Designing Compatible Ceramic/Polymer Composite Solid-State Electrolyte for Stable Silicon Nanosheet Anodes.

The commercialization of silicon anode for lithium-ion batteries has been hindered by severe structure fracture and continuous interfacial reaction against liquid electrolytes, which can be mitigated by solid-state electrolytes. However, rigid ceramic electrolyte suffers from large electrolyte/electrode interfacial resistance, and polymer electrolyte undergoes poor ionic conductivity, both of which are worsened by volume expansion of silicon. Herein, by dispersing Li1.3Al0.3Ti1.7(PO4)3 (LATP) into poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP) and poly(ethylene oxide) (PEO) matrix, the PVDF-HFP/PEO/LATP (PHP-L) solid-state electrolyte with high ionic conductivity (1.40 × 10-3 S cm-1), high tensile strength and flexibility is designed, achieving brilliant compatibility with silicon nanosheets. The chemical interactions between PVDF-HFP and PEO, LATP increase amorphous degree of polymer, accelerating Li+ transfer. Good flexibility of the PHP-L contributes to adaptive structure variation of electrolyte with silicon expansion/shrinkage, ensuring swift interfacial ions transfer. Moreover, the solid membrane with high tensile limits electrode structural degradation and eliminates continuous interfacial growth to form stable 2D solid electrolyte interface (SEI) film, achieving superior cyclic performance to liquid electrolytes. The Si//PHP-L15//LiFePO4 solid-state full-cell exhibits stable lithium storage with 81% capacity retention after 100 cycles. This work demonstrates the effectiveness of composite solid electrolyte in addressing fundamental interfacial and performance challenges of silicon anodes.

Niobium-Based Oxide for Anode Materials for Lithium-Ion Batteries.

Recently, it has become imperative to develop high energy density as well as high safety lithium-ion batteries (LIBS) to meet the growing energy demand. Among the anode materials used in LIBs, the currently used commercial graphite has low capacity and is a safety hazard due to the formation of lithium dendrites during the reaction. Among the transition metal oxide (TMO) anode materials, TMO based on the intercalation reaction mechanism has a more stable structure and is less prone to volume expansion than TMO based on the conversion reaction mechanism, especially the niobium-based oxide in it has attracted much attention. Niobium-based oxides have a high operating potential to inhibit the formation of lithium dendrites and lithium deposits to ensure safety, and have stable and fast lithium ion transport channels with excellent multiplicative performance. This review summarizes the recent developments of niobium-based oxides as anode materials for lithium-ion batteries, discusses the special structure and electrochemical reaction mechanism of the materials, the synthesis methods and morphology of nanostructures, deficiencies and improvement strategies, and looks into the future developments and challenges of niobium-based oxide anode materials.

Synthesis of heterointerfaces in NiO/SnO2 coated nitrogen-doped graphene for efficient lithium storage.

Currently, it remains a challenge to make comprehensive improvements to overcome the disadvantages of volume expansion, Li2O irreversibility and low conductivity of SnO2. Heterostructure construction has been investigated as an effective strategy to promote electron transfer and surface reaction kinetics, leading to high electrochemical performance. Herein, NiO/SnO2 heterojunction modified nitrogen doped graphene (NiO/SnO2@NG) anode materials were prepared using hydrothermal and carbonization techniques. Based on the excellent structural advantages, sufficiently small NiO/SnO2 heterojunction nanoparticles increase the interfacial density to promote Li2O decomposition, and the built-in electric field accelerates the charge transport rate to improve the conductivity. The three-dimensional porous graphene framework effectively mitigates volume expansion during cycling and stabilizes the reactive interface of electrode materials. The results show that the NiO/SnO2@NG mixture has high reversible specific capacity (938.8 mA h g-1 after 450 cycles at 0.1 A g-1), superior multiplicity performance (374.5 mA h g-1 at 3.0 A g-1) and long cycle life (685.3 mA h g-1 after 1000 cycles at 0.5 A g-1). Thus, this design of introducing NiO to form heterostructures with SnO2 is directly related to enhancing the electrochemical performance of lithium-ion batteries (LIBs).

Carbon-coated silicon/graphite oxide composites as anode materials for highly stable lithium-ion batteries.

