Hierarchical Engineering of Porous P2‐Na2/3Ni1/3Mn2/3O2 Nanofibers Assembled by Nanoparticles Enables Superior Sodium‐Ion Storage Cathodes

Layered transition metal oxides (TMOs) are appealing cathode candidates for sodium‐ion batteries (SIBs) by virtue of their facile 2D Na⁺ diffusion paths and high theoretical capacities but suffer from poor cycling stability. Herein, taking P2‐type Na_2/3Ni_1/3Mn_2/3O₂ as an example, it is demonstrated that the hierarchical engineering of porous nanofibers assembled by nanoparticles can effectively boost the reaction kinetics and stabilize the structure. The P2‐Na_2/3Ni_1/3Mn_2/3O₂ nanofibers exhibit exceptional rate capability (166.7 mA h g^?1 at 0.1 C with 73.4 mA h g^?1 at 20 C) and significantly improved cycle life (≈81% capacity retention after 500 cycles) as cathode materials for SIBs. The highly reversible structure evolution and Ni/Mn valence change during sodium insertion/extraction are verified by in operando X‐ray diffraction and ex situ X‐ray photoelectron spectroscopy, respectively. The facilitated electrode process kinetics are demonstrated by an additional study using the electrochemical measurements and density functional theory computations. More impressively, the prototype Na‐ion full battery built with a Na_2/3Ni_1/3Mn_2/3O₂ nanofibers cathode and hard carbon anode delivers a promising energy density of 212.5 Wh kg^?1. The concept of designing a fibrous framework composed of small nanograins offers a new and generally applicable strategy for enhancing the Na‐storage performance of layered TMO cathode materials.     

Cubic Perovskite Fluoride as Open Framework Cathode for Na‐Ion Batteries

Exploring novel structure prototype and mineral phase, especially open framework material, is crucial to developing high‐performance Na‐ion battery cathodes in view of potentially faster intrinsic diffusion of Na⁺ in lattices. Perovskite phases have been widely applied in solar cells, fuel cells, and electrocatalysis; however, they are rarely attempted as energy storage electrode materials. This study proposes pre‐expanding perovskite iron fluoride (KFeF₃) framework by stuffing large‐sized K⁺ as a channel filler, which is advantageous over Na⁺, NH₄⁺, and H₂O molecule filler in terms of structure robustness, symmetry, and connectivity. K⁺ stuffing leads to the preservation of a more “regular” cubic phase with fast isotropic 3D diffusion as a consequence of no distortion of FeF₆ octahedra during K‐Na electrochemical exchange and following Na‐insertion cycling. High‐rate Na‐storage is achievable with a reversible capacity of 110, 70, and 40 mAh g^?1 at 0.1, 2, and 10 C, respectively, for this open framework fluoride cathode, benefiting from solid solution electrochemical behavior and high intrinsic diffusion coefficient. It is thought that this rate performance is currently the best among Na‐storage fluoride materials.     

Layered P2‐Type K0.44Ni0.22Mn0.78O2 as a High‐Performance Cathode for Potassium‐Ion Batteries

Potassium‐ion batteries (KIBs) are emerging as one of the most promising candidates for large‐scale energy storage owing to the natural abundance of the materials required for their fabrication and the fact that their intercalation mechanism is identical to that of lithium‐ion batteries. However, the larger ionic radius of K⁺ is likely to induce larger volume expansion and sluggish kinetics, resulting in low specific capacity and unsatisfactory cycle stability. A new Ni/Mn‐based layered oxide, P2‐type K_0.44Ni_0.22Mn_0.78O₂, is designed and synthesized. A cathode designed using this material delivers a high specific capacity of 125.5 mAh g^?1 at 10 mA g^?1, good cycle stability with capacity retention of 67% over 500 cycles and fast kinetic properties. In situ X‐ray diffraction recorded for the initial two cycles reveals single solid‐solution processes under P2‐type framework with small volume change of 1.5%. Moreover, a cathode electrolyte interphase layer is observed on the surface of the electrode after cycling with possible components of K₂CO₃, RCO₂K, KOR, KF, etc. A full cell using K_0.44Ni_0.22Mn_0.78O₂ as the cathode and soft carbon as the anode also exhibits exceptional performance, with capacity retention of 90% over 500 cycles as well as superior rate performance. These findings suggest P2‐K_0.44Ni_0.22Mn_0.78O₂ is a promising candidate as a high‐performance cathode for KIBs.     

