Electrostatically Assembling 2D Nanosheets of MXene and MOF‐Derivatives into 3D Hollow Frameworks for Enhanced Lithium Storage

As an essential member of 2D materials, MXene (e.g., Ti₃C₂T_x) is highly preferred for energy storage owing to a high surface‐to‐volume ratio, shortened ion diffusion pathway, superior electronic conductivity, and neglectable volume change, which are beneficial for electrochemical kinetics. However, the low theoretical capacitance and restacking issues of MXene severely limit its practical application in lithium‐ion batteries (LIBs). Herein, a facile and controllable method is developed to engineer 2D nanosheets of negatively charged MXene and positively charged layered double hydroxides derived from ZIF‐67 polyhedrons into 3D hollow frameworks via electrostatic self‐assembling. After thermal annealing, transition metal oxides (TMOs)@MXene (CoO/Co₂Mo₃O₈@MXene) hollow frameworks are obtained and used as anode materials for LIBs. CoO/Co₂Mo₃O₈ nanosheets prevent MXene from aggregation and contribute remarkable lithium storage capacity, while MXene nanosheets provide a 3D conductive network and mechanical robustness to facilitate rapid charge transfer at the interface, and accommodate the volume expansion of the internal CoO/Co₂Mo₃O₈. Such hollow frameworks present a high reversible capacity of 947.4 mAh g^?1 at 0.1 A g^?1, an impressive rate behavior with 435.8 mAh g^?1 retained at 5 A g^?1, and good stability over 1200 cycles (545 mAh g^?1 at 2 A g^?1).     

NixMnyCozO Nanowire/CNT Composite Microspheres with 3D Interconnected Conductive Network Structure via Spray‐Drying Method: A High‐Capacity and Long‐Cycle‐Life Anode Material for Lithium‐Ion Batteries

The combination of high‐capacity and long‐term cycling stability is an important factor for practical application of anode materials for lithium‐ion batteries. Herein, Ni_xMn_yCo_zO nanowire (x + y + z = 1)/carbon nanotube (CNT) composite microspheres with a 3D interconnected conductive network structure (3DICN‐NCS) are prepared via a spray‐drying method. The 3D interconnected conductive network structure can facilitate the penetration of electrolyte into the microspheres and provide excellent connectivity for rapid Li⁺ ion/electron transfer in the microspheres, thus greatly reducing the concentration polarization in the electrode. Additionally, the empty spaces among the nanowires in the network accommodate microsphere volume expansion associated with Li⁺ intercalation during the cycling process, which improves the cycling stability of the electrode. The CNTs distribute uniformly in the microspheres, which act as conductive frameworks to greatly improve the electrical conductivity of the microspheres. As expected, the prepared 3DICN‐NCS demonstrates excellent electrochemical performance, showing a high capacity of 1277 mAh g^?1 at 1 A g^?1 after 2000 cycles and 790 mAh g^?1 at 5 A g^?1 after 1000 cycles. This work demonstrates a universal method to construct a 3D interconnected conductive network structure for anode materials     

Formation of Septuple‐Shelled (Co2/3Mn1/3)(Co5/6Mn1/6)2O4 Hollow Spheres as Electrode Material for Alkaline Rechargeable Battery

The multishelled (Co_2/3Mn_1/3)(Co_5/6Mn_1/6)2O₄ hollow microspheres with controllable shell numbers up to septuple shells are synthesized using developed sequential templating method. Exhilaratingly, the septuple‐shelled complex metal oxide hollow microsphere is synthesized for the first time by doping Mn into Co₃O₄, leading to the change of crystalline rate of precursor. Used as electrode materials for alkaline rechargeable battery, it shows a remarkable reversible capacity (236.39 mAh g^?1 at a current density of 1 A g^?1 by three‐electrode system and 106.85 mAh g^?1 at 0.5 A g^?1 in alkaline battery) and excellent cycling performance due to its unique structure.     