Silicon (Si) has been widely investigated as an anode material for lithium-ion batteries (LIBs) due to its high theoretical capacity. However, the huge volume expansion and low electrical conductivity limit its practical application to some extent. Here, we prepared silicon/reduced graphene oxide/amorphous carbon (Si/G/C) anode materials for lithium-ion batteries using a facile synergistic cladding layer. The protective effect of different carbon layers was explored and it was found that ternary composites have excellent electrochemical properties. In this work, the surface of Si was first modified using ammonia, and the positively charged Si was tightly anchored to the graphene sheet layer. In contrast, amorphous carbon was used as a reinforcing coating for further coating to synergistically build up the cladding layer of Si NPs with graphene oxide. The ternary composite (Si/G/C) material greatly ensures the structural integrity of the composites and shows excellent cycling as well as rate performance compared to Si/reduced graphene oxide and Si/carbon composites. For the Si/G/C composite, at a current density of 1 A g-1, it can be stably cycled over 267 times with 70% capacity retention (only 0.0711% capacity reduction per cycle).

Using Sandwiched Silicon/Reduced Graphene Oxide Composites with Dual Hybridization for Their Stable Lithium Storage Properties.

Using silicon/reduced graphene oxide (Si/rGO) composites as lithium-ion battery (LIB) anodes can effectively buffer the volumetric expansion and shrinkage of Si. Herein, we designed and prepared Si/rGO-b with a sandwiched structure, formed by a duple combination of ammonia-modified silicon (m-Si) nanoparticles (NP) with graphene oxide (GO). In the first composite process of m-Si and GO, a core-shell structure of primal Si/rGO-b (p-Si/rGO-b) was formed. The amino groups on the m-Si surface can not only hybridize with the GO surface to fix the Si particles, but also form covalent chemical bonds with the remaining carboxyl groups of rGO to enhance the stability of the composite. During the electrochemical reaction, the oxygen on the m-Si surface reacts with lithium ions (Li+) to form Li2O, which is a component of the solid-electrolyte interphase (SEI) and is beneficial to buffering the volume expansion of Si. Then, the p-Si/rGO-b recombines with GO again to finally form a sandwiched structure of Si/rGO-b. Covalent chemical bonds are formed between the rGO layers to tightly fix the p-Si/rGO-b, and the conductive network formed by the reintroduced rGO improves the conductivity of the Si/rGO-b composite. When used as an electrode, the Si/rGO-b composite exhibits excellent cycling performance (operated stably for more than 800 cycles at a high-capacity retention rate of 82.4%) and a superior rate capability (300 mA h/g at 5 A/g). After cycling, tiny cracks formed in some areas of the electrode surface, with an expansion rate of only 27.4%. The duple combination of rGO and the unique sandwiched structure presented here demonstrate great effectiveness in improving the electrochemical performance of alloy-type anodes.

A New Structure with Localized sp2 Bonding for Fivefold Twinning in Diamond.

Changes in atomic bonding configuration in carbon from sp3 to sp2 are known to exist in certain structural defects in diamond, such as twin boundaries, grain boundaries, and dislocations, which have a significant impact on many properties of diamond. In this work, the atomic structure of fivefold twinning in detonation synthesized ultra-dispersed diamonds is investigated using a combination of techniques, including spherical aberration-corrected high-resolution electron microscopy (HREM), HREM image simulations, and molecular mechanics (MM) calculations. The experimental HREM images reveal clearly that the fivefold twinning in diamond has two distinct structures. In addition to the concentric fivefold twins, where the core structure is the intersection of five {111} twinning boundaries, a new extended core structure with co-hybridization of bonding is identified and analyzed in fivefold twinning. The atomic structure forming these fivefold twinning boundaries and their respective core structures is proposed to involve both the tetrahedral sp3 and planar graphitic sp2 bonding configurations, in which a co-hybridized planar hexagon of carbon serves as a fundamental structural unit. The presence of this sp2 -bonded planar unit of hexagonal carbon rings in general grain boundaries is also discussed.

Mass Loading-Independent Lithium Storage of Transitional Metal Compounds Achieved by Multi-Dimensional Synergistic Nanoarchitecture.