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.     

Suppressing Manganese Dissolution in Potassium Manganate with Rich Oxygen Defects Engaged High‐Energy‐Density and Durable Aqueous Zinc‐Ion Battery

The manganese dissolution leading to sharp capacity decline as well as the sluggish reaction kinetic are still major issues for manganese‐based materials as aqueous zinc‐ion batteries (ZIBs) cathodes. Here, a potassium‐ion‐stabilized and oxygen‐defect K_0.8Mn₈O₁₆ is reported as a high‐energy‐density and durable cathode for neutral aqueous ZIBs. A new insight into suppressing manganese dissolution via incorporation of K⁺ ions to intrinsically stabilize the Mn‐based cathodes is provided. A comprehensive study suggests that oxygen defects improve electrical conductivity and open the MnO₆ polyhedron walls for ion diffusion, which plays a critical role in the fast reaction kinetics and capacity improvement of K_0.8Mn₈O₁₆. In addition, direct evidence for the mechanistic details of simultaneous insertion and conversion reaction based on H⁺‐storage mechanism is demonstrated. As expected, a significant energy output of 398 W h kg^?1 (based on the mass of cathode) and an impressive durability over 1000 cycles with no obvious capacity fading are obtained. Such a high‐energy Zn‐K_0.8Mn₈O₁₆ battery, as well as the basic understanding of manganese dissolution and oxygen defects may open new opportunities toward high‐performance aqueous ZIBs.     

Approaching the Downsizing Limit of Maricite NaFePO4 toward High‐Performance Cathode for Sodium‐Ion Batteries

Maricite NaFePO₄ nanodots with minimized sizes (≈1.6 nm) uniformly embedded in porous N‐doped carbon nanofibers (designated as NaFePO₄@C) are first prepared by electrospinning for maximized Na‐storage performance. The obtained flexible NaFePO₄@C fiber membrane adherent on aluminum foil is directly used as binder‐free cathode for sodium‐ion batteries, revealing that the ultrasmall nanosize effect as well as a high‐potential desodiation process can transform the generally perceived electrochemically inactive maricite NaFePO₄ into a highly active amorphous phase; meanwhile, remarkable electrochemical performance in terms of high reversible capacity (145 mA h g^?1 at 0.2 C), high rate capability (61 mA h g^?1 at 50 C), and unprecedentedly high cyclic stability (≈89% capacity retention over 6300 cycles) is achieved. Furthermore, the soft package Na‐ion full battery constructed by the NaFePO₄@C nanofibers cathode and the pure carbon nanofibers anode displays a promising energy density of 168.1 Wh kg^?1 and a notable capacity retention of 87% after 200 cycles. The distinctive 3D network structure of very fine NaFePO₄ nanoparticles homogeneously encapsulated in interconnected porous N‐doped carbon nanofibers, can effectively improve the active materials' utilization rate, facilitate the electrons/Na⁺ ions transport, and strengthen the electrode stability upon prolonged cycling, leading to the fascinating Na‐storage performance.     

All‐Cellulose‐Based Quasi‐Solid‐State Sodium‐Ion Hybrid Capacitors Enabled by Structural Hierarchy

Na‐ion hybrid capacitors consisting of battery‐type anodes and capacitor‐style cathodes are attracting increasing attention on account of the abundance of sodium‐based resources as well as the potential to bridge the gap between batteries (high energy) and supercapacitors (high power). Herein, hierarchically structured carbon materials inspired by multiscale building units of cellulose from nature are assembled with cellulose‐based gel electrolytes into Na‐ion capacitors. Nonporous hard carbon anodes are obtained through the direct thermal pyrolysis of cellulose nanocrystals. Nitrogen‐doped carbon cathodes with a coral‐like hierarchically porous architecture are prepared via hydrothermal carbonization and activation of cellulose microfibrils. The reversible charge capacity of the anode is 256.9 mAh g^?1 when operating at 0.1 A g^?1 from 0 to 1.5 V versus Na⁺/Na, and the discharge capacitance of cathodes tested within 1.5 to 4.2 V versus Na⁺/Na is 212.4 F g^?1 at 0.1 A g^?1. Utilizing Na⁺ and ClO₄^? as charge carriers, the energy density of the full Na‐ion capacitor with two asymmetric carbon electrodes can reach 181 Wh kg^?1 at 250 W kg^?1, which is one of the highest energy devices reported until now. Combined with macrocellulose‐based gel electrolytes, all‐cellulose‐based quasi‐solid‐state devices are demonstrated possessing additional advantages in terms of overall sustainability.     

