Higher Than 90% Initial Coulombic Efficiency with Staghorn-Coral-Like 3D Porous LiFeO2−x as Anode Materials for Li-Ion Batteries

Transition metal oxides represent a promising class of anode materials for high-capacity lithium-ion batteries. However, low initial coulombic efficiency (ICE, <80%) still remains a crucial challenge for practical applications. Herein, a unique 3D Fe(II)-rich porous LiFeO_2−x comprising of staghorn-coral-like skeleton measuring ≈100 nm in diameter is demonstrated, which is readily prepared by reacting Fe₂O₃ with LiH at 550 °C. When used as an anode material, the Fe(II)-rich LiFeO_2−x delivers the presently known highest ICE value of 90.2% with 1170 mAh g⁻¹ discharge capacity. The high ICE value can be ascribed to a fast conversion reaction of LiFeO_2−x upon lithiation/delithiation facilitated by the presence of Fe(II), which generates oxygen vacancies and makes electron transportation much easier, based on the experimental results and density functional theory (DFT) calculations.     

碗状C@FeS2@NC复合材料的制备及其电化学性能

在二氧化硅微球表面包覆一层酚醛树脂并在高温下将其转化为碳壳,然后进行溶剂热反应、多巴胺包覆、高温硫化以及氢氧化钠刻蚀,制备出碗状C@FeS₂@NC(氮掺杂碳层)复合材料。这种复合材料具有开放性三维碗状结构,能释放体积变化产生的应力,其较大的比表面积(70.67 m²·g^-1)有很多的活性点位。内外双层碳壳提高了这种复合材料的导电性并提供了稳定的机械结构,外层NC具有很好的保护作用。将这种复合材料用作锂离子电池负极,在0.2 A·g^-1电流密度下首圈放电比容量和充电比容量分别为954.3 mAh·g^-1和847.2 mAh·g^-1,对应的首圈库伦效率为88.78%。循环100圈后,其放电比容量稳定在793.8 mAh·g^-1。     

高性能自支撑CuS/SnS2锂电池负极材料

过渡金属硫化物作为锂电池负极材料具有极高比容量,但其制备的电极普遍存在导电性差、体积变化大等问题,本研究设计了一种新型的自支撑CuS/SnS₂镂空片状锂电池负极材料,以导电碳布作为基底,生长包覆CuS/SnS₂镂空纳米片,具备特殊的纳米包覆结构及双金属协同效应,使其在保持较高比容量的同时具备良好的循环稳定性,整体电化学性能优异。研究不同Cu/Sn含量对CuS/SnS₂负极材料电化学性能的影响,最佳配比的CuS/SnS₂负极材料在0.2 A·g?1电流密度下循环50次后比容量为1480 mAh·g?1,库伦效率稳定在99.5%,在2 A·g?1电流密度下循环200次后比容量仍能保持在697 mAh·g?1,库伦效率为99.8%。      

中空海胆状结构的碳包覆Fe2O3用作锂离子电池的高性能负极材料

Fe2O3由于成本低廉,储量丰富和理论比容量高(1007 mA hg^-1)等特点,在锂离子电池负极材料的应用中极具发展前景.然而一些问题仍然存在,如:充放电过程中比容量的迅速衰减,不可逆的体积膨胀以及较短的循环寿命等.这些问题严重制约了Fe2O3在锂离子电池中的实际应用.为了突破这些局限,本文以金属-有机骨架(MOF...     

球磨法制备锂金属氮化物及电化学性能研究

采用高能球磨法制备了锂离子电池负极材料锂金属氮化物Li_3-xM_xN(M=Co,Cu等)。制备的锂金属氮化物具有较高的电化学活性和充放电可逆性,可以用作锂离子电池的高容量负极材料。所制备的Li_2.6Co_0.4N前10次循环的脱嵌锂容量高达880mAh·g^-1。Li_2.6Co_0.2Cu_0.2N最初几个循环的脱嵌锂容量为750mAh·g^-1,45次充放电循环后的容量保持率为80％。Li_2.6Co_0.2Fe_0.2N是含有Li_2.6Co_0.4N的两相或多相混合物,40次充放电循环后脱锂容量为560mAh·g^-1,相对第二次脱锂容量的保持率为82％。     

高能球磨法制备PTFE/科琴黑-C柔性复合材料及其电化学应用

对荷叶进行多阶温度炭化得到前驱炭材料,将材料与科琴黑（KB）、聚四氟乙烯（PTFE）按照2:2:3的质量比球磨混合后真空抽滤制备一种锂硫电池中间层柔性材料,PTFE/KB-C复合材料的多孔结构能为高阶硫化物Li₂S_n（4≤n≤8）的进一步还原提供较多的三相反应位点,并利用PTFE/KB-C复合材料良好的多层多孔化学吸附作用来抑制可溶性多硫化物的穿梭。该中间层在以纯硫材料为正极的锂硫电池电性能测试表征中,1.0 C（电流密度1 675 mA·g-1）倍率下首次放电比容量达1 350 mAh·g-1,没有硝酸锂添加剂条件下经过100次充放电循环后比容量依旧保持在960 mAh·g-1,库伦效率基本在95%以上,保持了良好的循环稳定性。      

Edge‐Epitaxial Growth of 2D NbS2‐WS2 Lateral Metal‐Semiconductor Heterostructures

2D metal‐semiconductor heterostructures based on transition metal dichalcogenides (TMDs) are considered as intriguing building blocks for various fields, such as contact engineering and high‐frequency devices. Although, a series of p–n junctions utilizing semiconducting TMDs have been constructed hitherto, the realization of such a scheme using 2D metallic analogs has not been reported. Here, the synthesis of uniform monolayer metallic NbS₂ on sapphire substrate with domain size reaching to a millimeter scale via a facile chemical vapor deposition (CVD) route is demonstrated. More importantly, the epitaxial growth of NbS₂‐WS₂ lateral metal‐semiconductor heterostructures via a “two‐step” CVD method is realized. Both the lateral and vertical NbS₂‐WS₂ heterostructures are achieved here. Transmission electron microscopy studies reveal a clear chemical modulation with distinct interfaces. Raman and photoluminescence maps confirm the precisely controlled spatial modulation of the as‐grown NbS₂‐WS₂ heterostructures. The existence of the NbS₂‐WS₂ heterostructures is further manifested by electrical transport measurements. This work broadens the horizon of the in situ synthesis of TMD‐based heterostructures and enlightens the possibility of applications based on 2D metal‐semiconductor heterostructures.     

