CuF2 as Reversible Cathode for Fluoride Ion Batteries

In the search for novel battery systems with high energy density and low cost, fluoride ion batteries have recently emerged as a further option to store electricity with very high volumetric energy densities. Among metal fluorides, CuF₂ is an intriguing candidate for cathode materials due to its high specific capacity and high theoretical conversion potential. Here, the reversibility of CuF₂ as a cathode material in the fluoride ion battery system employing a high F^? conducting tysonite‐type La_0.9Ba_0.1F_2.9 as an electrolyte and a metallic La as an anode is investigated. For the first time, the reversible conversion mechanism of CuF₂ with the corresponding variation in fluorine content is reported on the basis of X‐ray photoelectron spectroscopy measurements and cathode/electrolyte interfacial studies by transmission electron microscopy. Investigation of the anode/electrolyte interface reveals structural variation upon cycling with the formation of intermediate layers consisting of i) hexagonal LaF₃ and monoclinic La₂O₃ phases in the pristine interface; ii) two main phases of distorted orthorhombic LaF₃ and monoclinic La₂O₃ after discharging; and iii) a tetragonal lanthanum oxyfluoride (LaOF) phase after charging. The fading mechanism of the cell capacity upon cycling can be explained by Cu diffusion into the electrolyte and side reactions due to the formation of the LaOF compound.     

Ultrafine Amorphous SnOx Embedded in Carbon Nanofiber/Carbon Nanotube Composites for Li‐Ion and Na‐Ion Batteries

Core–shell‐structured, ultrafine SnO_x/carbon nanofiber (CNF)/carbon nanotube composite films are in situ synthesized by electrospinning through a dual nozzle. The carbon shell layer functions as a buffer to prevent the separation of SnO_x particles from the CNF core, allowing full utilization of high‐capacity SnO_x in both Li‐ion and Na‐ion batteries. The composite electrodes reveal an anomalous Li‐ and Na‐ion storage mechanism where all the intermediate phases, like Li_xSn and Na_xSn alloys, maintain amorphous states during the entire charge/discharge process. The uniform dispersion on an atomic scale and the amorphous state of the SnO_x particles remain intact in the carbon matrix without growth or crystallization even after 300 cycles, which is responsible for sustaining excellent capacity retention of the electrodes. These discoveries not only shed new insights into fundamental understanding of the electrochemical behavior of SnO_x electrodes but also offer a potential strategy to improve the cyclic stability of other types of alloy anodes that suffer from rapid capacity decays due to large volume changes.     

A Family of High‐Performance Cathode Materials for Na‐ion Batteries,Na3(VO1−xPO4)2 F1+2x (0 ≤ x ≤ 1): Combined First‐Principles and Experimental Study

Room‐temperature Na‐ion batteries (NIBs) have recently attracted attention as potential alternatives to current Li‐ion batteries (LIBs). The natural abundance of sodium and the similarity between the electrochemical properties of NIBs and LIBs make NIBs well suited for applications requiring low cost and long‐term reliability. Here, the first successful synthesis of a series of Na₃(VO_1?x PO₄)₂F_1+2x (0 ≤ x ≤ 1) compounds as a new family of high‐performance cathode materials for NIBs is reported. The Na₃(VO_1?x PO₄)₂F_1+2x series can function as high‐performance cathodes for NIBs with high energy density and good cycle life, although the redox mechanism varies depending on the composition. The combined first‐principles calculations and experimental analysis reveal the detailed structural and electrochemical mechanisms of the various compositions in solid solutions of Na₃(VOPO₄)₂F and Na₃V₂(PO₄)₂F₃. The comparative data for the Na _y (VO_1?x PO₄)₂F_1+2x electrodes show a clear relationship among V³⁺/V⁴⁺/V⁵⁺ redox reactions, Na⁺?Na⁺ interactions, and Na⁺ intercalation mechanisms in NIBs. The new family of high‐energy cathode materials reported here is expected to spur the development of low‐cost, high‐performance NIBs.     

