SnO2/WO3 core-shell nanorods and their high reversible capacity as lithium-ion battery anodes

WO(3) nanorods are uniformly coated with SnO(2) nanoparticles via a facile wet-chemical route. The reversible capacity of SnO(2)/WO(3) core-shell nanorods is 845.9 mA h g(-1), higher than that of bare WO(3) nanorods, SnO(2) nanostructures, and traditional theoretical results. Such behavior can be attributed to a novel mechanism by which nanostructured metallic tungsten makes extra Li(2)O (from SnO(2)) reversibly convert to Li(+). This mechanism is confirmed by x-ray diffraction results. Our results open a way for enhancing the reversible capacity of alloy-type metal oxide anode materials.     

The synthesis and selective gas sensing characteristics of SnO(2)/α-Fe(2)O(3) hierarchical nanostructures

SnO(2)/α-Fe(2)O(3) hierarchical nanostructures, in which the SnO(2) nanorods grow on the side surface of α-Fe(2)O(3) nanorods as multiple rows, were synthesized via a three-step process. The diameters and lengths of the SnO(2) nanorods are 6-15?nm and about 120?nm. The growth direction of SnO(2) nanorods is [001], significantly affected by that of α-Fe(2)O(3) nanorods. The hetero-nanostructures exhibit very good selectivity to ethanol. The sensing characteristics are related to the special heterojunction structures, confirmed by high-resolution transmission electron microscopy observation. Therefore, a heterojunction barrier controlled gas sensing mechanism is realized. Our results demonstrate that the hetero-nanostructures are promising materials for fabricating sensors and other complex devices.     

超细Sn和SnO_2与碳复合的锂离子电池负极材料的制备及其电化学性能

采用溶液法以SnCl4.5H2O和葡萄糖为原料合成了颗粒尺寸为几个纳米的超细Sn及SnO2颗粒分布于无定形碳基体的复合材料,并在溶液过程中引入少量石墨。采用XRD、SEM和TEM等材料结构分析方法和恒电流充放电等电化学测试方法分析研究了前驱体的煅烧温度和石墨的引入对获得产物的结构及其作为锂离子电池负极材料的电化学性能的影响。研究结果表明,在500～700℃的煅烧温度下获得的Sn/C及含少量SnO2的Sn/SnO2/C复合材料,由于其中的Sn及SnO2的超细纳米尺寸及碳基体的缓冲有效减小了Sn在脱嵌锂过程中的应变和粉化,使材料具有良好的循环性能。石墨的引入有效提高了复合材料的容量和循环稳定性。经500℃煅烧的复合电极材料相对于其它材料具有更高的容量,其首次可逆容量达520mAh/g,经初始几个循环后,容量趋于稳定,经100次循环后,容量保持在350mAh/g。     

Highly conductive coaxial SnO(2)-In(2)O(3) heterostructured nanowires for Li ion battery electrodes

Novel SnO(2)-In(2)O(3) heterostructured nanowires were produced via a thermal evaporation method, and their possible nucleation/growth mechanism is proposed. We found that the electronic conductivity of the individual SnO(2)-In(2)O(3) nanowires was 2 orders of magnitude better than that of the pure SnO(2) nanowires, due to the formation of Sn-doped In(2)O(3) caused by the incorporation of Sn into the In(2)O(3) lattice during the nucleation and growth of the In(2)O(3) shell nanostructures. This provides the SnO(2)-In(2)O(3) nanowires with an outstanding lithium storage capacity, making them suitable for promising Li ion battery electrodes.     

Preparation and characterization of MgO nanorods coated with SnO2

MgO nanorods have been grown by thermal evaporation of Mg3N2 powders on Si (100) substrates coated with gold (Au) thin films. The MgO nanorods grown on Al2O3 (0001) were 0.1-0.2 microm in diameter and up to a few tens of micrometers in length. MgO/SnO2 coaxial nanorods have also been prepared by atomic layer deposition (ALD) of SnO2 onto the nanorods. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis results indicate that the MgO-cores and the SnO2 shells of the annealed coaxial nanorods are of a single crystalline nature with cubic and orthorhombic structures, respectively. The photoluminescence (PL) spectroscopy analysis results show that SnO2 coating slightly increases the PL emission intensity of MgO nanorods. The PL emission of the SnO2-coated MgO nanorods is found to be considerably enhanced by thermal annealing and to strongly depend on the annealing atmosphere. The PL emission intensity of the MgO/SnO2 coaxial nanorods has been significantly increased by annealing in a reducing atmosphere. The origin of the PL enhancement by annealing in a reducing atmosphere is discussed on the basis of energy-dispersive X-ray spectroscopy analyses.     

