Graphene‐Bonded and ‐Encapsulated Si Nanoparticles for Lithium Ion Battery Anodes

Silicon (Si) has been considered a very promising anode material for lithium ion batteries due to its high theoretical capacity. However, high‐capacity Si nanoparticles usually suffer from low electronic conductivity, large volume change, and severe aggregation problems during lithiation and delithiation. In this paper, a unique nanostructured anode with Si nanoparticles bonded and wrapped by graphene is synthesized by a one‐step aerosol spraying of surface‐modified Si nanoparticles and graphene oxide suspension. The functional groups on the surface of Si nanoparticles (50–100 nm) not only react with graphene oxide and bind Si nanoparticles to the graphene oxide shell, but also prevent Si nanoparticles from aggregation, thus contributing to a uniform Si suspension. A homogeneous graphene‐encapsulated Si nanoparticle morphology forms during the aerosol spraying process. The open‐ended graphene shell with defects allows fast electrochemical lithiation/delithiation, and the void space inside the graphene shell accompanied by its strong mechanical strength can effectively accommodate the volume expansion of Si upon lithiation. The graphene shell provides good electronic conductivity for Si nanoparticles and prevents them from aggregating during charge/discharge cycles. The functionalized Si encapsulated by graphene sample exhibits a capacity of 2250 mAh g^?1 (based on the total mass of graphene and Si) at 0.1C and 1000 mAh g^?1 at 10C, and retains 85% of its initial capacity even after 120 charge/discharge cycles. The exceptional performance of graphene‐encapsulated Si anodes combined with the scalable and one‐step aerosol synthesis technique makes this material very promising for lithium ion batteries.     

Lithiophilic 3D Nanoporous Nitrogen‐Doped Graphene for Dendrite‐Free and Ultrahigh‐Rate Lithium‐Metal Anodes

The key bottlenecks hindering the practical implementations of lithium‐metal anodes in high‐energy‐density rechargeable batteries are the uncontrolled dendrite growth and infinite volume changes during charging and discharging, which lead to short lifespan and catastrophic safety hazards. In principle, these problems can be mitigated or even solved by loading lithium into a high‐surface‐area, conductive, and lithiophilic porous scaffold. However, a suitable material that can synchronously host a large loading amount of lithium and endure a large current density has not been achieved. Here, a lithiophilic 3D nanoporous nitrogen‐doped graphene as the sought‐after scaffold material for lithium anodes is reported. The high surface area, large porosity, and high conductivity of the nanoporous graphene concede not only dendrite‐free stripping/plating but also abundant open space accommodating volume fluctuations of lithium. This ingenious scaffold endows the lithium composite anode with a long‐term cycling stability and ultrahigh rate capability, significantly improving the charge storage performance of high‐energy‐density rechargeable lithium batteries.     

Hierarchical Porous Nanosheets Constructed by Graphene‐Coated,Interconnected TiO2 Nanoparticles for Ultrafast Sodium Storage

Sodium‐ion batteries (SIBs) are considered promising next‐generation energy storage devices. However, a lack of appropriate high‐performance anode materials has prevented further improvements. Here, a hierarchical porous hybrid nanosheet composed of interconnected uniform TiO₂ nanoparticles and nitrogen‐doped graphene layer networks (TiO₂@NFG HPHNSs) that are synthesized using dual‐functional C₃N₄ nanosheets as both the self‐sacrificing template and hybrid carbon source is reported. These HPHNSs deliver high reversible capacities of 146 mA h g^?1 at 5 C for 8000 cycles, 129 mA h g^?1 at 10 C for 20 000 cycles, and 116 mA h g^?1 at 20 C for 10 000 cycles, as well as an ultrahigh rate capability up to 60 C with a capacity of 101 mA h g^?1. These results demonstrate the longest cyclabilities and best rate capability ever reported for TiO₂‐based anode materials for SIBs. The unprecedented sodium storage performance of the TiO₂@NFG HPHNSs is due to their unique composition and hierarchical porous 2D structure.     

Critical Insight into the Relentless Progression Toward Graphene and Graphene‐Containing Materials for Lithium‐Ion Battery Anodes

Used as a bare active material or component in hybrids, graphene has been the subject of numerous studies in recent years. Indeed, from the first report that appeared in late July 2008, almost 1600 papers were published as of the end 2015 that investigated the properties of graphene as an anode material for lithium‐ion batteries. Although an impressive amount of data has been collected, a real advance in the field still seems to be missing. In this framework, attention is focused on the most prominent research efforts in this field with the aim of identifying the causes of such relentless progression through an insightful and critical evaluation of the lithium‐ion storage performances (i.e., 1^st cycle irreversible capacity, specific gravimetric and volumetric capacities, average delithiation voltage profile, rate capability and stability upon cycling). The “graphene fever” has certainly provided a number of fundamental studies unveiling the electrochemical properties of this “wonder” material. However, analysis of the published literature also highlights a loss of focus from the final application. Hype‐driven claims, not fully appropriate metrics, and negligence of key parameters are probably some of the factors still hindering the application of graphene in commercial batteries.     