Sodium Storage Behavior in Natural Graphite using Ether‐based Electrolyte Systems

This work reports that natural graphite is capable of Na insertion and extraction with a remarkable reversibility using ether‐based electrolytes. Natural graphite (the most well‐known anode material for Li–ion batteries) has been barely studied as a suitable anode for Na rechargeable batteries due to the lack of Na intercalation capability. Herein, graphite is not only capable of Na intercalation but also exhibits outstanding performance as an anode for Na ion batteries. The graphite anode delivers a reversible capacity of ≈150 mAh g^?1 with a cycle stability for 2500 cycles, and more than 75 mAh g^?1 at 10 A g^?1 despite its micrometer‐size (≈100 μm). An Na storage mechanism in graphite, where Na⁺‐solvent co‐intercalation occurs combined with partial pseudocapacitive behaviors, is revealed in detail. It is demonstrated that the electrolyte solvent species significantly affect the electrochemical properties, not only rate capability but also redox potential. The feasibility of graphite in a Na full cell is also confirmed in conjunction with the Na_1.5VPO_4.8F_0.7 cathode, delivering an energy of ≈120 Wh kg^?1 while maintaining ≈70% of the initial capacity after 250 cycles. This exceptional behavior of natural graphite promises new avenues for the development of cost‐effective and reliable Na ion batteries.     

High‐Performance Manganese Hexacyanoferrate with Cubic Structure as Superior Cathode Material for Sodium‐Ion Batteries

Sodium manganese hexacyanoferrate (Na_xMnFe(CN)₆) is one of the most promising cathode materials for sodium‐ion batteries (SIBs) due to the high voltage and low cost. However, its cycling performance is limited by the multiple phase transitions during Na⁺ insertion/extraction. In this work, a facile strategy is developed to synthesize cubic and monoclinic structured Na_xMnFe(CN)₆, and their structure evolutions are investigated through in situ X‐ray diffraction (XRD), ex situ Raman, and X‐ray photoelectron spectroscopy (XPS) characterizations. It is revealed that the monoclinic phase undergoes undesirable multiple two‐phase reactions (monoclinic ? cubic ? tetragonal) due to the large lattice distortions caused by the Jahn–Teller effects of Mn³⁺, resulting in poor cycling performances with 38% capacity retention. The cubic Na_xMnFe(CN)₆ with high structural symmetry maintains the structural stability during the repeated Na⁺ insertion/extraction process, demonstrating impressive electrochemical performances with specific capacity of ≈120 mAh g^?1 at 3.5 V (vs Na/Na⁺), capacity retention of ≈70% over 500 cycles at 200 mA g^?1. In addition, the TiO₂//C‐MnHCF full battery is fabricated with an energy density of 111 Wh kg^?1, suggesting the great potential of cubic Na_xMnFe(CN)₆ for practical energy storage applications.     

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.     

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.     

3D Carbon Nanotube Network Bridged Hetero‐Structured Ni‐Fe‐S Nanocubes toward High‐Performance Lithium,Sodium, and Potassium Storage