Formation of N‐Doped Carbon‐Coated ZnO/ZnCo2O4/CuCo2O4 Derived from a Polymetallic Metal–Organic Framework: Toward High‐Rate and Long‐Cycle‐Life Lithium Storage

Metal–organic frameworks (MOFs) are very promising self‐sacrificing templates for the large‐scale fabrication of new functional materials owing to their versatile functionalities and tunable porosities. Most conventional metal oxide electrodes derived from MOFs are limited by the low abundance of incorporated metal elements. This study reports a new strategy for the synthesis of multicomponent active metal oxides by the pyrolysis of polymetallic MOF precursors. A hollow N‐doped carbon‐coated ZnO/ZnCo₂O₄/CuCo₂O₄ nanohybrid is prepared by the thermal annealing of a polymetallic MOF with ammonium bicarbonate as a pore‐forming agent. This is the first report on the rational design and preparation of a hybrid composed of three active metal oxide components originating from MOF precursors. Interestingly, as a lithium‐ion battery anode, the developed electrode delivers a reversible capacity of 1742 mAh g^?1 after 500 cycles at a current density of 0.3 mA g^?1. Furthermore, the material shows large storage capacities (1009 and 667 mAh g^?1), even at high current flow (3 and 10 A g^?1). The remarkable high‐rate capability and outstanding long‐life cycling stability of the multidoped metal oxide benefits from the carbon‐coated integrated nanostructure with a hollow interior and the three active metal oxide components.     

Synthesis of Uniquely Structured Yolk–Shell Metal Oxide Microspheres Filled with Nitrogen‐Doped Graphitic Carbon with Excellent Li–Ion Storage Performance

Novel structured composite microspheres of metal oxide and nitrogen‐doped graphitic carbon (NGC) have been developed as efficient anode materials for lithium‐ion batteries. A new strategy is first applied to a one‐pot preparation of composite (FeO_x‐NGC/Y) microspheres via spray pyrolysis. The FeO_x‐NGC/Y composite microspheres have a yolk–shell structure based on the iron oxide material. The void space of the yolk–shell microsphere is filled with NGC. Dicyandiamide additive plays a key role in the formation of the FeO_x‐NGC/Y composite microspheres by inducing Ostwald ripening to form a yolk–shell structure based on the iron oxide material. The FeO_x‐NGC/Y composite microspheres with the mixed crystal structure of rock salt FeO and spinel Fe₃O₄ phases show highly superior lithium‐ion storage performances compared to the dense‐structured FeO_x microspheres with and without carbon material. The discharge capacities of the FeO_x‐NGC/Y microspheres for the 1st and 1000th cycle at 1 A g^?1 are 1423 and 1071 mAh g^?1, respectively. The microspheres have a reversible discharge capacity of 598 mAh g^?1 at an extremely high current density of 10 A g^?1. Furthermore, the strategy described in this study is generally applied to multicomponent metal oxide–carbon composite microspheres with yolk–shell structures based on metal oxide materials.     

Hollow Multishelled Heterostructured Anatase/TiO2(B) with Superior Rate Capability and Cycling Performance

TiO₂ is a potential anode material for lithium‐ion batteries due to its high rate capability and high safety. Here, a controllable synthesis for hollow nanostructured TiO₂, with heterostructured shells of TiO₂(B) and anatase phases, is presented for the first time, by using a sequential templating approach. The hollow nanostructures can be easily controlled to produce core–shell and double‐shelled materials with different compositional ratios of anatase to TiO₂(B) by tuning the synthetic conditions. When used as the anode materials for lithium‐ion batteries, a specific discharge capacity of 215.4 mAh g^?1 for the double‐shelled anatase/TiO₂(B) hollow microspheres is achieved at a current rate of 1 C (335 mA g^?1) for the 100th cycle and shows high specific discharge capacities of 141.6 and 125.7 mAh g^?1 at the high rates of 10 and 20 C over 1000 cycles. These results are due to the unique stable hollow multishelled structure, which has a high specific surface area, as well as the interface between the heterostructured anatase/TiO₂(B) phases contributing a substantial number of lithium‐ion storage sites.     

Yolk–Shell MnO@ZnMn2O4/N–C Nanorods Derived from α‐MnO2/ZIF‐8 as Anode Materials for Lithium Ion Batteries

Manganese oxides (MnO_x) are promising anode materials for lithium ion batteries, but they generally exhibit mediocre performances due to intrinsic low ionic conductivity, high polarization, and poor stability. Herein, yolk–shell nanorods comprising of nitrogen‐doped carbon (N–C) coating on manganese monoxide (MnO) coupled with zinc manganate (ZnMn₂O₄) nanoparticles are manufactured via one‐step carbonization of α‐MnO₂/ZIF‐8 precursors. When evaluated as anodes for lithium ion batteries, MnO@ZnMn₂O₄/N–C exhibits an reversible capacity of 803 mAh g^?1 at 50 mA g^?1 after 100 cycles, excellent cyclability with a capacity of 595 mAh g^?1 at 1000 mAg^?1 after 200 cycles, as well as better rate capability compared with those non‐N–C shelled manganese oxides (MnO_x). The outstanding electrochemical performance is attributed to the unique yolk–shell nanorod structure, the coating effect of N–C and nanoscale size.     