Tuning the Solid Electrolyte Interphase for Selective Li‐ and Na‐Ion Storage in Hard Carbon

Solid‐electrolyte interphase (SEI) films with controllable properties are highly desirable for improving battery performance. In this paper, a combined experimental and theoretical approach is used to study SEI films formed on hard carbon in Li‐ and Na‐ion batteries. It is shown that a stable SEI layer can be designed by precycling an electrode in a desired Li‐ or Na‐based electrolyte, and that ionic transport can be kinetically controlled. Selective Li‐ and Na‐based SEI membranes are produced using Li‐ or Na‐based electrolytes, respectively. The Na‐based SEI allows easy transport of Li ions, while the Li‐based SEI shuts off Na‐ion transport. Na‐ion storage can be manipulated by tuning the SEI layer with film‐forming electrolyte additives, or by preforming an SEI layer on the electrode surface. The Na specific capacity can be controlled to < 25 mAh g^?1; ≈ 1/10 of the normal capacity (250 mAh g^?1). Unusual selective/preferential transport of Li ions is demonstrated by preforming an SEI layer on the electrode surface and corroborated with a mixed electrolyte. This work may provide new guidance for preparing good ion‐selective conductors using electrochemical approaches.     

焙烧室温条件固相反应制备前驱物合成SnO2纳米棒的研究

室温条件下通过固相反应合成了SnO2纳米颗粒前驱物.在600～780℃对前驱物进行焙烧,在NaCl、KCl和KCl＋NaCl的熔盐介质中SnO2前驱物纳米颗粒自组装生长形成SnO2 纳米棒.利用TEM、XRD和XPS对SnO2纳米棒结构、形貌和成分进行了研究.结果表明SnO2纳米棒直径为20～80nm,长度从几百纳米到十几微米.分析了SnO2 纳米颗粒前驱体熔盐介质中的生长,利用固相转变生长可以解释SnO2纳米棒在熔盐介质中的生长机制.     

Needle-like Zn-doped SnO2 nanorods with enhanced photocatalytic and gas sensing properties

Zn-doped SnO(2) nanorods have been prepared by a simple hydrothermal method on a large scale. The as-prepared samples were characterized by x-ray powder diffraction, scanning electron microscope, transmission electron microscope, energy dispersive spectrometer, x-ray photoelectron spectroscopy, UV-vis absorption spectra and photoluminescence spectra. Studies found that the products are needle-like single-crystalline nanorods grown along the [[Formula: see text]] orientation. The photocatalytic properties of the synthesized Zn-doped SnO(2) were investigated by decomposing acid fuchsine, showing much higher photocatalytic activity than pure SnO(2) nanorods and bulk SnO(2) powders. An enhanced gas sensing ability toward methanal, ethanol and acetone gases is also achieved in high sensitivity and fast response. The origins of the enhanced performances are discussed.     

Fine-tuning of stannic oxide anodes’ material properties through calcination

Journal of Materials Science: Materials in Electronics - Phase pure stannic oxide (SnO2) is an efficient and reliable anode material for Li ion batteries. Understanding of pure SnO2 phase formation...     

Preparation of nano-sized graphite-supported CuO and Cu-Sn as active materials in lithium ion batteries

Nano-sized Cu-Sn and Cu oxide particles supported on ball-milled graphite were synthesized, and their electrochemical characteristics for use as anode active materials in lithium-ion batteries were investigated. The samples were also characterized via FE-SEM, XRD, and TGA. Most of the Cu oxides on BMG were monoclinic CuO crystals, whereas the Cu-Sn particles were composed of hexagonal Cu3Sn and tetragonal SnO2 crystals. These particles may contribute to an increase in the reversible capacity of lithium ion batteries.     

