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.     

Fabrication of Electrospinning‐Derived Carbon Nanofiber Webs for the Anode Material of Lithium‐Ion Secondary Batteries

A carbon nanofiber‐based electrode, exhibiting a large accessible surface area (derived from the nanometer‐sized fiber diameter), high carbon purity (without binder), relatively high electrical conductivity, structural integrity, thin web macromorphology, a large reversible capacity (ca. 450 mA h g^–1), and a relatively linearly inclined voltage profile, is fabricated by nanofiber formation via electrospinning of a polymer solution and its subsequent thermal treatment. It is envisaged that these characteristics of this novel carbon material will make it an ideal candidate for the anode material of high‐power lithium‐ion batteries (where a high current is critically needed), owing to the highly reduced lithium‐ion diffusion path within the active material.     

Electrochemical Na Insertion and Solid Electrolyte Interphase for Hard‐Carbon Electrodes and Application to Na‐Ion Batteries

Recently, lithium‐ion batteries have been attracting more interest for use in automotive applications. Lithium resources are confirmed to be unevenly distributed in South America, and the cost of the lithium raw materials has roughly doubled from the first practical application in 1991 to the present and is increasing due to global demand for lithium‐ion accumulators. Since the electrochemical equivalent and standard potential of sodium are the most advantageous after lithium, sodium based energy storage is of great interest to realize lithium‐free high energy and high voltage batteries. However, to the best of our knowledge, there have been no successful reports on electrochemical sodium insertion materials for battery applications; the major challenge is the negative electrode and its passivation. In this study, we achieve high capacity and excellent reversibility sodium‐insertion performance of hard‐carbon and layered NaNi_0.5Mn_0.5O₂ electrodes in propylene carbonate electrolyte solutions. The structural change and passivation for hard‐carbon are investigated to study the reversible sodium insertion. The 3‐volt secondary Na‐ion battery possessing environmental and cost friendliness, Na⁺‐shuttlecock hard‐carbon/NaNi_0.5Mn_0.5O₂ cell, demonstrates steady cycling performance as next generation secondary batteries and an alternative to Li‐ion batteries.     

Dual Functions of Potassium Antimony(III)‐Tartrate in Tuning Antimony/Carbon Composites for Long‐Life Na‐Ion Batteries

Antimony holds a high‐specific capacity as a promising anode material for Na‐ion batteries (SIBs) and much research is focused on solving the poor cycling stability issue associated with its large volume expansion during alloying/dealloying processes. Here, self‐thermal‐reduction method is successfully applied to prepare antimony/carbon rods (Sb/C rods) utilizing potassium antimony(III)‐tartrate (C₈H₁₀O₁₅Sb₂K₂) as a dual source of carbon matrix and metallic antimony. According to theory calculations and experiment results, the formation process is explicitly explored as follows: C₈H₁₀O₁₅Sb₂K₂ → Sb₂O₃/C → Sb₂O₃/Sb/C → Sb/C rods. Notably, organic ligands in C₈H₁₀O₁₅Sb₂K₂ can be gradually turned into amorphous carbon with simultaneous reduction of Sb³⁺ to metal Sb. Moreover, potassium chloride acts as an activator and a template during the course of carbonization, and synchronous reduction is introduced. Consequently, an antimony/carbon electrode material denoted as Sb? O? C/C is formed, exhibiting a unique dual‐carbon‐modified structure and extensive Sb? O? C bridge bonds that give rise to outstanding cycling performance and rate capacity. Specifically, the capacity is maintained at 404 mA h g^?1 with 89% retention after 700 cycles at 500 mA g^?1. The low‐cost, self‐thermal‐reduction method and excellent electrode performances of electrode material make it attractive for large‐scale energy storage systems.     

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.     

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.     