Lithium‐ion, sodium‐ion, and potassium‐ion batteries have captured tremendous attention in power supplies for various electric vehicles and portable electronic devices. However, their practical applications are severely limited by factors such as poor rate capability, fast capacity decay, sluggish charge storage dynamics, and low reversibility. Herein, hetero‐structured bimetallic sulfide (NiS/FeS) encapsulated in N‐doped porous carbon cubes interconnected with CNTs (Ni‐Fe‐S‐CNT) are prepared through a convenient co‐precipitation and post‐heat treatment sulfurization technique of the corresponding Prussian‐blue analogue nanocage precursor. This special 3D hierarchical structure can offer a stable interconnect and conductive network and shorten the diffusion path of ions, thereby greatly enhancing the mobility efficiency of alkali (Li, Na, K) ions in electrode materials. The Ni‐Fe‐S‐CNT nanocomposite maintains a charge capacity of 1535 mAh g^?1 at 0.2 A g^?1 for lithium ion batteries, 431 mAh g^?1 at 0.1 A g^?1 for sodium ion batteries, and 181 mAh g^?1 at 0.1 A g^?1 for potassium‐ion batteries, respectively. The high performance is mainly attributed to the 3D hierarchically high‐conductivity network architecture, in which the hetero‐structured FeS/NiS nanocubes provide fast Li⁺/Na⁺/K⁺ insertion/extraction and reduced ion diffusion paths, and the distinctive 3D networks maintain the electrical contact and guarantee the structural integrity.     

Fast Potassium Storage in Hierarchical Ca0.5Ti2(PO4)3@C Microspheres Enabling High‐Performance Potassium‐Ion Capacitors

Hybrid potassium‐ion capacitors (KICs) show great promise for large‐scale storage on the power grid because of cost advantages, the weaker Lewis acidity of K⁺ and low redox potential of K⁺/K. However, a huge challenge remains for designing high‐performance K⁺ storage materials since K⁺ ions are heavier and larger than Li⁺ and Na⁺. Herein, the synthesis of hierarchical Ca_0.5Ti₂(PO₄)₃@C microspheres by use of the electrospraying method is reported. Benefiting from the rich vacancies in the crystal structure and rational nanostructural design, the hybrid Ca_0.5Ti₂(PO₄)₃@C electrode delivers a high reversible capacity (239 mA h g^?1) and superior rate performance (63 mA h g^?1 at 5 A g^?1). Moreover, the KIC employing a Ca_0.5Ti₂(PO₄)₃@C anode and activated carbon cathode, affords a high energy/power density (80 W h kg^?1 and 5144 W kg^?1) in a potential window of 1.0–4.0 V, as well as a long lifespan of over 4000 cycles. In addition, in situ X‐ray diffraction is used to unravel the structural transition in Ca_0.5Ti₂(PO₄)₃, suggesting a two‐phase transition above 0.5 V during the initial discharge and solid solution processes during the subsequent K⁺ insertion/extraction. The present study demonstrates a low‐cost potassium‐based energy storage device with high energy/power densities and a long lifespan.     

A Water Stable,Near‐Zero‐Strain O3‐Layered Titanium‐Based Anode for Long Cycle Sodium‐Ion Battery

Layered transition metal (TM) oxides of the stoichiometry Na_xMO₂ (M = TM) have shown great promise in sodium‐ion batteries (SIBs); however, they are extremely sensitive to moisture. To date, most reported titanium‐based layered anodes exhibit a P2‐type structure. In contrast, O3‐type compounds are rarely investigated and their synthesis is challenging due to their higher percentage of unstable Ti³⁺ than the P2 type. Here, a pure phase and highly crystalline O3‐type Na_0.73Li_0.36Ti_0.73O₂ with high performance is successfully proposed in SIBs. This material delivers a reversible capacity of 108 mAh g^?1 with a stable and safe potential of 0.75 V versus Na/Na⁺. In situ X‐ray diffraction reveals that this material does not undergo any phase transitions and exhibits a near‐zero volume change upon Na⁺ insertion/de‐insertion, which ensures exceptional long cycle life over 6000 cycles. Importantly, it is found that this O3‐Na_0.73Li_0.36Ti_0.73O₂ shows superior moisture stability, even when immersed into water, which are both elusive for conventional layered TM oxides in SIBs. It is believed that the small interlayer distance and high occupation of interlayer vacancy promise such unprecedented water stability.     