Three Electron Reversible Redox Reaction in Sodium Vanadium Chromium Phosphate as a High‐Energy‐Density Cathode for Sodium‐Ion Batteries

A sodium‐ion battery operating at room temperature is of great interest for large‐scale stationary energy storage because of its intrinsic cost advantage. However, the development of a high capacity cathode with high energy density remains a great challenge. In this work, sodium super ionic conductor‐structured Na₃V_2?xCr_x(PO₄)₃ is achieved through the sol–gel method; Na₃V_1.5Cr_0.5(PO₄)₃ is demonstrated to have a capacity of 150 mAh g^?1 with reversible three‐electron redox reactions after insertion of a Na⁺, consistent with the redox couples of V²⁺/³⁺, V³⁺/⁴⁺, and V⁴⁺/⁵⁺. Moreover, a symmetric sodium‐ion full cell utilizing Na₃V_1.5Cr_0.5(PO₄)₃ as both the cathode and anode exhibits an excellent rate capability and cyclability with a capacity of 70 mAh g^?1 at 1 A g^?1. Ex situ X‐ray diffraction analysis and in situ impedance measurements are performed to reveal the sodium storage mechanism and the structural evolution during cycling.     

Constructing Na‐Ion Cathodes via Alkali‐Site Substitution

Na‐ion batteries have experienced rapid development over the past decade and received significant attention from the academic and industrial communities. Although a large amount of effort has been made on material innovations, accessible design strategies on peculiar structural chemistry remain elusive. An approach to in situ construction of new Na‐based cathode materials by substitution in alkali sites is proposed to realize long‐term cycling stability and high‐energy density in low‐cost Na‐ion cathodes. A new compound, [K_0.444(1)Na_1.414(1)][Mn_3/4Fe_5/4](CN)₆, is obtained through a rational control of K⁺ content from electrochemical reaction. Results demonstrate that the remaining K⁺ (≈0.444 mol per unit) in the host matrix can stabilize the intrinsic K‐based structure during reversible Na⁺ extraction/insertion process without the structural evolution to the Na‐based structure after cycles. Thereby, the as‐prepared cathode shows the remarkably enhanced structural stability with the capacity retention of >78% after 1800 cycles, and a higher average operation voltage of ≈3.65 V versus Na⁺/Na, directly contrasting the non‐alkali‐site‐substitution cathode materials. This provides new insights into alkali‐site‐substitution constructing advanced Na‐ion cathode materials.     

Layer‐Based Heterostructured Cathodes for Lithium‐Ion and Sodium‐Ion Batteries

A critical bottleneck that hinders major performance improvement in lithium‐ion and sodium‐ion batteries is the inferior electrochemical activity of their cathode materials. While significant research progresses have been made, conventional single‐phase cathodes are still limited by intrinsic deficiencies such as low reversible capacity, enormous initial capacity loss, rapid capacity decay, and poor rate capability. In the past decade, layer‐based heterostructured cathodes acquired by combining multiple crystalline phases have emerged as candidates with a huge potential to realize performance breakthrough. Herein, recent studies on the structural properties, electrochemical behaviors, and synthesis route optimizations of these heterostructured cathodes are summarized for in‐depth discussions. Particular attention is paid to the latest mechanism discoveries and performance achievements. This review thus aims to promote a deeper understanding of the correlation between the crystal structure of cathodes and their electrochemical behavior, and offers guidance to design advance cathode materials from the aspect of crystal structure engineering.     

Novel Cathode Materials for Na‐Ion Batteries Composed of Spoke‐Like Nanorods of Na[Ni0.61Co0.12Mn0.27]O2 Assembled in Spherical Secondary Particles

The development of high‐energy and high‐power density sodium‐ion batteries is a great challenge for modern electrochemistry. The main hurdle to wide acceptance of sodium‐ion batteries lies in identifying and developing suitable new electrode materials. This study presents a composition‐graded cathode with average composition Na[Ni_0.61Co_0.12Mn_0.27]O₂, which exhibits excellent performance and stability. In addition to the concentration gradients of the transition metal ions, the cathode is composed of spoke‐like nanorods assembled into a spherical superstructure. Individual nanorod particles also possess strong crystallographic texture with respect to the center of the spherical particle. Such morphology allows the spoke‐like nanorods to assemble into a compact structure that minimizes its porosity and maximizes its mechanical strength while facilitating Na⁺‐ion transport into the particle interior. Microcompression tests have explicitly verified the mechanical robustness of the composition‐graded cathode and single particle electrochemical measurements have demonstrated the electrochemical stability during Na⁺‐ion insertion and extraction at high rates. These structural and morphological features contribute to the delivery of high discharge capacities of 160 mAh (g oxide)^?1 at 15 mA g^?1 (0.1 C rate) and 130 mAh g^?1 at 1500 mA g^?1 (10 C rate). The work is a pronounced step forward in the development of new Na ion insertion cathodes with a concentration gradient.     