Beaklike SnO2 nanorods with strong photoluminescent and field-emission properties

Beaklike SnO2 nanorods were synthesized by a vapor-liquid-solid approach using Au as a catalyst. The nanorods grow along the [10 1] direction and the beak is formed by switching the growth direction to [1 12] through controlling the growth conditions at the end of the synthesis. The photoluminescence (PL) spectrum of the nanorods exhibits visible light emission with a peak at 602 nm. The field-emission (FE) properties of the nanorods have been measured to exhibit a turn-on field of 5.8 V microm(-1). A comparative study of FE measurements between SnO2 nanorods with uniform diameters and these beaklike nanorods suggests that the shape and curved tips are important factors in determining the FE properties.     

In Operando Probing of Lithium‐Ion Storage on Single‐Layer Graphene

Despite high‐surface area carbons, e.g., graphene‐based materials, being investigated as anodes for lithium (Li)‐ion batteries, the fundamental mechanism of Li‐ion storage on such carbons is insufficiently understood. In this work, the evolution of the electrode/electrolyte interface is probed on a single‐layer graphene (SLG) film by performing Raman spectroscopy and Fourier transform infrared spectroscopy when the SLG film is electrochemically cycled as the anode in a half cell. The utilization of SLG eliminates the inevitable intercalation of Li ions in graphite or few‐layer graphene, which may have complicated the discussion in previous work. Combining the in situ studies with ex situ observations and ab initio simulations, the formation of solid electrolyte interphase and the structural evolution of SLG are discussed when the SLG is biased in an electrolyte. This study provides new insights into the understanding of Li‐ion storage on SLG and suggests how high‐surface‐area carbons could play proper roles in anodes for Li‐ion batteries.     

SnO2 nanoparticles distributed on multi-walled carbon nanotubes and ball-milled graphite as anode materials of lithium ion batteries

SnO2 nanoparticles were supported on ball-milled graphite (BMG) or carbon nanotubes (CNTs) using a chemical reduction method with ethylene glycol, and the electrochemical properties of the nanocomposites were evaluated as anode active materials of lithium-ion batteries. The BMG and CNTs contributed to an increase in both the capacity enhancement and cyclic stability compared to that of commercial graphite. In particular, the mixture electrode of SnO2/BMG:SnO2/CNT = 3:1 (in weight ratio) showed higher performance in the reversible capacity and cyclic stability than did the SnO2/BMG and SnO2/CNT electrodes. This might be resulted from the network formation for excellent electronic path by CNT distributed on SnO2/BMG composites.     

Nanoscale Energy Storage Materials Produced by Hydrogen‐Driven Metallurgical Reactions

Nanoscale energy storage materials offer enhanced kinetics, material stability and gravimetric capacity, with respect to their bulk counterparts. Hydrogen‐driven metallurgical reactions (HDMR) represent a novel method for synthesis of these nanomaterials. Nanoscale and nanocomposite electrodes for Li‐ion batteries synthesized by HDMR demonstrate reversible lithium cycling at low temperature (298 °C). The nanocomposite electrodes are composed of an electrochemically active species (Li‐Sn, Li‐Al‐Sn and Li‐Al‐Si) imbedded within an inert Li₂O matrix. These electrodes are prepared in the charged state and therefore do not suffer from the first cycle capacity loss that is characteristic of the intermetallic anodes. This novel synthesis technique may also be applied to the preparation of new hydrogen storage compounds.     

Synthesis and optical properties of SnO(2) nanorods

Well-crystalline SnO(2) nanorods have been synthesized successfully via a lithium-assisted solution-phase method. The structural and optical properties of the SnO(2) nanorods were investigated using x-ray powder diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, and infrared, Raman and photoluminescence spectroscopy. The experimental results show that lithium addition plays a critical role in the formation of SnO(2) nanorods, and the correlation between the surface energy change and morphological evolution of this material is also discussed. This approach provides an economically viable route for large-scale synthesis of this nanostructured material.     