Structure‐Properties Relationship in Iron Oxide‐Reduced Graphene Oxide Nanostructures for Li‐Ion Batteries

Non‐aqueous sol‐gel routes involving the reaction of metal oxide precursors in organic solvents (e.g., benzyl alcohol) at moderate temperature and pressure, offer advantages such as high purity, high reproducibility and the ability to control the crystal growth without the need of using additional ligands. In this paper, a study carried out on a series of iron oxide/reduced graphene oxide composites is presented to elucidate a structure‐properties relationship leading to an improved electrochemical performance of such composites. Moreover, it is demonstrated that the easy production of the composites in a variety of temperature and composition ranges, allows a fine control over the final particles size, density and distribution. The materials obtained are remarkable in terms of the particle's size homogeneity and dispersion onto the reduced graphene oxide surface. Moreover, the synthesis method used to obtain the graphene oxide clearly affects the performances of the final composites through the control of the restacking of the reduced graphene oxide sheets. It is shown that a homogeneous and less defective reduced graphene oxide enables good electrochemical performances even at high current densities (over 500 mAh/g delivered at current densities as high as 1600 mA/g). The electrochemical properties of improved samples reach the best compromise between specific capacity, rate capability and cycle stability reported so far.     

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.     

Amorphous GaN@Cu Freestanding Electrode for High‐Performance Li‐Ion Batteries

GaN is demonstrated to be an ideal anode for Li‐ion batteries (LIBs) for the first time. Amorphous GaN@Cu nanorods (a‐GaN@Cu) freestanding electrode is designed via a low‐temperature pulsed laser deposition method, which exhibits prominent rate capability and untralong lifespan as an anode for LIBs. With porous interconnected metal nanorods substrate to improve the structure integrity and electronic conductivity, the a‐GaN@Cu electrode delivers a capacity recovery of 980 mAh g^?1 after 150 cycles from 0.25 to 6.25 A g^?1 and a high discharge capacity of 509 mAh g^?1 after 3000 cycles at 10.0 A g^?1. The lithium storage in the a‐GaN is also systematically studied, which suggests a redox reaction mechanism.     

General Synthesis of Transition Metal Oxide Ultrafine Nanoparticles Embedded in Hierarchically Porous Carbon Nanofibers as Advanced Electrodes for Lithium Storage

A unique general, large‐scale, simple, and cost‐effective strategy, i.e., foaming‐assisted electrospinning, for fabricating various transition metal oxides into ultrafine nanoparticles (TMOs UNPs) that are uniformly embedded in hierarchically porous carbon nanofibers (HPCNFs) has been developed. Taking advantage of the strong repulsive forces of metal azides as the pore generator during carbonization, the formation of uniform TMOs UNPs with homogeneous distribution and HPCNFs is simultaneously implemented. The combination of uniform ultrasmall TMOs UNPs with homogeneous distribution and hierarchically porous carbon nanofibers with interconnected nanostructure can effectively avoid the aggregation, dissolution, and pulverization of TMOs, promote the rapid 3D transport of both Li ions and electrons throughout the whole electrode, and enhance the electrical conductivity and structural integrity of the electrode. As a result, when evaluated as binder‐free anode materials in Li‐ion batteries, they displayed extraordinary electrochemical properties with outstanding reversible capacity, excellent capacity retention, high Coulombic efficiency, good rate capability, and superior cycling performance at high rates. More importantly, the present work opens up a wide horizon for the fabrication of a wide range of ultrasmall metal/metal oxides distributed in 1D porous carbon structures, leading to advanced performance and enabling their great potential for promising large‐scale applications.     

Iron Oxide Nanoparticle and Graphene Nanoribbon Composite as an Anode Material for High‐Performance Li‐Ion Batteries

A composite material made of graphene nanoribbons and iron oxide nanoparticles provides a remarkable route to lithium‐ion battery anode with high specific capacity and cycle stability. At a rate of 100 mA/g, the material exhibits a high discharge capacity of ~910 mAh/g after 134 cycles, which is >90% of the theoretical li‐ion storage capacity of iron oxide. Carbon black, carbon nanotubes, and graphene flakes have been employed by researchers to achieve conductivity and stability in lithium‐ion electrode materials. Herein, the use of graphene nanoribbons as a conductive platform on which iron oxide nanoparticles are formed combines the advantages of long carbon nanotubes and flat graphene surfaces. The high capacity over prolonged cycling achieved is due to the synergy between an electrically percolating networks of conductive graphene nanoribbons and the high lithium‐ion storage capability of iron oxide nanoparticles.     