A General Metal‐Organic Framework (MOF)‐Derived Selenidation Strategy for In Situ Carbon‐Encapsulated Metal Selenides as High‐Rate Anodes for Na‐Ion Batteries

On account of increasing demand for energy storage devices, sodium‐ion batteries (SIBs) with abundant reserve, low cost, and similar electrochemical properties have the potential to partly replace the commercial lithium‐ion batteries. In this study, a facile metal‐organic framework (MOF)‐derived selenidation strategy to synthesize in situ carbon‐encapsulated selenides as superior anode for SIBs is rationally designed. These selenides with particular micro‐ and nanostructured features deliver ultrastable cycling performance at high charge–discharge rate and demonstrate ultraexcellent rate capability. For example, the uniform peapod‐like Fe₇Se₈@C nanorods represent a high specific capacity of 218 mAh g^?1 after 500 cycles at 3 A g^?1 and the porous NiSe@C spheres display a high specific capacity of 160 mAh g^?1 after 2000 cycles at 3 A g^?1. The current simple MOF‐derived method could be a promising strategy for boosting the development of new functional inorganic materials for energy storage, catalysis, and sensors.     

Conversion‐Type MnO Nanorods as a Surprisingly Stable Anode Framework for Sodium‐Ion Batteries

The emergence of nanomaterials in the past decades has greatly advanced modern energy storage devices. Nanomaterials can offer high capacity and fast kinetics yet are prone to rapid morphological evolution and degradation. As a result, they are often hybridized with a stable framework in order to gain stability and fully utilize its advantages. However, candidates for such framework materials are rather limited, with carbon, conductive polymers, and Ti‐based oxides being the only choices; note these are all inactive or intercalation compounds. Conventionally, alloying‐/conversion‐type electrodes, which are thought to be electrochemically unstable by themselves, have never been considered as framework materials. This concept is challenged. Successful application of conversion‐type MnO nanorod as a anode framework for high‐capacity Mo₂C/MoO_x nanoparticles has been demonstrated in sodium‐ion batteries. Surprisingly, it can stably deliver 110 mAh g^?1 under extremely high rate of 8000 mA g^?1 (≈70 C) over 40 000 cycles with no capacity decay. More generally, this is considered as a proof of concept and much more alloying‐/conversion‐type materials are expected to be explored for such applications.     

Anodic Synthesis of Hierarchical SnS/SnOx Hollow Nanospheres and Their Application for High‐Performance Na‐Ion Batteries

Constructing hollow nanostructures is attractive for both fundamental research and practical applications. However, how to prepare hollow nanostructures in a simple, scalable, and cost‐effective way still remains a great challenge. In this study, for the first time, the anodization technique is applied to construct hollow nanostructures. Specifically, hollow nanospheres of SnS/SnO_x with a hierarchical porous structure are self‐assembled directly on the Sn substrate, via a convenient one‐step anodization method. When applied for sodium‐ion batteries, the thus fabricated SnS/SnO_x hollow nanospheres on the substrate readily serve as a binder‐free electrode, delivering remarkably high cycling stability and rate capability.     

Prussian Blue@C Composite as an Ultrahigh‐Rate and Long‐Life Sodium‐Ion Battery Cathode

Rechargeable sodium ion batteries (SIBs) are surfacing as promising candidates for applications in large‐scale energy‐storage systems. Prussian blue (PB) and its analogues (PBAs) have been considered as potential cathodes because of their rigid open framework and low‐cost synthesis. Nevertheless, PBAs suffer from inferior rate capability and poor cycling stability resulting from the low electronic conductivity and deficiencies in the PBAs framework. Herein, to understand the vacancy‐impacted sodium storage and Na‐insertion reaction kinetics, we report on an in‐situ synthesized PB@C composite as a high‐performance SIB cathode. Perfectly shaped, nanosized PB cubes were grown directly on carbon chains, assuring fast charge transfer and Na‐ion diffusion. The existence of [Fe(CN)₆] vacancies in the PB crystal is found to greatly degrade the electrochemical activity of the Fe^LS(C) redox couple via first‐principles computation. Superior reaction kinetics are demonstrated for the redox reactions of the Fe^HS(N) couple, which rely on the partial insertion of Na ions to enhance the electron conduction. The synergistic effects of the structure and morphology results in the PB@C composite achieving an unprecedented rate capability and outstanding cycling stability (77.5 mAh g^?1 at 90 C, 90 mAh g?¹ after 2000 cycles at 20 C with 90% capacity retention).     