Nanostructured transitional metal compounds (TMCs) have demonstrated extraordinary promise for high-efficient and rapid lithium storage. However, good performance is usually limited to electrodes with low mass loading (≤1.0 mg cm-2 ) and is difficult to realize at higher mass loading due to increased electrons/ions transport limitations in the thicker electrode. Herein, the multi-dimensional synergistic nanoarchitecture design of graphene-wrapped MnO@carbon microcapsules (capsule-like MnO@C-G) is reported, which demonstrates impressive mass loading-independent lithium storage properties. Highly porous MnO nanoclusters assembled by 0D nanocrystals facilitate sufficient electrolyte infiltration and shorten the solid-state ions transport path. 1D carbon shell, 2D graphene, and 3D continuous network with tight interconnection accelerate electrons transport inside the thick electrode. The capsule-like MnO@C-G delivers ultrahigh gravimetric capacity retention of 91.0% as the mass loading increases 4.3 times, while the areal capacities increase linearly with the mass loading at various current densities. Specifically, the capsule-like MnO@C electrode delivers a remarkable areal capacity of 2.0 mAh cm-2 at a mass loading of 3.0 mg cm-2 . Moreover, the capsule-like MnO@C also demonstrates excellent performance in full battery applications. This study demonstrates the effectiveness of multi-dimensional synergistic nanoarchitecture in achieving mass loading-independent performance, which can be extended to other TMCs for electrochemical energy storage.

Amorphous hollow manganese silicate nanosphere oxidase mimic for ultrasensitive and high-reliable colorimetric detection of biothiols.

Metal-based nanozymes with exceptional physicochemical property and intrinsic enzymatic properties have been widely used in industrial, medical, and diagnostic fields. However, low substrate affinity results in unsatisfying catalytic kinetic and instability in complicated conditions, which significantly decreases their sensitivity and reliability. Herein, an amorphous hollow manganese silicate nanosphere (defined as AHMS) has been successfully synthesized via a facile one-step hydrothermal method and utilized in the archetype for colorimetric detection of biothiols with high sensitivity and high reliability. The experimental data demonstrates that ultrafast affinity of the substrate contributes to enhanced sensitivity with outstanding catalytic kinetic features (Km = 27.1 µM) and low limit of detection (LODGSH = 20 nM). The designed sensor demonstrates a reliable applicability for analysis of biological liquids (fetal calf serum and Staphylococcus aureus) and design of visual logic gates. Therefore, AHMS provides a promising strategy for ultrasensitive and high-reliable biosensing.

Deformable BCN/Fe3O4/PCL composites through electromagnetic wave remote control.

Electromagnetic wave (EMW) induction of shape memory polymer (SMP) composites with multifunctional inorganic fillers is a high efficiency, uniform, and non-contact method. Herein, the shape memory effect of ternary BCN/Fe3O4/PCL composites induced by EMWs are explored. The components of Fe3O4 and the BCN nanotubes serve as wave-absorbing materials. The electromagnetic properties and EMW absorption performance of BCN/Fe3O4/PCL are discussed in detail. The EMWs absorbed by BCN/Fe3O4/PCL are dissipated by dielectric loss and magnetic loss. The shape memory mechanism of BCN/Fe3O4/PCL is based on the Fe3O4 and BCN nanotubes dissipating absorbed EMW energy into heat to boost the temperature of the composites, thereby responding to EMW remote control. This work introduces a new direction for SMPs induced by EMWs as potential candidates in the application of shape recovery in a restricted space.

A facile coprecipitation method to synthesize FexOy/Fe decorated graphite sheets with enhanced microwave absorption properties.

FexOy/Fe decorated graphite sheets (DGS) are synthesized using a facile coprecipitation method followed by heat treatment under different conditions. The size and chemical composition of the particles loaded on graphite sheets can be tailored by adjusting the heat treatment temperature and atmosphere. The obtained α-Fe2O3 DGS (S1), Fe3O4 DGS (S2 and S3), and Fe DGS (S4) all exhibit excellent electromagnetic (EM) wave absorption when compared with conventional graphite/magnetic-particle composites. The minimum reflection loss (RL) can reach -42.1 dB at 4.16 GHz in the S2/paraffin composites. The bandwidth of the RL below -10 dB covers 4.4 GHz (11.04-15.44 GHz) with a thickness of 2 mm. A possible EM wave loss mechanism has been proposed in detail. The multiple absorbing mechanisms could control the excellent absorption, resulting in a product with a feasible application in stealth materials.