A Flexible Film toward High‐Performance Lithium Storage: Designing Nanosheet‐Assembled Hollow Single‐Hole Ni–Co–Mn–O Spheres with Oxygen Vacancy Embedded in 3D Carbon Nanotube/Graphene Network

Ternary transition metal oxides (TMOs) are highly potential electrode materials for lithium ion batteries (LIBs) due to abundant defects and synergistic effects with various metal elements in a single structure. However, low electronic/ionic conductivity and severe volume change hamper their practical application for lithium storage. Herein, nanosheet‐assembled hollow single‐hole Ni–Co–Mn oxide (NHSNCM) spheres with oxygen vacancies can be obtained through a facile hydrothermal reaction, which makes both ends of each nanosheet exposed to sufficient free space for volume variation, electrolyte for extra active surface area, and dual ion diffusion paths compared with airtight hollow structures. Furthermore, oxygen vacancies could improve ion/electronic transport and ion insertion/extraction process of NHSNCM spheres. Thus, oxygen‐vacancy‐rich NHSNCM spheres embedded into a 3D porous carbon nanotube/graphene network as the anode film ensure efficient electrolyte infiltration into both the exterior and interior of porous and open spheres for a high utilization of the active material, showing an excellent electrochemical performance for LIBs (1595 mAh g^?1 over 300 cycles at 2 A g^?1, 441.6 mAh g^?1 over 4000 cycles at 10 A g^?1). Besides, this straightforward synthetic method opens an efficacious avenue for the construction of various nanosheet‐assembled hollow single‐hole TMO spheres for potential applications.     

Composition and Architecture Design of Double‐Shelled Co0.85Se1−xSx@Carbon/Graphene Hollow Polyhedron with Superior Alkali (Li,Na, K)‐Ion Storage

The exploration of materials with reversible and stable electrochemical performance is crucial in energy storage, which can (de) intercalate all the alkali‐metal ions (Li⁺, Na⁺, and K⁺). Although transition‐metal chalcogenides are investigated continually, the design and controllable preparation of hierarchical nanostructure and subtle composite withstable properties are still great challenges. Herein, component‐optimal Co_0.85Se_1?xS_x nanoparticles are fabricated by in situ sulfidization of metal organic framework, which are wrapped by the S‐doped graphene, constructing a hollow polyhedron framework with double carbon shells (CoSSe@C/G). Benefiting from the synergistic effect of composition regulation and architecture design by S‐substitution, the electrochemical kinetic is enhanced by the boosted electrochemistry‐active sites, and the volume variation is mitigated by the designed structure, resulting in the advanced alkali‐ion storage performance. Thus, it delivers an outstanding reversible capacity of 636.2 mAh g^?1 at 2 A g^?1 after 1400 cycles for Li‐ion batteries. Remarkably, satisfactory initial charge capacities of 548.1 and 532.9 mAh g^?1 at 0.1 A g^?1 can be obtained for Na‐ion and K‐ion batteries, respectively. The prominent performance combined with the theory calculation confirms that the synergistic strategy can improve the alkali‐ion transportation and structure stability, providing an instructive guide for designing high‐performance anode materials for universal alkali‐ion storage.     

Synthesis of Bimetallic Conductive 2D Metal–Organic Framework (CoxNiy‐CAT) and Its Mass Production: Enhanced Electrochemical Oxygen Reduction Activity

The development of new electrocatalysts for electrochemical oxygen reduction to replace expensive and rare platinum‐based catalysts is an important issue in energy storage and conversion research. In this context, conductive and porous metal–organic frameworks (MOFs) are considered promising materials for the oxygen reduction reaction (ORR) due to not only their high surface area and well‐developed pores but also versatile structural features and chemical compositions. Herein, the preparation of bimetallic conductive 2D MOFs (Co_xNi_y‐CATs) are reported for use as catalysts in the ORR. The ratio of the two metal ions (Co²⁺ and Ni²⁺) in the bimetallic Co_xNi_y‐CATs is rationally controlled to determine the optimal composition of Co_xNi_y‐CAT for efficient performance in the ORR. Indeed, bimetallic MOFs display enhanced ORR activity compared to their monometallic counterparts (Co‐CAT or Ni‐CAT). During the ORR, bimetallic Co_xNi_y‐CATs retain an advantageous characteristic of Co‐CAT in relation to its high diffusion‐limiting current density, as well as a key advantage of Ni‐CAT in relation to its high onset potential. Moreover, the ORR‐active bimetallic Co_xNi_y‐CAT with excellent ORR activity is prepared at a large scale via a convenient method using a ball‐mill reactor.     