Atomic Structure and Kinetics of NASICON NaxV2(PO4)3 Cathode for Sodium‐Ion Batteries

Na₃V₂(PO₄)₃ is one of the most important cathode materials for sodium‐ion batteries, delivering about two Na extraction/insertion from/into the unit structure. To understand the mechanism of sodium storage, a detailed structure of rhombohedral Na₃V₂(PO₄)₃ and its sodium extracted phase of NaV₂(PO₄)₃ are investigated at the atomic scale using a variety of advanced techniques. It is found that two different Na sites (6b, M1 and 18e, M2) with different coordination environments co‐exist in Na₃V₂(PO₄)₃, whereas only one Na site (6b, M1) exists in NaV₂(PO₄)₃. When Na is extracted from Na₃V₂(PO₄)₃ to form NaV₂(PO₄)₃, Na⁺ occupying the M2 site (CN = 8) is extracted and the rest of the Na remains at M1 site (CN = 6). In addition, the Na atoms are not randomly distributed, possibly with an ordered arrangement in M2 sites locally for Na₃V₂(PO₄)₃. Na⁺ ions at the M1 sites in Na₃V₂(PO₄)₃ tend to remain immobilized, suggesting a direct M2‐to‐M2 conduction pathway. Only Na occupying the M2 sites can be extracted, suggesting about two Na atoms able to be extracted from the Na₃V₂(PO₄)₃ structure.     

Tungsten‐Based Materials for Lithium‐Ion Batteries

Lithium‐ion batteries are widely used as reliable electrochemical energy storage devices due to their high energy density and excellent cycling performance. The search for anode materials with excellent electrochemical performances remains critical to the further development of lithium‐ion batteries. Tungsten‐based materials are receiving considerable attention as promising anode materials for lithium‐ion batteries owing to their high intrinsic density and rich framework diversity. This review describes the advances of exploratory research on tungsten‐based materials (tungsten oxide, tungsten sulfide, tungsten diselenide, and their composites) in lithium‐ion batteries, including synthesis methods, microstructures, and electrochemical performance. Some personal prospects for the further development of this field are also proposed.     

Cathode Design for Aqueous Rechargeable Multivalent Ion Batteries: Challenges and Opportunities

With the rapid growth in energy consumption, renewable energy is a promising solution. However, renewable energy (e.g., wind, solar, and tidal) is discontinuous and irregular by nature, which poses new challenges to the new generation of large-scale energy storage devices. Rechargeable batteries using aqueous electrolyte and multivalent ion charge are considered more suitable candidates compared to lithium-ion and lead-acid batteries, owing to their low cost, ease of manufacture, good safety, and environmentally benign characteristics. However, some substantial challenges hinder the development of aqueous rechargeable multivalent ion batteries (AMVIBs), including the narrow stable electrochemical window of water (≈1.23 V), sluggish ion diffusion kinetics, and stability issues of electrode materials. To address these challenges, a range of encouraging strategies has been developed in recent years, in the aspects of electrolyte optimization, material structure engineering and theoretical investigations. To inspire new research directions, this review focuses on the latest advances in cathode materials for aqueous batteries based on the multivalent ions (Zn²⁺, Mg²⁺, Ca²⁺, Al³⁺), their common challenges, and promising strategies for improvement. In addition, further suggestions for development directions and a comparison of the different AMVIBs are covered.     

Rational Molecular Design of Benzoquinone‐Derived Cathode Materials for High‐Performance Lithium‐Ion Batteries

p‐Benzoquinone (BQ) is a promising cathode material for lithium‐ion batteries (LIBs) due to its high theoretical specific capacity and voltage. However, it suffers from a serious dissolution problem in organic electrolytes, leading to poor electrochemical performance. Herein, two BQ‐derived molecules with a near‐plane structure and relative large skeleton: 1,4‐bis(p‐benzoquinonyl)benzene (BBQB) and 1,3,5‐tris(p‐benzoquinonyl)benzene (TBQB) are designed and synthesized. They show greatly decreased solubility as a result of strong intermolecular interactions. As cathode materials for LIBs, they exhibit high carbonyl utilizations of 100% with high initial capacities of 367 and 397 mAh g^?1, respectively. Especially, BBQB with better planarity presents remarkably improved cyclability, retaining a high capacity of 306 mAh g^?1 after 100 cycles. The cycling stability of BBQB surpasses all reported BQ‐derived small molecules and most polymers. This work provides a new molecular structure design strategy to suppress the dissolution of organic electrode materials for achieving high performance rechargeable batteries.     

