Graphene‐Based Mesoporous SnO2 with Enhanced Electrochemical Performance for Lithium‐Ion Batteries

Graphene‐based metal oxides generally show outstanding electrochemical performance due to the superior properties of graphene. However, the aggregation of active metal oxide nanoparticles on the graphene surface may result in a capacity fading and poor cycle performance. Here, a mesostructured graphene‐based SnO₂ composite is prepared through in situ growth of SnO₂ particles on the graphene surface using cetyltrimethylammonium bromide as the structure‐directing agent. This novel mesoporous composite inherits the advantages of graphene nanosheets and mesoporous materials and exhibits higher reversible capacity, better cycle performance, and better rate capability compared to pure mesoporous SnO₂ and graphene‐based nonporous SnO₂. It is concluded that the synergetic effect between graphene and mesostructure benefits the improvement of the electrochemical properties of the hybrid composites. This facile method may offer an attractive alternative approach for preparation of the graphene‐based mesoporous composites as high‐ performance electrodes for lithium‐ion batteries.     

Hierarchical Double‐Shell Nanostructures of TiO2 Nanosheets on SnO2 Hollow Spheres for High‐Efficiency,Solid‐State,Dye‐Sensitized Solar Cells

A high‐energy conversion efficiency of 8.2% at 100 mW cm^?2 is reported, one of the highest values for N719‐based, solid‐state, dye‐sensitized solar cells (ssDSSCs). The solar cells are based on hierarchical double‐shell nanostructures consisting of inner SnO₂ hollow spheres (SHS) surrounded by outer TiO₂ nanosheets (TNSs). Deposition of the TNS on the SHS outer surface is performed via solvothermal reactions in order to generate a double‐shell SHS@TNS nanostructure that provides a large surface area and suppresses recombination of photogenerated electrons. An organized mesoporous (OM)‐TiO₂ film with high porosity, large pores, and good interconnectivity is also prepared via a sol‐gel process using a poly(vinyl chloride)‐g‐poly(oxyethylene methacrylate) (PVC‐g‐POEM) graft copolymer template. This film is utilized as a matrix to disperse the double‐shell nanostructures. Such nanostructures provide good pore‐filling for solid polymer electrolytes, faster electron transfer, and enhanced light scattering, as confirmed by reflectance spectroscopy, incident photon‐to‐electron conversion efficiency (IPCE), and intensity‐modulated photocurrent spectroscopy (IMPS)/intensity‐modulated photovoltage spectroscopy (IMVS).     

Lithium Tin Sulfide—a High‐Refractive‐Index 2D Material for Humidity‐Responsive Photonic Crystals

Extending the portfolio of novel stimuli‐responsive, high‐refractive‐index (RI) materials besides titania is key to improve the optical quality and sensing performance of existing photonic devices. Herein, lithium tin sulfide (LTS) nanosheets are introduced as a novel solution processable ultrahigh RI material (n = 2.50), which can be casted into homogeneous thin films using wet‐chemical deposition methods. Owing to its 2D morphology, thin films of LTS nanosheets are able to swell in response to changes of relative humidity. Integration of LTS nanosheets into Bragg stacks (BSs) based on TiO₂, SiO₂, nanoparticles or H₃Sb₃P₂O₁₄ nanosheets affords multilayer systems with high optical quality at an extremely low device thickness of below 1 µm. Owing to the ultrahigh RI of LTS nanosheets and the high transparency of the thin films, BSs based on porous titania as the low‐RI material are realized for the first time, showing potential application in light‐managing devices. Moreover, the highest RI contrast ever realized in BSs based on SiO₂ and LTS nanosheets is reported. Finally, exceptional swelling capability of an all‐nanosheet BS based on LTS and H₃Sb₃P₂O₁₄ nanosheets is demonstrated, which bodes well for a new generation of humidity sensors with extremely high sensitivity.     