Construction of Complex Co3O4@Co3V2O8 Hollow Structures from Metal–Organic Frameworks with Enhanced Lithium Storage Properties

A novel metal–organic‐framework‐engaged strategy is demonstrated for the preparation of multishelled Co₃O₄@Co₃V₂O₈ hybrid nanoboxes. This strategy relies on the unique reaction of zeolitic imidazolate framework‐67 with the vanadium source of vanadium oxytriisopropoxide. Benefitting from the synthetic versatility, a series of nanostructures can be realized including triple‐shelled and double‐shelled Co₃O₄@Co₃V₂O₈ nanoboxes and single‐shelled Co₃V₂O₈ nanoboxes. When evaluated as electrode materials for lithium‐ion batteries, these unique hollow structures demonstrate remarkable lithium storage properties. For example, the triple‐shelled Co₃O₄@Co₃V₂O₈ nanoboxes retain a high capacity of 948 mAh g^?1 after 100 cycles at 100 mA g^?1.     

Core–Shell Structure of Hierarchical Quasi‐Hollow MoS2 Microspheres Encapsulated Porous Carbon as Stable Anode for Li‐Ion Batteries

Monodisperse sulfonated polystyrene (SPS) microspheres are employed as both the template and carbon source to prepare MoS₂ quasi‐hollow microspheres‐encapsulated porous carbon. The synthesis procedure involves the hydrothermal growth of MoS₂ ultrathin nanosheets on the surface of SPS microspheres and subsequent annealing to remove SPS core. Incomplete decomposition of SPS during annealing due to the confining effect of MoS₂ shells leaves residual porous carbon in the interior. When being evaluated as the anode materials of Li‐ion batteries, the as‐prepared C@MoS₂ microspheres exhibit excellent cycling stability (95% of capacity retained after 100 cycles) and high rate behavior (560 mAh g^?1 at 5 A g^?1).     

Ultrafine Co3O4 Nanoparticles within Nitrogen‐Doped Carbon Matrix Derived from Metal–Organic Complex for Boosting Lithium Storage and Oxygen Evolution Reaction

Transition metal oxides have recently received great attention for application in advanced lithium‐ion batteries (LIBs) and oxygen evolution reaction (OER). Herein, the ethylenediaminetetraacetic cobalt complex as a precursor to synthesize ultrafine Co₃O₄ nanoparticles encapsulated into a nitrogen‐doped carbon matrix (NC) composites is presented. The as‐prepared Co₃O₄/NC‐350 obtained by pyrolysis at 350 °C demonstrates superior rate performance (372 mAh g^?1 at 5.0 A g^?1) and high cycling stability (92% capacity retention after 300 cycles at 1.0 A g^?1) as anode for LIBs. When evaluated as an electrocatalyst for OER, the Co₃O₄/NC‐350 achieves an overpotential of 298 mV at a current density of 10 mA cm^?2. The NC‐encapsualted porous hierarchical structure assures fast and continuous electron transportation, high activity sites, and strong structural integrity. This works offers novel complex precursors for synthesizing transition metal–based electrodes for boosting electrochemical energy conversion and storage.     

Bimetal‐Organic‐Framework Derivation of Ball‐Cactus‐Like Ni‐Sn‐P@C‐CNT as Long‐Cycle Anode for Lithium Ion Battery

Metal phosphides are a new class of potential high‐capacity anodes for lithium ion batteries, but their short cycle life is the critical problem to hinder its practical application. A unique ball‐cactus‐like microsphere of carbon coated NiP₂/Ni₃Sn₄ with deep‐rooted carbon nanotubes (Ni‐Sn‐P@C‐CNT) is demonstrated in this work to solve this problem. Bimetal‐organic‐frameworks (BMOFs, Ni‐Sn‐BTC, BTC refers to 1,3,5‐benzenetricarboxylic acid) are formed by a two‐step uniform microwave‐assisted irradiation approach and used as the precursor to grow Ni‐Sn@C‐CNT, Ni‐Sn‐P@C‐CNT, yolk–shell Ni‐Sn@C, and Ni‐Sn‐P@C. The uniform carbon overlayer is formed by the decomposition of organic ligands from MOFs and small CNTs are deeply rooted in Ni‐Sn‐P@C microsphere due to the in situ catalysis effect of Ni‐Sn. Among these potential anode materials, the Ni‐Sn‐P@C‐CNT is found to be a promising anode with best electrochemical properties. It exhibits a large reversible capacity of 704 mA h g^?1 after 200 cycles at 100 mA g^?1 and excellent high‐rate cycling performance (a stable capacity of 504 mA h g^?1 retained after 800 cycles at 1 A g^?1). These good electrochemical properties are mainly ascribed to the unique 3D mesoporous structure design along with dual active components showing synergistic electrochemical activity within different voltage windows.     