Sodium‐Ion Batteries: Building Effective Layered Cathode Materials with Long‐Term Cycling by Modifying the Surface via Sodium Phosphate

Surface stabilization of cathode materials is urgent for guaranteeing long‐term cyclability, and is important in Na cells where a corrosive Na‐based electrolyte is used. The surface of P2‐type layered Na_2/3[Ni_1/3Mn_2/3]O₂ is modified with ionic, conducting sodium phosphate (NaPO₃) nanolayers, ≈10 nm in thickness, via melt‐impregnation at 300 °C; the nanolayers are autogenously formed from the reaction of NH₄H₂PO₄ with surface sodium residues. Although the material suffers from a large anisotropic change in the c‐axis due to transformation from the P2 to O2 phase above 4 V versus Na⁺/Na, the NaPO₃‐coated Na_2/3[Ni_1/3Mn_2/3]O₂/hard carbon full cell exhibits excellent capacity retention for 300 cycles, with 73% retention. The surface NaPO₃ nanolayers positively impact the cell performance by scavenging HF and H₂O in the electrolyte, leading to less formation of byproducts on the surface of the cathodes, which lowers the cell resistance, as evidenced by X‐ray photoelectron spectroscopy and time‐of‐flight secondary‐ion mass spectroscopy. Time‐resolved in situ high‐temperature X‐ray diffraction study reveals that the NaPO₃ coating layer is delayed for decomposition to Mn₃O₄, thereby suppressing oxygen release in the highly desodiated state, enabling delay of exothermic decomposition. The findings presented herein are applicable to the development of high‐voltage cathode materials for sodium batteries.     

Fast Rate and Long Life Potassium‐Ion Based Dual‐Ion Battery through 3D Porous Organic Negative Electrode

Potassium‐based dual ion batteries (K‐DIBs) with potassium cation (K⁺) intercalation graphitic anodes have been investigated for their potential in large‐scale energy storage applications owing to their merits of low cost and environmental friendly. Nonetheless, graphite anodes are plagued by volume expansion from the large K⁺ ions and the co‐intercalation of solvent molecules during the charging. Accordingly, organic materials stand out for the flexible adjustable structures and abundant active sites, which can accommodate cations by multiple functional groups without structural collapse. However, K‐DIBs based on organic anodes have rarely been investigated. Herein, 3D porous dipotassium terephthalate nanosheets are synthesized via a freeze‐dry method as the K‐DIB anode, which can reversibly store K⁺ ions at a fast rate with a high specific capacity and robust stability due to the sufficient redox active sites and diffusion pathways of K⁺ ions in the 3D porous structure. Consequently, a novel K‐DIB configuration combining this fast kinetics organic anode and environmental friendly expanded graphite (EG) cathode is constructed (pK2TP//EG), which exhibits a high specific capacity (68 mAh g^‐1 at 2 C), good rate performance up to 20 C, and long cycling life with a capacity retention ~100% after 2000 cycles, which is the best performance observed among reported K‐DIBs.     

Potassium Prussian Blue Nanoparticles: A Low‐Cost Cathode Material for Potassium‐Ion Batteries

Potassium‐ion batteries (KIBs) in organic electrolytes hold great promise as an electrochemical energy storage technology owing to the abundance of potassium, close redox potential to lithium, and similar electrochemistry with lithium system. Although carbon materials have been studied as KIB anodes, investigations on KIB cathodes have been scarcely reported. A comprehensive study on potassium Prussian blue K_0.220Fe[Fe(CN)₆]_0.805?4.01H₂O nanoparticles as a potential cathode material is for the first time reported. The cathode exhibits a high discharge voltage of 3.1–3.4 V, a high reversible capacity of 73.2 mAh g^?1, and great cyclability at both low and high rates with a very small capacity decay rate of ≈0.09% per cycle. Electrochemical reaction mechanism analysis identifies the carbon‐coordinated Fe^III/Fe^II couple as redox‐active site and proves structural stability of the cathode during charge/discharge. Furthermore, for the first time, a KIB full‐cell is presented by coupling the nanoparticles with commercial carbon materials. The full‐cell delivers a capacity of 68.5 mAh g^?1 at 100 mA g^?1 and retains 93.4% of the capacity after 50 cycles. Considering the low cost and material sustainability as well as the great electrochemical performances, this work may pave the way toward more studies on KIB cathodes and trigger future attention on rechargeable KIBs.     