Ionic Liquid‐Assisted Synthesis of TiO2–Carbon Hybrid Nanostructures for Lithium‐Ion Batteries

Building nanocomposite architectures based on nanocarbon materials (such as carbon nanotubes and graphene nanosheets) and metal‐oxide nanoparticles is of great interests for electrochemical energy storage. Here, an ionic‐liquid‐assisted strategy is presented to mediate the in situ growth of TiO₂ nanocrystals with controlled size on carbon nanotubes and graphene, and also reduce the modified carbon supports to recover the graphitic structure simultaneously. The as‐prepared nanocomposites exhibit a highly porous and robust structure with intimate coupling between TiO₂ nanocrystals and carbon supports, which offers facile ion and electron transport pathway as well as high mechanical stability. When evaluated as electrode materials for lithium‐ion batteries, the nanocomposites manifest high specific capacity, long cycling lifetime, and excellent rate capability, showing their promising application in high‐performance energy storage devices.     

A General Synthesis of Crumpled Metal Oxide Nanosheets as Superior Chemiresistive Sensing Layers

Metal oxide nanosheets having high mesoporosity, grain size distribution of 5–10 nm, and ultrathin thickness have attracted much attention due to their intriguing properties such as high surface‐to‐volume ratio and superior chemical activities. However, 2D nanostructures tend to restack, inducing a decrease in accessible surface area and a number of pores. To solve this problem, herein, a unique synthetic method of crumpled metal oxide nanosheets using spray pyrolysis of metal ion–coated graphene oxide, followed by heat treatment, is reported. This method is applicable not only to single‐component metal oxides but also to heterogeneous multicomponent metal oxides in which composition can be controlled. Crumpled SnO₂, ZnO, and Co₃O₄ as well as SnO₂/ZnO and SnO₂/Co₃O₄ nanosheets with heterogeneous interfaces are successfully synthesized and used as superior gas sensing layers. Because of the abundant reaction sites, well‐developed porosity for high gas accessibility, the formation of heterojunctions, the crumpled SnO₂/ZnO and SnO₂/Co₃O₄ nanosheets exhibit outstanding sensing performance (R_air/R_gas = 20.25 toward 5 ppm formaldehyde, and R_air/R_gas = 14.13 toward 5 ppm acetone, respectively). This study can contribute to the realization of a family of heterogeneous crumpled metal oxide nanosheets that can be applied to various research fields.     

Enhanced Stability of Perovskite Solar Cells with Low‐Temperature Hydrothermally Grown SnO2 Electron Transport Layers

Perovskite solar cells (PSCs) may offer huge potential in photovoltaic conversion, yet their practical applications face one major obstacle: their low stability, or quick degradation of their initial efficiencies. Here, a new design scheme is presented to enhance the PSC stability by using low‐temperature hydrothermally grown hierarchical nano‐SnO₂ electron transport layers (ETLs). The ETL contains a thin compact SnO₂ layer underneath a mesoporous layer of SnO₂ nanosheets. The mesoporous layer plays multiple roles of enhancing photon collection, preventing moisture penetration and improving the long‐term stability. Through such simple approaches, PSCs with power conversion efficiencies of ≈13% can be readily obtained, with the highest efficiency to be 16.17%. A prototypical PSC preserves 90% of its initial efficiency even after storage in air at room temperature for 130 d without encapsulation. This study demonstrates that hierarchical SnO₂ is a potential ETL for fabricating low‐cost and efficient PSCs with long‐term stability.     

Tin Oxide with Controlled Morphology and Crystallinity by Atomic Layer Deposition onto Graphene Nanosheets for Enhanced Lithium Storage

As one of the most promising negative electrode materials in lithium‐ion batteries (LIBs), SnO₂ experiences intense investigation due to its high specific capacity and energy density, relative to conventional graphite anodes. In this study, for the first time, atomic layer deposition (ALD) is used to deposit SnO₂, containing both amorphous and crystalline phases, onto graphene nanosheets (GNS) as anodes for LIBs. The resultant SnO₂‐graphene nanocomposites exhibit a sandwich structure, and, when cycled against a lithium counter electrode, demonstrate a promising electrochemical performance. It is demonstrated that the introduction of GNS into the nanocomposites is beneficial for the anodes by increasing their electrical conductivity and releasing strain energy: thus, the nanocomposite electrode materials maintain a high electrical conductivity and flexibility. It is found that the amorphous SnO₂‐GNS is more effective than the crystalline SnO₂‐GNS in overcoming electrochemical and mechanical degradation; this observation is consistent with the intrinsically isotropic nature of the amorphous SnO₂, which can mitigate the large volume changes associated with charge/discharge processes. It is observed that after 150 charge/discharge cycles, 793 mA h g^?1 is achieved. Moreover, a higher coulombic efficiency is obtained for the amorphous SnO₂‐GNS composite anode. This study provides an approach to fabricate novel anode materials and clarifies the influence of SnO₂ phases on the electrochemical performance of LIBs.     