Synergism of Rare Earth Trihydrides and Graphite in Lithium Storage: Evidence of Hydrogen‐Enhanced Lithiation

The lithium storage capacity of graphite can be significantly promoted by rare earth trihydrides (REH₃, RE = Y, La, and Gd) through a synergetic mechanism. High reversible capacity of 720 mA h g^?1 after 250 cycles is achieved in YH₃–graphite nanocomposite, far exceeding the total contribution from the individual components and the effect of ball milling. Comparative study on LaH₃–graphite and GdH₃–graphite composites suggests that the enhancement factor is 3.1–3.4 Li per active H in REH₃, almost independent of the RE metal, which is evident of a hydrogen‐enhanced lithium storage mechanism. Theoretical calculation suggests that the active H from REH₃ can enhance the Li⁺ binding to the graphene layer by introducing negatively charged sites, leading to energetically favorable lithiation up to a composition Li₅C₁₆H instead of LiC₆ for conventional graphite anode.     

Rationally Integrating 2D Confinement and High Sodiophilicity toward SnO2/Ti3C2Tx Composites for High-Performance Sodium-Metal Anodes

The metallic sodium (Na) is characterized by high theoretical specific capacity, low electrode potential and abundant resources, and its advantages manifests itself as a promising candidate anode of sodium metal batteries (SMBs). However, the vaporization during the plating/stripping or uncontrolled growth of sodium dendrites in sodium metal anodes (SMAs) has posed major challenges to its practical applications. To address this issue, here, the SnO₂/Ti₃C₂T_x composite is rationally fabricated, in which sodiophilic SnO₂ nanoparticles are in situ dispersed on the 2D Ti₃C₂T_x, providing the acceptor sites of Na⁺ that can control vaporization and dendrites. The SnO₂/Ti₃C₂T_x composite anode exhibits smooth and homogeneous morphology after Na-metal deposition cycles, stable Coulombic efficiency (CE) of half cells, long stable cycles of symmetric cells due to highly sodiophilic sites, and confinement effect. In addition, the full cells assembled with Na_0.6MnO₂ also show excellent rate performance and cycling performance. These discoveries demonstrate the effectiveness of the acceptor sites and the confinement effect provided by the SnO₂/Ti₃C₂T_x composite, and thus provide an additional degree of freedom for designing SMBs.     

3D Graphene Networks Encapsulated with Ultrathin SnS Nanosheets@Hollow Mesoporous Carbon Spheres Nanocomposite with Pseudocapacitance‐Enhanced Lithium and Sodium Storage Kinetics

The lithium and sodium storage performances of SnS anode often undergo rapid capacity decay and poor rate capability owing to its huge volume fluctuation and structural instability upon the repeated charge/discharge processes. Herein, a novel and versatile method is described for in situ synthesis of ultrathin SnS nanosheets inside and outside hollow mesoporous carbon spheres crosslinked reduced graphene oxide networks. Thus, 3D honeycomb‐like network architecture is formed. Systematic electrochemical studies manifest that this nanocomposite as anode material for lithium‐ion batteries delivers a high charge capacity of 1027 mAh g^?1 at 0.2 A g^?1 after 100 cycles. Meanwhile, the as‐developed nanocomposite still retains a charge capacity of 524 mAh g^?1 at 0.1 A g^?1 after 100 cycles for sodium‐ion batteries. In addition, the electrochemical kinetics analysis verifies the basic principles of enhanced rate capacity. The appealing electrochemical performance for both lithium‐ion batteries and sodium‐ion batteries can be mainly related to the porous 3D interconnected architecture, in which the nanoscale SnS nanosheets not only offer decreased ion diffusion pathways and fast Li⁺/Na⁺ transport kinetics, but also the 3D interconnected conductive networks constructed from the hollow mesoporous carbon spheres and reduced graphene oxide enhance the conductivity and ensure the structural integrity.     

Metal–Organic Gel‐Derived FexOy/Nitrogen‐Doped Carbon Films for Enhanced Lithium Storage

The development of cost‐effective and flexible electrodes is demanding in the field of energy storage. Herein, flexible Fe_xO_y/nitrogen‐doped carbon films (Fe_xO_y/NC‐MOG) are prepared by facile electrospinning of Fe‐based metal–organic gels (MOGs) followed by high‐temperature carbonization. This approach allows the even mixing of fragile coordination polymers with polyacrylonitrile into flexible films while reserving the structural characteristics of coordination polymers. After thermal treatment, Fe_xO_y/NC‐MOG films possess uniformly distributed Fe_xO_y nanoparticles and larger accessible surface areas than traditional Fe_xO_y‐NC films without MOG. Taking advantage of the unique structure, Fe_xO_y/NC‐MOG exhibits a superior rate performance (449.8 mA h g^?1 at 5000 mA g^–1) and long cycle life (629.3 mA h g^–1 after 500 cycles at 1000 mA g^–1) when used as additive‐free anodes in lithium‐ion batteries.     

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).