Doping of Ni and Zn Elements in MnCO3: High‐Power Anode Material for Lithium–Ion Batteries

Herein, Ni and Zn elements are doped simultaneously in MnCO₃ and microspheric Mn_xNi_yZn_zCO₃ is successfully obtained. Atomic mapping images reveal that the Ni and Zn elements have been successfully doped in MnCO₃ and thus the prepared sample is not a mixture of MnCO₃, NiCO₃, and ZnCO₃. It is the first time that the atomic mapping images of ternary transition metal carbonates have been demonstrated so far. The scanning transmission electron microscopy ‐ annular bright field (STEM‐ABF) image successfully confirms the formation of oxygen vacancies in Mn_xNi_yZn_zCO₃, which is beneficial to improve the electrical conductivity. The evolution of the microstructure from crystal to amorphization during cycling process confirmed by the fast Fourier transform patterns effectively lowers the overpotential of the conversion reaction and accelerates the conversion between Mn²⁺ and much higher valence of Mn element, contributing to the superior capacity of Mn_xNi_yZn_zCO₃ electrode. As anode material for lithium‐ion batteries, the prepared Mn_xNi_yZn_zCO₃ exhibits excellent long‐term cycling stability and outstanding rate performance, delivering the superior reversible discharge capacities of 1066 mA h g^?1 at 500 mA g^?1 after 500 cycles and 760 mA h g^?1 at 1 A g^?1 after 1000 cycles. It is the first time that Mn_xNi_yZn_zCO₃ has been synthesized and used as anode for lithium‐ion batteries so far.     

O3‐Type Layered Ni‐Rich Oxide: A High‐Capacity and Superior‐Rate Cathode for Sodium‐Ion Batteries

Inspired by its high‐active and open layered framework for fast Li⁺ extraction/insertion reactions, layered Ni‐rich oxide is proposed as an outstanding Na‐intercalated cathode for high‐performance sodium‐ion batteries. An O3‐type Na_0.75Ni_0.82Co_0.12Mn_0.06O₂ is achieved through a facile electrochemical ion‐exchange strategy in which Li⁺ ions are first extracted from the LiNi_0.82Co_0.12Mn_0.06O₂ cathode and Na⁺ ions are then inserted into a layered oxide framework. Furthermore, the reaction mechanism of layered Ni‐rich oxide during Na⁺ extraction/insertion is investigated in detail by combining ex situ X‐ray diffraction, X‐ray photoelectron spectroscopy, and electron energy loss spectroscopy. As an excellent cathode for Na‐ion batteries, O3‐type Na_0.75Ni_0.82Co_0.12Mn_0.06O₂ delivers a high reversible capacity of 171 mAh g^?1 and a remarkably stable discharge voltage of 2.8 V during long‐term cycling. In addition, the fast Na⁺ transport in the cathode enables high rate capability with 89 mAh g^?1 at 9 C. The as‐prepared Ni‐rich oxide cathode is expected to significantly break through the limited performance of current sodium‐ion batteries.     

Collaborative Design of Hollow Nanocubes,In Situ Cross‐Linked Binder,and Amorphous Void@SiOx@C as a Three‐Pronged Strategy for Ultrastable Lithium Storage

