Controllable Design of MoS2 Nanosheets Grown on Nitrogen‐Doped Branched TiO2/C Nanofibers: Toward Enhanced Sodium Storage Performance Induced by Pseudocapacitance Behavior

In this work, expanded MoS₂ nanosheets grown on nitrogen‐doped branched TiO₂/C nanofibers (NBT/C@MoS₂ NFs) are prepared through electrospinning and hydrothermal treatment method as anode materials for sodium‐ion batteries (SIBs). The continuous 1D branched TiO₂/C nanofibers provide a large surface area to grow expanded MoS₂ nanosheets and enhance the electronic conductivity and cycling stability of the electrode. The large surface area and doping of nitrogen can facilitate the transfer of both Na⁺ ions and electrons. With the merits of these unique design and extrinsic pseudocapacitance behavior, the NBT/C@MoS₂ NFs can deliver ultralong cycle stability of 448.2 mA h g^?1 at 200 mA g^?1 after 600 cycles. Even at a high rate of 2000 mA g^?1, a reversible capacity of 258.3 mA h g^?1 can still be achieved. The kinetic analysis demonstrates that pseudocapacitive contribution is the major factor to achieve excellent rate performance. The rational design and excellent electrochemical performance endow the NBT/C@MoS₂ NFs with potentials as promising anode materials for SIBs.     

N‐Doped Carbon Nanofibers with Interweaved Nanochannels for High‐Performance Sodium‐Ion Storage

Although graphite materials have been applied as commercial anodes in lithium‐ion batteries (LIBs), there still remain abundant spaces in the development of carbon‐based anode materials for sodium‐ion batteries (SIBs). Herein, an electrospinning route is reported to fabricate nitrogen‐doped carbon nanofibers with interweaved nanochannels (NCNFs‐IWNC) that contain robust interconnected 1D porous channels, produced by removal of a Te nanowire template that is coelectrospun within carbon nanofibers during the electrospinning process. The NCNFs‐IWNC features favorable properties, including a conductive 1D interconnected porous structure, a large specific surface area, expanded interlayer graphite‐like spacing, enriched N‐doped defects and active sites, toward rapid access and transport of electrolyte and electron/sodium ions. Systematic electrochemical studies indicate that the NCNFs‐IWNC exhibits an impressively high rate capability, delivering a capacity of 148 mA h g^?1 at current density of as high as 10 A g^?1, and has an attractively stable performance over 5000 cycles. The practical application of the as‐designed NCNFs‐IWNC for a full SIBs cell is further verified by coupling the NCNFs‐IWNC anode with a FeFe(CN)₆ cathode, which displays a desirable cycle performance, maintaining acapacity of 97 mA h g^?1 over 100 cycles.     

In Situ Fabrication of Hierarchically Branched TiO2 Nanostructures: Enhanced Performance in Photocatalytic H2 Evolution and Li–Ion Batteries

1D branched TiO₂ nanomaterials play a significant role in efficient photocatalysis and high‐performance lithium ion batteries. In contrast to the typical methods which generally have to employ epitaxial growth, the direct in situ growth of hierarchically branched TiO₂ nanofibers by a combination of the electrospinning technique and the alkali‐hydrothermal process is presented in this work. Such the branched nanofibers exhibit improvement in terms of photocatalytic hydrogen evolution (0.41 mmol g⁻¹ h⁻¹), in comparison to the conventional TiO₂ nanofibers (0.11 mmol g⁻¹ h⁻¹) and P25 (0.082 mmol g⁻¹ h⁻¹). Furthermore, these nanofibers also deliver higher lithium specific capacity at different current densities, and the specific capacity at the rate of 2 C is as high as 201. 0 mAh g⁻¹, roughly two times higher than that of the pristine TiO₂ nanofibers.     