Facile approach to fabricate BCN/Fe x (B/C/N) y nano-architectures with enhanced electromagnetic wave absorption.

Carbon-based materials have excited extensive interest for their remarkable electrical properties and low density for application in electromagnetic (EM) wave absorbents. However, the processing of heteroatoms doping in carbon nanostructures is an insuperable challenge for attaining effective reflection loss and EM matching. Herein, a facile method for large-scale synthesis of boron and nitrogen doped carbon nanotubes decorated by ferrites particles is proposed. The BCN nanotubes (50-100 nm in diameter) imbedded with nanosized Fe x (B/C/N) y (10-20 nm) are successfully constructed by two steps of polymerization and carbonthermic reduction. The product exhibits an outstanding reflection loss (RL) performance, in that the minimum RL is -47.97 dB at 11.44 GHz with a broad bandwidth 11.2 GHz (from 3.76 to 14.9 GHz) below -10 dB indicating a competitive absorbent in stealth materials. Crystalline and theoretical studies of the absorption mechanism indicate a unique dielectric dispersion effect in the absorbing bandwidth.

A general strategy toward graphitized carbon coating on iron oxides as advanced anodes for lithium-ion batteries.

Integration of carbon materials with benign iron oxides is blazing a trail in constructing high-performance anodes for lithium-ion batteries (LIBs). In this paper, a unique general, simple, and controllable strategy is developed toward in situ uniform coating of iron oxide nanostructures with graphitized carbon (GrC) layers. The basic synthetic procedure only involves a simple dip-coating process for the loading of Ni-containing seeds and a subsequent Ni-catalyzed chemical vapor deposition (CVD) process for the growth of GrC layers. More importantly, the CVD treatment is conducted at a quite low temperature (450 °C) and with extremely facile liquid carbon sources consisting of ethylene glycol (EG) and ethanol (EA). The GrC content of the resulting hybrids can be controllably regulated by altering the amount of carbon sources. The electrochemical results reveal remarkable performance enhancements of iron oxide@GrC hybrids compared with pristine iron oxides in terms of high specific capacity, excellent rate and cycling performance. This can be attributed to the network-like GrC coating, which can improve not only the electronic conductivity but also the structural integrity of iron oxides. Moreover, the lithium storage performance of samples with different GrC contents is measured, manifesting that optimized electrochemical property can be achieved with appropriate carbon content. Additionally, the superiority of GrC coating is demonstrated by the advanced performance of iron oxide@GrC compared with its corresponding counterpart, i.e., iron oxides with amorphous carbon (AmC) coating. All these results indicate the as-proposed protocol of GrC coating may pave the way for iron oxides to be promising anodes for LIBs.

Electrochemical depositing rGO-Ti-rGO heterogeneous substrates with higher thermal conductivity and heat transfer performance compared to pure Ti.

Titanium (Ti) and its alloys are widely applied in many high strength, light weight applications, but their thermal conductivity is lower compared to that of other metals, which limits their further applications. In this paper, we demonstrated experimentally that rGO-Ti-rGO heterogeneous substrates with higher thermal conductivity, up to ∼38.8% higher than Ti, could be fabricated by electrochemical depositing rGO on their surface. The rGO layers are grown on the surface of Ti substrates, with appearance of bedclothes on the beds. The thickness of rGO layers is around 300-500 nm and around 600-1000 nm when deposited for 5 cycles and 10 cycles, respectively. According to the cooling experiment results, as-prepared Ti + rGO substrates can present excellent thermal conduction performance, and reduce the chip temperature close to 3.2 °C-13.1 °C lower than Ti alloy substrates with the heat flow density of 0.4-3.6 W cm-2. Finally, the approach to electro-chemically deposit hundreds of nanometer rGO layers on the surface of Ti substrates can improve their thermal conductivity and heat transfer performance, which may have further application in the increasing thermal conduction of other metal-alloys, ceramics and polymers.

Porous-carbon-nanotube decorated carbon nanofibers with effective microwave absorption properties.