Although silicon‐based materials are ideal candidate anodes for high energy density lithium‐ion batteries, the large volumetric expansion seriously damages the integrity of the electrodes and impedes commercial processes. Reasonable electrode design based on adjustable structures of silicon and strong binders prepared by a facile method is still a great challenge. Herein, a three‐pronged collaborative strategy via hollow nanocubes, amorphous Void@SiO_x@C, and in situ cross‐linked polyacrylic acid and d ‐sorbitol 3D network binder (c‐PAA‐DS) is adopted to maintain structural/electrode integrality and stability. The all‐integrated c‐PAA‐DS/Void@SiO_x@C electrode delivers excellent mechanical property, which is attributed to ductility of the c‐PAA‐DS binder and high adhesion energy between Void@SiO_x@C and c‐PAA‐DS calculated by density functional theory. Benefiting from the synergistic effect of accommodation of the hollow structure, protection of outer carbon shell, amorphous Void@SiO_x@C, and strong adhesive c‐PAA‐DS binder, c‐PAA‐DS/Void@SiO_x@C shows excellent electrochemical performance. Long cycling stability with a reversible capacity of 696 mAh g^?1 is obtained, as well as tiny capacity decay after 500 cycles at 0.5 A g^?1 and high‐rate performance. The prelithiated Void@SiO_x@C||LiNi_0.5Co_0.2Mn_0.3O₂ (NCM523) full cell is also assembled and shows a reversible capacity of 157 mAh g^?1 at 0.5 C, delivering an excellent capacity retention of 94% after 160 cycles.     

High‐Performance Li–SeSx All‐Solid‐State Lithium Batteries

All‐solid‐state Li–S batteries are promising candidates for next‐generation energy‐storage systems considering their high energy density and high safety. However, their development is hindered by the sluggish electrochemical kinetics and low S utilization due to high interfacial resistance and the electronic insulating nature of S. Herein, Se is introduced into S cathodes by forming SeS_x solid solutions to modify the electronic and ionic conductivities and ultimately enhance cathode utilization in all‐solid‐state lithium batteries (ASSLBs). Theoretical calculations confirm the redistribution of electron densities after introducing Se. The interfacial ionic conductivities of all achieved SeS_x–Li₃PS₄ (x = 3, 2, 1, and 0.33) composites are 10^?6 S cm^?1. Stable and highly reversible SeS_x cathodes for sulfide‐based ASSLBs can be developed. Surprisingly, the SeS₂/Li₁₀GeP₂S₁₂–Li₃PS₄/Li solid‐state cells exhibit excellent performance and deliver a high capacity over 1100 mAh g^?1 (98.5% of its theoretical capacity) at 50 mA g^?1 and remained highly stable for 100 cycles. Moreover, high loading cells can achieve high areal capacities up to 12.6 mAh cm^?2. This research deepens the understanding of Se–S solid solution chemistry in ASSLB systems and offers a new strategy to achieve high‐performance S‐based cathodes for application in ASSLBs.     

Ultrathin Nanosheet Assembled Sn0.91Co0.19S2 Nanocages with Exposed (100) Facets for High‐Performance Lithium‐Ion Batteries

Ultrathin 2D inorganic nanomaterials are good candidates for lithium‐ion batteries, as well as the micro/nanocage structures with unique and tunable morphologies. Meanwhile, as a cost‐effective method, chemical doping plays a vital role in manipulating physical and chemical properties of metal oxides and sulfides. Thus, the design of ultrathin, hollow, and chemical doped metal sulfides shows great promise for the application of Li‐ion batteries by shortening the diffusion pathway of Li ions as well as minimizing the electrode volume change. Herein, ultrathin nanosheet assembled Sn_0.91Co_0.19S₂ nanocages with exposed (100) facets are first synthesized. The as‐prepared electrode delivers an excellent discharge capacity of 809 mA h g^?1 at a current density of 100 mA g^?1 with a 91% retention after 60 discharge–charge cycles. The electrochemical performance reveals that the Li‐ion batteries prepared by Sn_0.91Co_0.19S₂ nanocages have high capacity and great cycling stability.     

Surface Coating Constraint Induced Anisotropic Swelling of Silicon in Si–Void@SiO x Nanowire Anode for Lithium‐Ion Batteries

Here a simple and an environmentally friendly approach is developed for the fabrication of Si–void@SiO_x nanowires of a high‐capacity Li‐ion anode material. The outer surface of the robust SiO_x backbone and the inside void structure in Si–void@SiO_x nanowires appropriately suppress the volume expansion and lead to anisotropic swelling morphologies of Si nanowires during lithiation/delithiation, which is first demonstrated by the in situ lithiation process. Remarkably, the Si–void@SiO_x nanowire electrode exhibits excellent overall lithium‐storage performance, including high specific capacity, high rate property, and excellent cycling stability. A reversible capacity of 1981 mAh g^?1 is obtained in the fourth cycle, and the capacity is maintained at 2197 mAh g^?1 after 200 cycles at a current density of 0.5 C. The outstanding overall properties of the Si–void@SiO_x nanowire composite make it a promising anode material of lithium‐ion batteries for the power‐intensive energy storage applications.