3DOM SnO2-SiO2锂离子电池负极材料的制备及电化学性能

针对SnO2锂离子电池负极材料长循环性能差的缺点,把非晶SiO2引入SnO2材料中,形成SnO2-SiO2纳米复合材料。采用聚苯乙烯(PS)胶晶作为模板,制备出三维有序大孔SnO2-SiO2纳米复合材料。研究结果表明,3DOM SnO2材料晶体结构和3DOM SnO2-SiO2材料相似,但是加入SiO2以后,3DOM SnO2-SiO2材料的长循环性能得到显著提高。在500 mAh/g的电流密度下循环100次,此时加0%Si的3DOM SnO2-SiO2材料的充电比容量急剧衰减为147 mAh/g,加5%Si的3DOM SnO2-SiO2材料的充电比容量达654 mAh/g,此外500次循环后加5%Si的3DOM SnO2-SiO2材料充电比容量增至728 mAh/g。这些结果表明SiO2能够改善3DOM SnO2材料长循环稳定性。     

Plant Leaf-Inspired Separators with Hierarchical Structure and Exquisite Fluidic Channels for Dendrite-Free Lithium Metal Batteries (Small 35/2023)

Lithium (Li) metal batteries are among the most promising devices for high energy storage applications but suffer from severe and irregular Li dendrite growth. Here, it is demonstrated that the issue can be well tackled by precisely designing the leaf-like membrane with hierarchical structure and exquisite fluidic channels. As a proof of concept, plant leaf-inspired membrane (PLIM) separators are prepared using natural attapulgite nanorods. The PLIM separators feature super-electrolyte-philicity, high thermal stability and high ion-selectivity. Thus, the separators can guide uniform and directed Li growth on the Li anode. The Li//PLIM//Li cell with limited Li anode shows high Coulombic efficiency and cycling stability over 1500 h with small overpotential and interface impedance. The Li//PLIM//S battery exhibits high initial capacity (1352 mAh g⁻¹), cycling stability (0.019% capacity decay per cycle at 1 C over 500 cycles), rate performance (673 mAh g⁻¹ at 4 C), and high operating temperature (65 °C). The separators can also effectively improve reversibility and cycling stability of the Li/Li cell and Li//LFP battery with carbonate-based electrolyte. As such, this work provides fresh insights into the design of bioinspired separators for dendrite-free metal batteries.     

SnO2纳米棒的制备及表征

在聚氧乙烯五醚（NP5），聚氧乙烯九醚（NP9），乳化剂（OP）和环己烷组成的微乳体系中制备二氧化锡前驱物。然后再经800－820℃熔烧2.5h，成功地制备了直径为30－90nm，长5－10μm的金红石结构的二氧化锡纳米棒，并用透射电子显微镜，电子衍射，X射线衍射对二氧化锡纳米棒的结构进行了表征。用熔盐合成机理对其形成进行了讨论，初步认为是成核、长大过程形成了二氧化锡纳米棒。     

Synthesis of tin oxide nanoparticle film by cathodic electrodeposition

Three-dimensional SnO2 nanoparticle films were deposited onto a copper substrate by cathodic electrodeposition in a nitric acid solution. A new formation mechanism for SnO2 films is proposed based on the oxidation of Sn2+ ion to Sn4+ ion by NO+ ion and the hydrolysis of Sn4+. The particle size of SnO2 was controlled by deposition potential. The SnO2 showed excellent charge capacity (729 mAh/g) at a 0.2 C rate and high rate capability (460 mAh/g) at a 5 C rate.     

An Electron/Ion Dual‐Conductive Alloy Framework for High‐Rate and High‐Capacity Solid‐State Lithium‐Metal Batteries

The solid‐state Li battery is a promising energy‐storage system that is both safe and features a high energy density. A main obstacle to its application is the poor interface contact between the solid electrodes and the ceramic electrolyte. Surface treatment methods have been proposed to improve the interface of the ceramic electrolytes, but they are generally limited to low‐capacity or short‐term cycling. Herein, an electron/ion dual‐conductive solid framework is proposed by partially dealloying the Li–Mg alloy anode on a garnet‐type solid‐state electrolyte. The Li–Mg alloy framework serves as a solid electron/ion dual‐conductive Li host during cell cycling, in which the Li metal can cycle as a Li‐rich or Li‐deficient alloy anode, free from interface deterioration or volume collapse. Thus, the capacity, current density, and cycle life of the solid Li anode are improved. The cycle capability of this solid anode is demonstrated by cycling for 500 h at 1 mA cm^?2, followed by another 500 h at 2 mA cm^?2 without short‐circuiting, realizing a record high cumulative capacity of 750 mA h cm^?2 for garnet‐type all‐solid‐state Li batteries. This alloy framework with electron/ion dual‐conductive pathways creates the possibility to realize high‐energy solid‐state Li batteries with extended lifespans.