics of lithium polysulfides (LiPS) hamper the practical application of lithium–sulfur batteries (LSBs). Toward overcoming these limitations, herein an in situ grown C2N@NbSe2 heterostructure is presented with remarkable specific surface area, as a Li–S catalyst and LiPS absorber. Density functional theory (DFT) calculations and experimental results comprehensively demonstrate that C2N@NbSe2 is characterized by a suitable electronic structure and charge rearrangement that strongly accelerates the LiPS electrocatalytic conversion. In addition, heterostructured C2N@NbSe2 strongly interacts with LiPS species, confining them at the cathode. As a result, LSBs cathodes based on C2N@NbSe2/S exhibit a high initial capacity of 1545 mAh g−1 at 0.1 C. Even more excitingly, C2N@NbSe2/S cathodes are characterized by impressive cycling stability with only 0.012% capacity decay per cycle after 2000 cycles at 3 C. Even at a sulfur loading of 5.6 mg cm−2, a high areal capacity of 5.65 mAh cm−2 is delivered. These results demonstrate that C2N@NbSe2 heterostructures can act as multifunctional polysulfide mediators to chemically adsorb LiPS, accelerate Li‐ion diffusion, chemically catalyze LiPS conversion, and lower the energy barrier for Li2S precipitation/decomposition, realizing the "adsorption‐diffusion‐conversion" of polysulfides. [ABSTRACT FROM AUTHOR]

Intercalation‐based anode materials can be considered as the most promising anode candidates for large‐scale sodium‐ion batteries (SIBs), owing to their long‐term cycling stability and environmental friendliness, as well as their natural abundance. Nevertheless, their low energy density, low initial coulombic efficiency, and poor cycling lifespan, as well as sluggish sodium diffusion dynamics are still the main issues for the application of intercalation‐based anode materials in SIBs in terms of meeting the benchmark requirements for commercialization. Over the past few years, tremendous efforts have been devoted to improving the performance of SIBs. In this Review, recent progress in the development of intercalation‐based anode materials, including TiO2, Li4Ti5O12, Na2Ti3O7, and NaTi2(PO4)3, is summarized in terms of their sodium storage performance, critical issues, sodiation/desodiation behavior, and effective strategies to enhance their electrochemical performance. Additionally, challenges and perspectives are provided to further understand these intercalation‐based anode materials. [ABSTRACT FROM AUTHOR]