静电纺制备二氧化锡/碳纳米纤维锂离子电池负极材料的研究进展

二氧化锡纳米材料具有毒性小、成本低、可逆容量高等优点,是当前研究最为广泛的锂离子动力电池负极材料之一。构建与碳复合的二氧化锡基纳米结构是缓解二氧化锡在长时间的嵌/脱锂循环过程中体积膨胀、控制纳米颗粒团聚问题以及增加材料导电性的有效方法。用高效、可控的静电纺丝技术,结合高温煅烧、水热合成、化学沉积等方法,可制备出结构型二氧化锡/碳复合纳米纤维。本文讨论了具有不同碳层分布的均匀型、核壳型及三明治型结构的二氧化锡/碳复合纳米纤维的制备方法,以及不同碳层分布对其锂电性能的改善状况及机理分析。     

CuO Quantum Dots Embedded in Carbon Nanofibers as Binder‐Free Anode for Sodium Ion Batteries with Enhanced Properties

The design of sodium ion batteries is proposed based on the use of flexible membrane composed of ultrasmall transition metal oxides. In this paper, the preparation of CuO quantum dots (≈2 nm) delicately embedded in carbon nanofibers (denoted as 2‐CuO@C) with a thin film via a feasible electrospinning method is reported. The CuO content can be controlled by altering the synthetic conditions and is optimized to 54 wt%. As binder‐free anode for sodium ion batteries, 2‐CuO@C delivers an initial reversible capacity of 528 mA h g^?1 at the current density of 100 mA g^?1, an exceptional rate capability of 250 mA h g^?1 at 5000 mA g^?1, and an ultra‐stable capacity of 401 mA h g^?1 after 500 cycles at 500 mA g^?1. The enhancement of electrochemical performance is attributed to the unique structure of 2‐CuO@C, which offers a variety of advantages: highly conductive carbon matrix suppressing agglomeration of CuO grains, interconnected nanofibers ensuring short transport length for electrons, well‐dispersed CuO quantum dots leading to highly utilization rate, and good mechanical properties resulting in strong electrode integrity.     

Dendrite‐Free Sodium‐Metal Anodes for High‐Energy Sodium‐Metal Batteries

Sodium (Na) metal is one of the most promising electrode materials for next‐generation low‐cost rechargeable batteries. However, the challenges caused by dendrite growth on Na metal anodes restrict practical applications of rechargeable Na metal batteries. Herein, a nitrogen and sulfur co‐doped carbon nanotube (NSCNT) paper is used as the interlayer to control Na nucleation behavior and suppress the Na dendrite growth. The N‐ and S‐containing functional groups on the carbon nanotubes induce the NSCNTs to be highly “sodiophilic,” which can guide the initial Na nucleation and direct Na to distribute uniformly on the NSCNT paper. As a result, the Na‐metal‐based anode (Na/NSCNT anode) exhibits a dendrite‐free morphology during repeated Na plating and striping and excellent cycling stability. As a proof of concept, it is also demonstrated that the electrochemical performance of sodium–oxygen (Na–O₂) batteries using the Na/NSCNT anodes show significantly improved cycling performances compared with Na–O₂ batteries with bare Na metal anodes. This work opens a new avenue for the development of next‐generation high‐energy‐density sodium‐metal batteries.     

Mesoporous Hollow Sb/ZnS@C Core–Shell Heterostructures as Anodes for High‐Performance Sodium‐Ion Batteries

Combining the advantage of metal, metal sulfide, and carbon, mesoporous hollow core–shell Sb/ZnS@C hybrid heterostructures composed of Sb/ZnS inner core and carbon outer shell are rationally designed based on a robust template of ZnS nanosphere, as anodes for high‐performance sodium‐ion batteries (SIBs). A partial cation exchange reaction based on the solubility difference between Sb₂S₃ and ZnS can transform mesoporous ZnS to Sb₂S₃/ZnS heterostructure. To get a stable structure, a thin contiguous resorcinol‐formaldehyde (RF) layer is introduced on the surface of Sb₂S₃/ZnS heterostructure. The effectively protective carbon layer from RF can be designed as the reducing agent to convert Sb₂S₃ to metallic Sb to obtain core–shell Sb/ZnS@C hybrid heterostructures. Simultaneously, the carbon outer shell is beneficial to the charge transfer kinetics, and can maintain the structure stability during the repeated sodiation/desodiation process. Owing to its unique stable architecture and synergistic effects between the components, the core–shell porous Sb/ZnS@C hybrid heterostructure SIB anode shows a high reversible capacity, good rate capability, and excellent cycling stability by turning the optimized voltage range. This novel strategy to prepare carbon‐layer‐protected metal/metal sulfide core–shell heterostructure can be further extended to design other novel nanostructured systems for high‐performance energy storage devices.     