Ultrasmall Sn Nanoparticles Embedded in Carbon as High‐Performance Anode for Sodium‐Ion Batteries

Designed as a high‐capacity, high‐rate, and long‐cycle life anode for sodium‐ion batteries, ultrasmall Sn nanoparticles (≈8 nm) homogeneously embedded in spherical carbon network (denoted as 8‐Sn@C) is prepared using an aerosol spray pyrolysis method. Instrumental analyses show that 8‐Sn@C nanocomposite with 46 wt% Sn and a BET surface area of 150.43 m² g^?1 delivers an initial reversible capacity of ≈493.6 mA h g^?1 at the current density of 200 mA g^?1, a high‐rate capacity of 349 mA h g^?1 even at 4000 mA g^?1, and a stable capacity of ≈415 mA h g^?1 after 500 cycles at 1000 mA g^?1. The remarkable electrochemical performance of 8‐Sn@C is owing to the synergetic effects between the well‐dispersed ultrasmall Sn nanoparticles and the conductive carbon network. This unique structure of very‐fine Sn nanoparticles embedded in the porous carbon network can effectively suppress the volume fluctuation and particle aggregation of tin during prolonged sodiation/desodiation process, thus solving the major problems of pulverization, loss of electrical contact and low utilization rate facing Sn anode.     

Copper‐Stabilized Sulfur‐Microporous Carbon Cathodes for Li–S Batteries

A copper‐stabilized sulfur‐microporous carbon ( MC‐Cu‐S) composite is synthesized by uniformly dispersing 10% highly electronically conductive Cu nanoparticles into microporous carbon (MC), followed by wet‐impregnating S. In the MC‐Cu‐S composite, the MC host that physically confines S/polysulfides provides free space to accommodate volumetric expansion of S during lithiation, while the Cu nanoparticles that are anchored in the MC further chemically interact with S/polysulfides through bonding between Cu and S/polysulfides. The Cu loading allows the S content to increase from 30 to 50% in the carbon‐S cathode material without scarifying the electrochemical performance in a low‐cost carbonate electrolyte. At a current density of 100 mA g^‐1, the MC‐Cu‐S cathode shows that Coulumbic efficiency is close to 100% and capacity maintains more than 600 mAh g^‐1 with progressive cycling up to more than 500 cycles. In addition, the Cu nano‐inclusins also enhance the electronic conductivity of the MC‐Cu‐S composite, remarkably increasing the rate capabilities. Even the current density increases 10.0 A g^‐1, the MC‐Cu‐S cathode can still deliver a capacity of 200 mAh g^‐1. This strategy of stabilization of S with small amount of metal nanoparticles anchored in MC provides an effective approach to improve the cycling stability, Coulumbic efficiency, and S loading for Li–S batteries.     

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.     

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.     

B‐doped Carbon Coating Improves the Electrochemical Performance of Electrode Materials for Li‐ion Batteries

An evolutionary modification approach, boron doped carbon coating, is initially used to improve the electrochemical properties of electrode materials of lithium‐ion batteries, such as Li₃V₂(PO₄)₃, and demonstrates apparent and significant modification effects. Based on the precise analysis of X‐ray photoemission spectroscopy results, Raman spectra, and electrochemical impedance spectroscopy results for various B‐doped carbon coated Li₃V₂(PO₄)₃ samples, it is found that, among various B‐doping types (B₄C, BC₃, BC₂O and BCO₂), the graphite‐like BC₃ dopant species plays a huge role on improving the electronic conductivity and electrochemical activity of the carbon coated layer on Li₃V₂(PO₄)₃ surface. As a result, when compared with the bare carbon coated Li₃V₂(PO₄)₃, the electrochemical performances of the B‐doped carbon coated Li₃V₂(PO₄)₃ electrode with a moderate doping amount are greatly improved. For example, when cycled under 1 C and 20 C in the potential range of 3.0–4.3 V, this sample shows an initial capacity of 122.5 and 118.4 mAh g^?1, respectively; after 200 cycles, nearly 100% of the initial capacity is retained. Moreover, the modification effects of B‐doped carbon coating approach are further validated on Li₄Ti₅O₁₂ anode material.     