Carbon nanofibers decorated with porous carbon nanotubes were prepared by electrospinning and annealing methods. The microwave reflection loss of the products was investigated in the frequency range of 2-18 GHz. The bandwidth with a reflection loss less than -10 dB covers a wide frequency, ranging from 7.0 to 14.1 GHz with thickness of 3.0-5.5 mm, and the minimum reflection loss is -44.5 dB at 10.7 GHz with thickness of 2.0 mm. The large reflection loss and wide reflection band reveal that the products could be a promising candidate for microwave absorption.

Template-free fabrication of graphene-wrapped mesoporous ZnMn2O4 nanorings as anode materials for lithium-ion batteries.

We rationally designed a facile two-step approach to synthesize ZnMn2O4@G composite anode material for lithium-ion batteries (LIBs), involving a template-free fabrication of ZnMn2O4 nanorings and subsequent coating of graphene sheets. Notably, it is the first time that ring-like ZnMn2O4 nanostructure is reported. Moreover, our system has been demonstrated to be quite powerful in producing ZnMn2O4 nanorings regardless of the types of Zn and Mn-containing metal salts reactants. The well-known inside-out Ostwald ripening process is tentatively proposed to clarify the formation mechanism of the hollow nanorings. When evaluated as anode material for LIBs, the resulting ZnMn2O4@G hybrid displays significantly improved lithium-storage performance with high specific capacity, good rate capability, and excellent cyclability. After 500 cycles, the ZnMn2O4@G hybrid can still deliver a reversible capacity of 958 mAh g-1 at a current density of 200 mA g-1, much higher than the theoretical capacity of 784 mAh g-1 for pure ZnMn2O4. The outstanding electrochemical performance should be reasonably ascribed to the synergistic interaction between hollow and porous ZnMn2O4 nanorings and the three-dimensional interconnected graphene sheets.

A novel one-step strategy toward ZnMn2O4/N-doped graphene nanosheets with robust chemical interaction for superior lithium storage.

Ingenious hybrid electrode design, especially realized with a facile strategy, is appealing yet challenging for electrochemical energy storage devices. Here, we report the synthesis of a novel ZnMn2O4/N-doped graphene (ZMO/NG) nanohybrid with sandwiched structure via a facile one-step approach, in which ultrafine ZMO nanoparticles with diameters of 10-12 nm are well dispersed on both surfaces of N-doped graphene (NG) nanosheets. Note that one-step synthetic strategies are rarely reported for ZMO-based nanostructures. Systematical control experiments reveal that the formation of well-dispersed ZMO nanoparticles is not solely ascribed to the restriction effect of the functional groups on graphene oxide (GO), but also to the presence of ammonia. Benefitting from the synergistic effects and robust chemical interaction between ZMO nanoparticles and N-doped graphene nanosheets, the ZMO/NG hybrids deliver a reversible capacity up to 747 mAh g(-1) after 200 cycles at a current density of 500 mA g(-1). Even at a high current density of 3200 mA g(-1), an unrivaled capacity of 500 mAh g(-1) can still be retained, corroborating the good rate capability.

Hierarchically constructed NiCo2S4@Ni(1-x)Co x (OH)2 core/shell nanoarrays and their application in energy storage.

We report a new type of core-shell heterostructure consisting of a rod-like NiCo2S4 (NCS) core and an urchin-like Ni(1-x)Co x (OH)2 (NCOH) shell via a simple hydrothermal route coupled with a facile electrodeposition. NCS nanorod arrays (NRAs) can not only act as excellent electrochemically active materials by themselves, but they can also serve as hierarchical porous scaffolds capable of fast electron conduction and ion diffusion for loading a large amount of additional active materials. Moreover, it is observed that the urchin-like NCOH nanosheets coating could bind the inner NCS nanorods together and thereby reinforce the whole structure mechanically. Meanwhile, more effective pathways for electrons are available in the NCS@NCOH hybrids than an individual NCS nanorod. Benefiting from both structural and compositional features, the NCS@NCOH electrode exhibits greatly improved electrochemical performance with high capacity (3.54 C cm(-2) at 1 mA cm(-2)) and excellent cycling stability (78% capacity retention after 4000 cycles). Moreover, a battery-type device is also fabricated by using NCS@NCOH as a positive electrode and activated carbon (AC) as a negative electrode, displaying high capacity (2.51 C cm(-2) at 2 mA cm(-2)) and good durability (88.8% capacity retention after 4000 cycles) as well.