Applications of Tin Sulfide‐Based Materials in Lithium‐Ion Batteries and Sodium‐Ion Batteries

SnS_x (x = 1, 2) compounds are composed of earth‐abundant elements and are nontoxic and low‐cost materials that have received increasing attention as energy materials over the past decades, owing to their huge potential in batteries. Generally, SnS_x materials have excellent chemical stability and high theoretical capacity and reversibility due to their unique 2D‐layered structure and semiconductor properties. As a promising matrix material for storing different alkali metal ions through alloying/dealloying reactions, SnS_x compounds have broad electrochemical prospects in batteries. Herein, the structural properties of SnS_x materials and their advantages as electrode materials are discussed. Furthermore, detailed accounts of various synthesis methods and applications of SnS_x materials in lithium‐ion batteries, sodium‐ion batteries, and other new rechargeable batteries are emphasized. Ultimately, the challenges and opportunities for future research on SnS_x compounds are discussed based on the available academic knowledge, including recent scientific advances.     

Bottom‐Up Synthesis of Advanced Carbonaceous Anode Materials Containing Sulfur for Na‐Ion Batteries

The fabrication of sulfur‐containing carbonaceous anode materials (CS) that show exceptional activity as anode material in Na‐ions batteries is reported. To do so, a general and straightforward bottom‐up synthesis of CS materials with precise control over the sulfur content and functionality is introduced. The new synthetic path combined with a detailed structural analysis and electrochemical studies provide correlations between i) the sulfur content and chemical species and ii) the structural, electronic, and electrochemical performance of the associated materials. As a result, the new CS substances demonstrate excellent activity as Na‐ion battery anode materials, reaching capacity values above 500 mAh g^?1 at a current density of 0.1 A g^?1, as well as high reversible sodium storage capabilities and excellent cycling durability. The results reveal the underlying working principles of carbonaceous materials, alongside the storage mechanism of the Na⁺ ions in these advanced sodium‐ion battery anode materials and provide a new avenue for their practical realization.     

Layered P2‐Type K0.65Fe0.5Mn0.5O2 Microspheres as Superior Cathode for High‐Energy Potassium‐Ion Batteries

Potassium‐ion batteries have been regarded as the potential alternatives to lithium‐ion batteries (LIBs) due to the low cost, earth abundance, and low potential of K (?2.936 vs standard hydrogen electrode (SHE)). However, the lack of low‐cost cathodes with high energy density and long cycle life always limits its application. In this work, high‐energy layered P2‐type hierarchical K_0.65Fe_0.5Mn_0.5O₂ (P2‐KFMO) microspheres, assembled by the primary nanoparticles, are fabricated via a modified solvent‐thermal method. Benefiting from the unique microspheres with primary nanoparticles, the K⁺ intercalation/deintercalation kinetics of P2‐KFMO is greatly enhanced with a stabilized cathodic electrolyte interphase on the cathode. The P2‐KFMO microsphere presents a highly reversible potassium storage capacity of 151 mAh g^?1 at 20 mA g^?1, fast rate capability of 103 mAh g^?1 at 100 mA g^?1, and long cycling stability with 78% capacity retention after 350 cycles. A full cell with P2‐KFMO microspheres as cathode and hard carbon as anode is constructed, which exhibits long‐term cycling stability (>80% of retention after 100 cycles). The present high‐performance P2‐KFMO microsphere cathode synthesized using earth‐abundant elements provides a new cost‐effective alternative to LIBs for large‐scale energy storage.     

CoFe–Cl Layered Double Hydroxide: A New Cathode Material for High‐Performance Chloride Ion Batteries

Chloride ion batteries (CIBs) are regarded as promising energy storage systems due to their large theoretical volumetric energy density, high abundance, and low cost of chloride resources. Herein, the synthesis of CoFe layered double hydroxide in the chloride form (CoFe–Cl LDH), for use as a new cathode material for CIBs, is demonstrated for the first time. The CoFe–Cl LDH exhibits a maximum capacity of 239.3 mAh g^?1 and a high reversible capacity of ≈160 mAh g^?1 over 100 cycles. The superb Cl^? ion storage of CoFe–Cl LDH is attributed to its unique topochemical transformation property during the charge/discharge process: a reversible intercalation/deintercalation of Cl^? ions in cathode with slight expansion/contraction of basal spacing, accompanied by chemical state changes in Co²⁺/Co³⁺ and Fe²⁺/Fe³⁺ couples. First‐principles calculations reveal that CoFe–Cl LDH is an excellent Cl^? ion conductor, with extremely low energy barriers (0.12?0.25 eV) for Cl^? diffusion. This work opens a new avenue for LDH materials as promising cathodes for anion‐type rechargeable batteries, which are regarded as formidable competitors to traditional metal ion‐shuttling batteries.