A High‐Potential Anion‐Insertion Carbon Cathode for Aqueous Zinc Dual‐Ion Battery

Aqueous dual‐ion batteries (DIBs) are promising for large‐scale energy storage due to low cost and inherent safety. However, DIBs are limited by low capacity and poor cycling of cathode materials and the challenge of electrolyte decomposition. In this study, a new cathode material of nitrogen‐doped microcrystalline graphene‐like carbon is investigated in a water‐in‐salt electrolyte of 30 m ZnCl₂, where this carbon cathode stores anions reversibly via both electrical double layer adsorption and ion insertion. The (de)insertion of anions in carbon lattice delivers a high‐potential plateau at 1.85 V versus Zn²⁺/Zn, contributing nearly 1/3 of the capacity of 134 mAh g^?1 and half of the stored energy. This study shows that both the unique carbon structure and concentrated ZnCl₂ electrolyte play critical roles in allowing anion storage in carbon cathode for this aqueous DIB.     

Preparation of Short Carbon Nanotubes and Application as an Electrode Material in Li‐Ion Batteries

A new approach is developed for cutting conventional micrometer‐long entangled carbon nanotubes (CNTs) to short ca. 200 nm long segments with excellent dispersion. CNTs with different lengths are used as anode materials in Li‐ion batteries. The reversible capacity of the Li‐ion batteries is increased and the irreversible capacity is decreased upon shortening the length of the CNTs. The reason for this is that the insertion/extraction of Li ions is easier into/from short CNTs as compared to long CNTs because of the shortened length and the presence of lateral defects. Moreover, short CNTs have a lower electrical resistance and Warburg prefactor, resulting in better rate performance at high current densities. The present study suggests that short segments of CNTs obtained by cutting long CNTs may possess novel properties that may be useful for a wide variety of applications.     

Self‐Standing Porous LiCoO2 Nanosheet Arrays as 3D Cathodes for Flexible Li‐Ion Batteries

Self‐standing electrodes are the key to realize flexible Li‐ion batteries. However, fabrication of self‐standing cathodes is still a major challenge. In this work, porous LiCoO₂ nanosheet arrays are grown on Au‐coated stainless steel (Au/SS) substrates via a facile “hydrothermal lithiation” method using Co₃O₄ nanosheet arrays as the template followed by quick annealing in air. The binder‐free and self‐standing LiCoO₂ nanosheet arrays represent the 3D cathode and exhibit superior rate capability and cycling stability. In specific, the LiCoO₂ nanosheet array electrode can deliver a high reversible capacity of 104.6 mA h g^?1 at 10 C rate and achieve a capacity retention of 81.8% at 0.1 C rate after 1000 cycles. By coupling with Li₄Ti₅O₁₂ nanosheet arrays as anode, an all‐nanosheet array based LiCoO₂//Li₄Ti₅O₁₂ flexible Li‐ion battery is constructed. Benefiting from the 3D nanoarchitectures for both cathode and anode, the flexible LiCoO₂//Li₄Ti₅O₁₂ battery can deliver large specific reversible capacities of 130.7 mA h g^?1 at 0.1 C rate and 85.3 mA h g^?1 at 10 C rate (based on the weight of cathode material). The full cell device also exhibits good cycling stability with 80.5% capacity retention after 1000 cycles at 0.1 C rate, making it promising for the application in flexible Li‐ion batteries.