Near-Unity Polarization of Valley-Dependent Second-Harmonic Generation in Stacked TMDC Layers and Heterostructures at Room Temperature

With unique valley-dependent optical and optoelectronic properties, 2D transition metal dichalcogenides (2D TMDCs) are promising materials for valleytronics. Second-harmonic generation (SHG) in 2D TMDCs monolayers has shown valley-dependent optical selection rules. However, SHG in monolayer TMDCs is generally weak; it is important to obtain materials with both strong SHG signals and a large degree of polarization. In the work, a variety of inversion-symmetry-breaking (3R-like phase) TMDCs (WSe₂, WS₂, MoS₂) atomic layers, spiral structures, and heterostructures are prepared, and their SHG polarization is studied. Through circular-polarization-resolved SHG experiments, it is demonstrated that the SHG intensity is enhanced in thicker samples by breaking inversion symmetry while maintaining the degree of polarization close to unity at room temperature. By studying TMDCs with different twist angles and the spiral structures, it is found that there is no significant effect of multilayer interlayer interaction on valley-dependent SHG. The realization of strong SHG with high degree of polarization may pave the way toward a new platform for nonlinear optical valleytronics devices based on 2D semiconductors.     

Direct Growth of Perovskite Crystals on Metallic Electrodes for High‐Performance Electronic and Optoelectronic Devices

Metal halide perovskite has attracted enhanced interest for its diverse electronic and optoelectronic applications. However, the fabrication of micro‐ or nanoscale crystalline perovskite functional devices remains a great challenge due to the fragility, solvent, and heat sensitivity of perovskite crystals. Here, a strategy is proposed to fabricate electronic and optoelectronic devices by directly growing perovskite crystals on microscale metallic structures in liquid phase. The well‐contacted perovskite/metal interfaces ensure these heterostructures serve as high‐performance field effect transistors (FETs) and excellent photodetector devices. When serving as an FET, the on/off ratio is as large as 10⁶ and the mobility reaches up to ≈2.3 cm² V^?1 s^?1. A photodetector is displayed with high photoconductive switching ratio of ≈10⁶ and short response time of ≈4 ms. Furthermore, the photoconductive response is proved to be band‐bending‐assisted separation of photoexcited carriers at the Schottky barrier of the silver and p‐type perovskites.     

A High‐On/Off‐Ratio Floating‐Gate Memristor Array on a Flexible Substrate via CVD‐Grown Large‐Area 2D Layer Stacking

Memristors such as phase‐change memory and resistive memory have been proposed to emulate the synaptic activities in neuromorphic systems. However, the low reliability of these types of memories is their biggest challenge for commercialization. Here, a highly reliable memristor array using floating‐gate memory operated by two terminals (source and drain) using van der Waals layered materials is demonstrated. Centimeter‐scale samples (1.5 cm × 1.5 cm) of MoS₂ as a channel and graphene as a trap layer grown by chemical vapor deposition (CVD) are used for array fabrication with Al₂O₃ as the tunneling barrier. With regard to the memory characteristics, 93% of the devices exhibit an on/off ratio of over 10³ with an average ratio of 10⁴. The high on/off ratio and reliable endurance in the devices allow stable 6‐level memory applications. The devices also exhibit excellent memory durability over 8000 cycles with a negligible shift in the threshold voltage and on‐current, which is a significant improvement over other types of memristors. In addition, the devices can be strained up to 1% by fabricating on a flexible substrate. This demonstration opens a practical route for next‐generation electronics with CVD‐grown van der Waals layered materials.     

预嵌锂多壁碳纳米管的性能

使用稳定锂金属粉末(SLMP)/多壁碳纳米管(MWCNTs)作为负极、以活性炭(AC)作为正极组装锂离子电容器,研究其电化学性能。根据恒流充放电(GCD)和交流阻抗谱(EIS)研究了预嵌锂前后锂离子电容器的电化学性能。结果表明,嵌入适量的SLMP可消除碳纳米管大部分固有的不可逆容量并提高电容器的电化学性能。这种电容器具有较高的能量密度、功率密度和优异的循环性能。电流密度为0.05 A/g时预嵌锂碳纳米管锂离子电容器的比电容达到85.18 F/g,电流密度为0.05~4 A/g时最大能量密度和最大功率密度分别为140.4 Wh/kg和5.25 KW/kg,经过3000次循环后容量保持率仍约为82%。     

25th Anniversary Article: Hybrid Nanostructures Based on Two‐Dimensional Nanomaterials

Two‐dimensional (2D) nanomaterials, such as graphene and transition metal dichalcogenides (TMDs), receive a lot of attention, because of their intriguing properties and wide applications in catalysis, energy‐storage devices, electronics, optoelectronics, and so on. To further enhance the performance of their application, these 2D nanomaterials are hybridized with other functional nanostructures. In this review, the latest studies of 2D nanomaterial‐based hybrid nanostructures are discussed, focusing on their preparation methods, properties, and applications.