High Tap Density Co and Ni Containing P2‐Na0.66MnO2 Buckyballs: A Promising High Voltage Cathode for Stable Sodium‐Ion Batteries

Constructing high voltage (>4.5 V) cathode materials for sodium‐ion batteries has emerged in recent years to replace lithium batteries for large scale energy storage applications. Herein, an electrochemically stable Na_0.66(Ni_0.13Mn_0.54Co_0.13)O₂ (Na‐NMC) buckyballs with an uniform size of 5 µm and a high tap density of 2.34 g cm^?3, which exhibit excellent cyclability even at the high current with a cut‐off voltage of 4.7 V, is demonstrated. The Na‐NMC buckyballs are prepared from (Ni_0.13Mn_0.54Co_0.13)CO₃ (NMC) precursor synthesized using a facile hydrothermal method. The Na‐NMC delivers a reversible capacity of around 120 mAh g^?1 between 4.7 and 2 V at 1 C rate along with an excellent cyclic stability (90%) until 150 cycles, which is one of the best outcomes among the reported P2‐type cathodes tested at the high operating voltage range. Furthermore, Na‐NMC‐180 buckyballs with a high tap density is offering an enhanced volumetric energy density, a superior rate performance and an outstanding cyclic stability. The X‐ray adsorption fine structure analysis is used to study the local electronic structure changes around the Co, Mn, and Ni after cycling process at 1 C rate. The findings open opportunities for tailoring high‐performance and high‐energy cathode materials for sodium‐ion batteries.     

Half‐Cell and Full‐Cell Applications of Highly Stable and Binder‐Free Sodium Ion Batteries Based on Cu3P Nanowire Anodes

Sodium‐ion battery (SIB) is especially attractive in cost‐effective energy storage device as an alternative to lithium‐ion battery. Particularly, metal phosphides as potential anodes for SIBs have recently been demonstrated owing to their higher specific capacities compared with those of carbonaceous materials. Unfortunately, most reported metal phosphides consist of irregular particles ranged from several hundreds nanometers to tens of micrometers, thus delivering limited cyclic stability. This paper reports the sodium storage properties of additive‐free Cu₃P nanowire (CPNW) anode directly grown on copper current collector via an in situ growth followed by phosphidation method. Therefore, as a result of its structure features, CPNW anode demonstrates highly stable cycling ability with an ≈70% retention in capacity at the 260th cycle, whereas most reported metal phosphides have limited cycle numbers ranged between 30 and 150. Besides, the reaction mechanism between Cu₃P and Na is investigated by examining the intermediate products at different charge/discharge stages using ex situ X‐ray diffraction measurements. Furthermore, to explore the practical application of CPNW anode, a pouch‐type Na⁺ full cell consisting of CPNW anode and Na₃V₂(PO₄)₃ cathode is assembled and characterized. As a demonstration, a 10 cm × 10 cm light‐emmiting diode (LED) screen is successfully powered by the Na⁺ full cell.     

3D Ordered Porous Hybrid of ZnSe/N-doped Carbon with Anomalously High Na+ Mobility and Ultrathin Solid Electrolyte Interphase for Sodium-Ion Batteries

Transition metal selenides have been widely used in alkali metal ion batteries owing to their high specific capacities and low cost. However, their reaction kinetics and structural stability are usually poor during cycling, along with ambiguous differences in Li/Na/K-storage behaviors. Herein, it is revealed that ZnSe possesses better Na⁺-diffusion kinetics (including lower diffusion barrier, smaller activation energy, and higher diffusion coefficients) in comparison with Li⁺ and K⁺, as evidenced by theoretical calculations and electrochemical studies. The architectural designs of ZnSe-based anode, including nitrogen-doped carbon (N,C) and 3D ordered hierarchical pores (3DOHP) to form a 3DOHP ZnSe@N,C hybrid combined with regulating solid electrolyte interphase (SEI), significantly enhance Na⁺ reaction kinetics and accommodate volume changes. The resulting 3DOHP ZnSe@N,C electrodes exhibit outstanding rate capability and good cycling stability (241.6 mAh g⁻¹ in sodium-ion batteries (SIBs) at 10 A g⁻¹ after 800 cycles), originating from improved electrical conductivity and shortened ion diffusion paths, accompanied by ultrathin and stable SEI with less Na₂CO₃/NaF in organic components and boosted Na₂Se adsorption as sodiation. Moreover, the Na-storage mechanism in 3DOHP ZnSe@N,C hybrid is further revealed by in situ studies. Accordingly, this study provides a new perspective for designing high-performance electrode materials for SIBs.