High‐Performance Amorphous Multilayered ZnO‐SnO2 Heterostructure Thin‐Film Transistors: Fabrication and Characteristics

Multilayered ZnO‐SnO₂ heterostructure thin films consisting of ZnO and SnO₂ layers are produced by alternating the pulsed laser ablation of ZnO and SnO₂ targets, and their structural and field‐effect electronic transport properties are investigated as a function of the thickness of the ZnO and SnO₂ layers. The performance parameters of amorphous multilayered ZnO‐SnO₂ heterostructure thin‐film transistors (TFTs) are highly dependent on the thickness of the ZnO and SnO₂ layers. A highest electron mobility of 43 cm²/V·s, a low subthreshold swing of a 0.22 V/dec, a threshold voltage of 1 V, and a high drain current on‐to‐off ratio of 10¹⁰ are obtained for the amorphous multilayered ZnO(1.5 nm)‐SnO₂(1.5 nm) heterostructure TFTs, which is adequate for the operation of next‐generation microelectronic devices. These results are presumed to be due to the unique electronic structure of amorphous multilayered ZnO‐SnO₂ heterostructure film consisting of ZnO, SnO₂, and ZnO‐SnO₂ interface layers.     

An efficient titanium‐based photoanode for dye‐sensitized solar cell under back‐side illumination

Pretreatment of H₂O₂ is performed on titanium (Ti) foil as an efficient photoanode substrate for dye‐sensitized solar cell (DSSC). The H₂O₂‐treated Ti shows high surface area because of the formation of networked TiO₂ nanosheets, which enhances electrical contact between screen‐printed TiO₂ nanoparticles and Ti foil. Electron transfer on the photoanode is improved, as identified by reduced charge transfer resistance and improved electron transport properties. Compared with DSSC based on non‐treated Ti photoanode, DSSC with this H₂O₂‐treated Ti photoanode exhibits remarkable increases in short‐circuit current density (from 8.55 to 14.38 mA/cm²) and energy conversion efficiency (from 4.68 to 7.10%) under AM1.5 back‐side illumination. Copyright © 2011 John Wiley & Sons, Ltd.     

Overcoming Zinc Oxide Interface Instability with a Methylammonium‐Free Perovskite for High‐Performance Solar Cells

Perovskite solar cells have achieved the highest power conversion efficiencies on metal oxide n‐type layers, including SnO₂ and TiO₂. Despite ZnO having superior optoelectronic properties to these metal oxides, such as improved transmittance, higher conductivity, and closer conduction band alignment to methylammonium (MA)PbI₃, ZnO is largely overlooked due to a chemical instability when in contact with metal halide perovskites, which leads to rapid decomposition of the perovskite. While surface passivation techniques have somewhat mitigated this instability, investigations as to whether all metal halide perovskites exhibit this instability with ZnO are yet to be undertaken. Experimental methods to elucidate the degradation mechanisms at ZnO–MAPbI₃ interfaces are developed. By substituting MA with formamidinium (FA) and cesium (Cs), the stability of the perovskite–ZnO interface is greatly enhanced and it is found that stability compares favorably with SnO₂‐based devices after high‐intensity UV irradiation and 85 °C thermal stressing. For devices comprising FA‐ and Cs‐based metal halide perovskite absorber layers on ZnO, a 21.1% scanned power conversion efficiency and 18% steady‐state power output are achieved. This work demonstrates that ZnO appears to be as feasible an n‐type charge extraction layer as SnO₂, with many foreseeable advantages, provided that MA cations are avoided.     