Investigation of photoelectrical properties of α-Si3N4 nanobelts with surface modifications using first-principles calculations.

The structural stability, electronic and optical properties of α-Si3N4 nanobelts orientating along the different directions with surface H, F and Cl modifications are investigated using first-principles methods. The stabilities of α-Si3N4 nanobelts are greatly affected by the surface modifications and increased in the order of H, Cl and F. All the modified α-Si3N4 nanobelts exhibit semiconductor characteristics. The effective masses of nanobelts are mainly affected by their orientations as well as surface modifications. The band gaps of α-Si3N4 nanobelts are found to be modulated by surface modifications. The Cl-modified nanobelts result in a smaller band gap than that of H- or F-modified ones. The electronic properties of α-Si3N4 nanobelts have significantly affected their optical properties. The linear light response ranges are mainly located in the ultraviolet region, where the absorption and refraction of light mainly occur, while the reflection is very weak. As the halogen coverage increases to 100%, the absorption edges of α-Si3N4 nanobelts have an obvious red-shift and new dielectric peaks appear. The Cl-modified nanobelts possess higher ε2(ω) peaks, lower absorption edges and better photoelectric characteristics than those of H- or F-modified nanobelts. The static optical parameters ε(0) and n(0) of 100% Cl-modified α-Si3N4 nanobelts are significantly larger than those of other nanobelts, indicating special applications in certain optical components.

Orientation- and passivation-dependent stability and electronic properties of α-Si3N4 nanobelts.

The energetic stability and electronic properties of unpassivated, hydrogen (-H) and hydroxyl (-OH) passivated α-Si3N4 nanobelts orientating along the [101], [210], [011], [100], [001], and [110] directions are investigated by first-principles calculations. Calculations show that the energetic stabilities of α-Si3N4 nanobelts depend weakly upon orientations of nanobelts, but sensitively on passivation treatments. The most stable nanobelt is the OH cluster partially passivated α-Si3N4, followed by the H atom fully passivated and the unpassivated systems. All the unpassivated nanobelts show metallic characteristics due to the presence of dangling bonds of surficial atoms in nanobelts, while all the passivated nanobelts exhibit semiconducting characteristics. The valence band maximum (VBM) and the conduction band minimum (CBM) mainly originate from the surface N-2p and Si-3p states, respectively. For α-Si3N4 nanobelts orientating along [101], [210], [011] and [110] directions, the OH passivated systems exhibit a much smaller band gap than the H passivated systems, while the [100] and [001] orientated nanobelts exhibit the opposite band-gap properties.

Facile synthesis of morphology-controlled hybrid structure of ZnCo2O4 nanosheets and nanowires for high-performance asymmetric supercapacitors.

Controllable synthesis of electrode materials with desirable morphology and size is of significant importance and challenging for high-performance supercapacitors. Herein, we propose an efficient hydrothermal approach to controllable synthesis of hierarchical porous three-dimensional (3D) ZnCo2O4 composite films directly on Ni foam substrates. The composite films consisted of two-dimensional (2D) nanosheets array anchored with one-dimensional (1D) nanowires. The morphologies of ZnCo2O4 arrays can be easily controlled by adjusting the concentration of NH4F. The effect of NH4F in the formation of these 3D hierarchical porous ZnCo2O4 nanosheets@nanowires films is systematically investigated based on the NH4F-independent experiments. This unique 3D hierarchical structure can help enlarge the electroactive surface area, accelerate the ion and electron transfer, and accommodate structural strain. The as-prepared hierarchical porous ZnCo2O4 nanosheets@nanowires films exhibited inspiring electrochemical performance with high specific capacitance of 1289.6 and 743.2 F g-1 at the current density of 1 and 30 A g-1, respectively, and a remarkable long cycle stability with 86.8% capacity retention after 10 000 cycles at the current density of 1 A g-1. Furthermore, the assembled asymmetric supercapacitor using the as-prepared ZnCo2O4 nanosheets@nanowires films as the positive electrode and active carbon as negative electrode delivered a high energy density of 39.7 W h kg-1 at a power density of 400 W kg-1. Our results show that these unique hierarchical porous 3D ZnCo2O4 nanosheets@nanowires films are promising candidates as high-performance electrodes for energy storage applications.