An Advanced MoS2/Carbon Anode for High‐Performance Sodium‐Ion Batteries

Molybdenum disulfide (MoS₂) is a promising anode for high performance sodium‐ion batteries due to high specific capacity, abundance, and low cost. However, poor cycling stability, low rate capability and unclear electrochemical reaction mechanism are the main challenges for MoS₂ anode in Na‐ion batteries. In this study, molybdenum disulfide/carbon (MoS₂/C) nanospheres are fabricated and used for Na‐ion battery anodes. MoS₂/C nanospheres deliver a reversible capacity of 520 mAh g^?1 at 0.1 C and maintain at 400 mAh g^?1 for 300 cycles at a high current density of 1 C, demonstrating the best cycling performance of MoS₂ for Na‐ion batteries to date. The high capacity is attributed to the short ion and electron diffusion pathway, which enables fast charge transfer and low concentration polarization. The stable cycling performance and high coulombic efficiency (～100%) of MoS₂/C nanospheres are ascribed to (1) highly reversible conversion reaction of MoS₂ during sodiation/desodiation as evidenced by ex‐situ X‐ray diffraction (XRD) and (2) the formation of a stable solid electrolyte interface (SEI) layer in fluoroethylene carbonate (FEC) based electrolyte as demonstrated by fourier transform infrared spectroscopy (FTIR) measurements.     

In Situ Carbon‐Doped Mo(Se0.85S0.15)2 Hierarchical Nanotubes as Stable Anodes for High‐Performance Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) are promising energy storage devices, but suffer from poor cycling stability and low rate capability. In this work, carbon doped Mo(Se_0.85S_0.15)₂ (i.e., Mo(Se_0.85S_0.15)₂:C) hierarchical nanotubes have been synthesized for the first time and serve as a robust and high‐performance anode material. The hierarchical nanotubes with diameters of 300 nm and wall thicknesses of 50 nm consist of numerous 2D layered nanosheets, and can act as a robust host for sodiation/desodiation cycling. The Mo(Se_0.85S_0.15)₂:C hierarchical nanotubes deliver a discharge capacity of 360 mAh g⁻¹ at a high current density of 2000 mA g⁻¹ and keep a 81.8% capacity retention compared to that at a current density of 50 mA g⁻¹, showing superior rate capability. Comparing with the second cycle discharge capacities, the nanotube anode can maintain capacities of 102.2%, 101.9%, and 97.8% after 100 cycles at current densities of 200, 500, and 1000 mA g⁻¹, respectively. This work demonstrates the best cycling performance and high‐rate sodium storage capabilities of MoSe₂ for SIBs to date. The hollow interior, hierarchical organization, layered structure, and carbon doping are beneficial for fast Na⁺‐ion and electron kinetics and are responsible for the stable cycling performance and high rate capabilities.     

Bismuth Nanoparticle@Carbon Composite Anodes for Ultralong Cycle Life and High‐Rate Sodium‐Ion Batteries

Bismuth has emerged as a promising anode material for sodium‐ion batteries (SIBs), owing to its high capacity and suitable operating potential. However, large volume changes during alloying/dealloying processes lead to poor cycling performance. Herein, bismuth nanoparticle@carbon (Bi@C) composite is prepared via a facile annealing method using a commercial coordination compound precursor of bismuth citrate. The composite has a uniform structure with Bi nanoparticles embedded within a carbon framework. The nanosized structure ensures a fast kinetics and efficient alleviation of stress/strain caused by the volume change, and the resilient and conductive carbon matrix provides an interconnected electron transportation pathway. The Bi@C composite delivers outstanding sodium‐storage performance with an ultralong cycle life of 30 000 cycles at a high current density of 8 A g^?1 and an excellent rate capability of 71% capacity retention at an ultrahigh current rate of 60 A g^?1. Even at a high mass loading of 11.5 mg cm^?2, a stable reversible capacity of 280 mA h g^?1 can be obtained after 200 cycles. More importantly, full SIBs by pairing with a Na₃V₂(PO₄)₃ cathode demonstrates superior performance. Combining the facile synthesis and the commercial precursor, the exceptional performance makes the Bi@C composite very promising for practical large‐scale applications.