A Band‐Edge Potential Gradient Heterostructure to Enhance Electron Extraction Efficiency of the Electron Transport Layer in High‐Performance Perovskite Solar Cells

As the key component in efficient perovskite solar cells, the electron transport layer (ETL) can selectively collect photogenerated charge carriers produced in perovskite absorbers and prevent the recombination of carriers at interfaces, thus ensuring a high power conversion efficiency. Compared with the conventional single‐ or dual‐layered ETLs, a gradient heterojunction (GHJ) strategy is more attractive to facilitate charge separation because the potential gradient created at an appropriately structured heterojunction can act as a driving force to regulate the electron transport toward a desired direction. Here, a SnO₂/TiO₂ GHJ interlayer configuration inside the ETL is reported to simultaneously achieve effective extraction and efficient transport of photoelectrons. With such an interlayer configuration, the GHJs formed at the perovskite/ETL interface act collectively to extract photogenerated electrons from the perovskite layer, while GHJs formed at the boundaries of the interconnected SnO₂ and TiO₂ networks throughout the entire ETL layer can extract electron from the slow electron mobility TiO₂ network to the high electron mobility SnO₂ network. Devices based on GHJ ETL exhibit a champion power conversion efficiency of 18.08%, which is significantly higher than that obtained from the compact TiO₂ ETL constructed under the comparable conditions.     

ZnO–SnO2 Hollow Spheres and Hierarchical Nanosheets: Hydrothermal Preparation,Formation Mechanism,and Photocatalytic Properties

ZnO–SnO₂ hollow spheres and hierarchical nanosheets are successfully synthesized using an aqueous solution containing ZnO rods, SnCl₄, and NaOH by using a simple hydrothermal method. The effects of hydrothermal temperature and time on the morphology of ZnO–SnO₂ are investigated. The formation process of ZnO–SnO₂ hollow spheres and nanosheets is discussed. The samples are characterized using X‐ray powder diffraction, transmission electron microscopy, scanning electron microscopy, and UV‐vis absorption spectroscopy. Both hollow spheres and hierarchical nanosheets show higher photocatalytic activities in the degradation of methyl orange than that of ZnO rods or SnO₂.     

An Integrated Free‐Standing Flexible Electrode with Holey‐Structured 2D Bimetallic Phosphide Nanosheets for Sodium‐Ion Batteries

An integrated, free‐standing, and binder‐free type of flexible anode electrode is fabricated from numerous holey‐structured, 2D nickel‐based phosphide nanosheets connected with carbon nanotubes. This electrode architecture can not only uniformly disperse the nanosheets throughout the whole electrode to avoid aggregation or detachment, but also provide an ideal sodium ion and electrolyte diffusion and penetration network with high electronic conductivity. Meanwhile, bimetallic phosphide formation by introducing secondary metal species will lead to a synergistic effect to modify the electrochemical properties. Due to the excellent compositional and structural characteristics of this electrode, it delivers superior performance. This designed flexible anode with Ni_1.5Co_0.5P_x nanosheets demonstrates a reversible capacity of 496.4 mAh g^?1 at 0.5 C and a good rate capacity of 276.1 mAh g^?1 at 8 C. Meanwhile, this connected integrated network woven from carbon nanotubes can effectively restrain volumetric expansion and shrinkage, and affect the conversion reaction products formation as well, from large‐sized microspheres to film structure, which is primarily credited with the improvement in electrochemical performance. This work may open up a new path for the synthesis of morphology‐controlled phosphides and promote the further development of flexible devices.     

Mass Production of High‐Quality Transition Metal Dichalcogenides Nanosheets via a Molten Salt Method

2D transition metal dichalcogenides (TMDs) are well suited for energy storage and field–effect transistors because of their thickness‐dependent chemical and physical properties. However, as current synthetic methods for 2D TMDs cannot integrate both advantages of liquid‐phase syntheses (i.e., massive production and homogeneity) and chemical vapor deposition (i.e., high quality and large lateral size), it still remains a great challenge for mass production of high‐quality 2D TMDs. Here, a molten salt method to massively synthesize various high‐crystalline TMDs nanosheets (MoS₂, WS₂, MoSe₂, and WSe₂) with the thicknesses less than 5 nm is reported, with the production yield over 68% with the reaction time of only several minutes. Additionally, the thickness and size of the as‐synthesized nanosheets can be readily controlled through adjusting reaction time and temperature. The as‐synthesized MoSe₂ nanosheets exhibit good electrochemical performance as pseudocapacitive materials. It is further anticipates that this work will provide a promising strategy for rapid mass production of high‐quality nonoxides nanosheets for energy‐related applications and beyond.     

Band‐Edge Engineered Hybrid Structures for Dye‐Sensitized Solar Cells Based on SnO2 Nanowires

In this report, we show for the first time that SnO₂ nanowire based dye sensitized solar cells exhibit an open circuit voltage of 560 mV, which is 200 mV higher than that using SnO₂ nanoparticle based cells. This is attributed to the more negative flat band potential of nanowires compared to the nanoparticles as determined by open circuit photo voltage measurements made at high light intensities. The nanowires were employed in hybrid structures consisting of highly interconnected SnO₂ nanowire matrix coated with TiO₂ nanoparticles, which showed an open circuit voltage of 720 mV and an efficiency of 4.1% compared to 2.1% obtained with pure SnO₂ nanowire matrix. The electron transport time constants for SnO₂ nanowire matrix were an order of magnitude lower and the recombination time constants are about 100 times higher than that of TiO₂ nanoparticles. The higher efficiency observed for DSSCs based on hybrid structure is attributed to the band edge positions of SnO₂ relative to that of TiO₂ and faster electron transport in SnO₂ nanowires.     

The Role of NiO Doping in Reducing the Impact of Humidity on the Performance of SnO2‐Based Gas Sensors: Synthesis Strategies,and Phenomenological and Spectroscopic Studies

The humidity dependence of the gas‐sensing characteristics in SnO₂‐based sensors, one of the greatest obstacles in gas‐sensor applications, is reduced to a negligible level by NiO doping. In a dry atmosphere, undoped hierarchical SnO₂ nanostructures prepared by the self‐assembly of crystalline nanosheets show a high CO response and a rapid response speed. However, the gas response, response/recovery speeds, and resistance in air are deteriorated or changed significantly in a humid atmosphere. When hierarchical SnO₂ nanostructures are doped with 0.64–1.27 wt% NiO, all of the gas‐sensing characteristics remain similar, even after changing the atmosphere from a dry to wet one. According to diffuse‐reflectance Fourier transform IR measurements, it is found that the most of the water‐driven species are predominantly absorbed not by the SnO₂ but by the NiO, and thus the electrochemical interaction between the humidity and the SnO₂ sensor surface is totally blocked. NiO‐doped hierarchical SnO₂ sensors exhibit an exceptionally fast response speed (1.6 s), a fast recovery speed (2.8 s) and a superior gas response (R_a/R_g = 2.8 at 50 ppm CO (R_a: resistance in air, R_g: resistance in gas)) even in a 25% r.h. atmosphere. The doping of hierarchical SnO₂ nanostructures with NiO is a very‐promising approach to reduce the dependence of the gas‐sensing characteristics on humidity without sacrificing the high gas response, the ultrafast response and the ultrafast recovery.     

Engineering of Facets,Band Structure,and Gas‐Sensing Properties of Hierarchical Sn2+‐Doped SnO2 Nanostructures

Hierarchical SnO₂ nanoflowers, assembled from single‐crystalline SnO₂ nanosheets with high‐index (11$ \bar 3 $ ) and (10$ \bar 2 $ ) facets exposed, are prepared via a hydrothermal method using sodium fluoride as the morphology controlling agent. Formation of the 3D hierarchical architecture comprising of SnO₂ nanosheets takes place via Ostwald ripening mechanism, with the growth orientation regulated by the adsorbate fluorine species. The use of Sn(II) precursor results in simultaneous Sn²⁺ self‐doping of SnO₂ nanoflowers with tunable oxygen vacancy bandgap states. The latter further results in the shifting of semiconductor Fermi levels and extended absorption in the visible spectral range. With increased density of states of Sn²⁺‐doped SnO₂ selective facets, this gives rise to enhanced interfacial charge transfer, that is, high sensing response, and selectivity towards oxidizing NO₂ gas. The better gas sensing performance over (10$ \bar 2 $ ) compared to (11$ \bar 3 $ ) faceted SnO₂ nanostructures is elucidated by surface energetic calculations and Bader analyses. This work highlights the possibility of simultaneous engineering of surface energetics and electronic properties of SnO₂ based materials.     

Fully High‐Temperature‐Processed SnO2 as Blocking Layer and Scaffold for Efficient,Stable, and Hysteresis‐Free Mesoporous Perovskite Solar Cells

Planar perovskite solar cells (PSCs) based on low‐temperature‐processed (LTP) SnO₂ have demonstrated excellent photovoltaic properties duo to the high electron mobility, wide bandgap, and suitable band energy alignment of LTP SnO₂. However, planar PSCs or mesoporous (mp) PSCs based on high‐temperature‐processed (HTP) SnO₂ show much degraded performance. Here, a new strategy with fully HTP Mg‐doped quantum dot SnO₂ as blocking layer (bl) and a quite thin SnO₂ nanoparticle as mp layer are developed. The performances of both planar and mp PSCs has been greatly improved. The use of Mg‐SnO₂ in planar PSCs yields a high‐stabilized power conversion efficiency (PCE) of close to 17%. The champion of mp cells exhibits hysteresis free and stable performance with a high‐stabilized PCE of 19.12%. The inclusion of thin mp SnO₂ in PSCs not only plays a role of an energy bridge, facilitating electrons transfer from perovskite to SnO₂ bl, but also enhances the contact area of SnO₂ with perovskite absorber. Impedance analysis suggests that the thin mp layer is an “active scaffold” selectively collecting electrons from perovskite and can eliminate hysteresis and effectively suppress recombination. This is an inspiring advance toward high‐performance PSCs with HTP mp SnO₂.     

Honeycomb‐Like Organized TiO2 Photoanodes with Dual Pores for Solid‐State Dye‐Sensitized Solar Cells

A solid‐state dye‐sensitized solar cell (ssDSSC) with 7.4% efficiency at 100 mW/cm² is reported. This efficiency is one of the highest observed for N719 dye. High performance is achieved via a honeycomb‐like, organized mesoporous TiO₂ photoanode with dual pores, high porosity, good interconnectivity, and excellent light scattering properties. The TiO₂ photoanodes are prepared without any TiCl₄ treatment via a one‐step, direct self‐assembly of hydrophilically preformed TiO₂ nanocrystals and poly(vinyl chloride)‐g‐poly(oxyethylene methacrylate) (PVC‐g‐POEM) graft copolymer as a titania source and a structure‐directing agent, respectively. Upon controlling the secondary forces between the polymer/TiO₂ hybrid and the solvent by varying the amounts of HCl/H₂O mixture or toluene, honeycomb‐like structures are generated to improve light scattering properties. Such multifunctional nanostructures with dual pores provide good pore‐filling of solid polymer electrolyte with large volume, enhanced light harvesting and reduced charge recombination, as confirmed by reflectance spectroscopy, incident photon‐to‐electron conversion efficiency (IPCE), and electrochemical impedance spectroscopy (EIS) analysis.     

Epitaxy of Radial High‐Energy‐Facetted Ultrathin TiO2 Nanosheets onto Nanowires for Enhanced Photoreactivities

Rational design and construction of novel nanostructures with outstanding functions, and investigation on the relationship between their structures and properties have continuously been intriguing but are still challenging now. In this work, 1D TiO₂(B) hierarchitectures with epitaxial {100} and {010} high‐energy‐facetted ultrathin 2D nanosheets that are parallel to the c‐axis are demonstrated for the first time. These hierarchitectures show much improved photochemical properties as compared with the nanoparticles and nanowires as well as the physical mixture of nanosheets and nanowires. These include photodegradation of methyl orange and water splitting, due to the remarkably increased surface area and active sites, and enhanced separation and transport of charge carriers. The findings reported here may inspire the engineering of highly active nanostructures for energy and environment related applications.