Vanadium Oxide Cathode Coinserted by Ni2+ and NH4+ for High-Performance Aqueous Zinc-Ion Batteries.

Vanadium-based oxides have garnered significant attention as cathode materials for aqueous zinc-ion batteries (AZIBs) because of their high theoretical capacity and low cost. However, the limited reaction kinetics and poor long-term cycle stability hinder their widespread application. In this paper, we propose a novel approach by coinserting Ni2+ and NH4+ ions into V2O5·3H2O, i.e., NNVO. Structural characterization shows that the coinsertion of Ni2+ and NH4+ not only extends the interlayer spacing of V2O5·3H2O but also significantly promotes the transport kinetics of Zn2+ because of the synergistic "pillar" effect of Ni2+ and NH4+, as well as the increased oxygen vacancies that effectively lower the energy barrier for Zn2+ insertion. As a result, the AZIBs with an NNVO electrode exhibit a high capacity of 398.1 mAh g-1 (at 1.0 A g-1) and good cycle stability with 89.1% capacity retention even after 2000 cycles at 5.0 A g-1. At the same time, a highly competitive energy density of 262.9 Wh kg-1 is delivered at 382.9 W kg-1. Considering the simple scheme and the resultant high performance, this study may provide a positive attempt to develop high-performance AZIBs.

A Mott-Schottky Heterojunction with Strong Chemisorption and Fast Conversion Effects for Room-Temperature Na-S Batteries.

The practical application of the room-temperature sodium-sulfur (RT Na-S) batteries is currently limited by low reversible capacity and serious capacity decay due to the sluggish reaction kinetics and shuttle effect. It is necessary to design a suitable sulfur host integrated with electrocatalysts to realize effective chemisorption and catalysis of sodium polysulfides (NaPSs). Herein, under the guidance of theoretical calculation, the Mott-Schottky heterojunction with a built-in electric field composed of iron (Fe) and iron disulfide (FeS2 ) components anchored on a porous carbon matrix (Fe/FeS2 -PC) is designed and prepared. The enhanced chemisorption effect of Fe, the fast electrocatalytic effect of FeS2 , and the fast transfer effect of the built-in electric field within the Fe/FeS2 heterojunction in the cathode of RT Na-S batteries work together to effectively improve the electrochemical performance. As a result, the Fe/FeS2 -PC@S cathode exhibits high reversible capacity (815 mAh g-1 after 150 cycles at 0.2 A g-1 ) and excellent stability (516 mAh g-1 after 600 cycles at 5 A g-1 , with only 0.07% decay per cycle). The design of the Fe/FeS2 heterojunction electrocatalyst provides a new strategy for the development of highly stable RT Na-S batteries.

Metal Nanoclusters as a Superior Polysulfides Immobilizer toward Highly Stable Lithium-Sulfur Batteries.

Due to their high designability, unique geometric and electronic structures, and surface coordination chemistry, atomically precise metal nanoclusters are an emerging class of functional nanomaterials at the forefront of materials research. However, the current research on metal nanoclusters is mainly fundamental, and their practical applications are still uncharted. The surface binding properties and redox activity of Au24 Pt(PET)18 (PET: phenylethanethiolate, SCH2 CH2 Ph) nanoclusters are herein harnessed as an high-efficiency electrocatalyst for the anchoring and rapid conversion of lithium polysulfides in lithium-sulfur batteries (LSBs). Au24 Pt(PET)18 @G composites are prepared by using the large specific surface area, high porosity, and conductive network of graphene (G) for the construction of battery separator that can inhibit polysulfide shuttle and accelerate electrochemical kinetics. Resultantly, the LSB using a Au24 Pt(PET)18 @G-based separator presents a high reversible specific capacity of 1535.4 mA h g-1 for the first cycle at 0.2 A g-1 and a rate capability of 887 mA h g-1 at 5 A g-1 . After 1000 cycles at 5 A g-1 , the capacity is 558.5 mA h g-1 . This study is a significant step toward the application of metal nanoclusters as optimal electrocatalysts for LSBs and other sustainable energy storage systems.

Notable Performance Enhancement of CsPbI2Br Solar Cells by a Dual-Function Strategy with CsPbBr3 Nanocrystals.

Herein, a dual-function strategy, in which CsPbI2Br is treated by CsPbBr3 nanocrystals (NCs) via addition and surface modification to construct the "electron bridge" and gradient heterojunction, respectively, to notably improve the performance of the CsPbI2Br solar cells, is proposed. The "electron bridge" formed by the CsPbBr3 NCs provides an extra transport channel for the photogenerated electrons in the CsPbI2Br layer, thus facilitating electron transport. Meanwhile, surface modification of CsPbI2Br by the CsPbBr3 NCs forms a gradient heterojunction between the CsPbI2Br layer and the P3HT layer, enhancing hole extraction accordingly. In addition, the CsPbBr3 NC treatment passivates the defects at the bulk and surface of the CsPbI2Br layers, thus suppressing carrier recombination. Thanks to these positive effects of the CsPbBr3 NCs, the demonstration device with a simple configuration of ITO/SnO2/CsPbI2Br/P3HT/Ag achieves a notable power conversion efficiency of 17.03%, which is among the highest efficiencies reported for CsPbI2Br-based solar cells.

A high linearity and multilevel polymer-based conductive-bridging memristor for artificial synapses.

Conductive-bridging memristors based on a metal ion redox mechanism have good application potential in future neuromorphic computing nanodevices owing to their high resistance switch ratio, fast operating speed, low power consumption and small size. Conductive-bridging memristor devices rely on the redox reaction of metal ions in the dielectric layer to form metal conductive filaments to control the conductance state. However, the migration of metal ions is uncontrollable by the applied bias, resulting in the random generation of conductive filaments, and the conductance state is difficult to accurately control. Herein, we report an organic polymer carboxylated chitosan-based memristor doped with a small amount of the conductive polymer PEDOT:PSS to improve the polymer ionic conductivity and regulate the redox of metal ions. The resulting device exhibits uniform conductive filaments during device operation, more than 100 and non-volatile conductance states with a ∼1 V range, and linear conductance regulation. Moreover, simulation using handwritten digital datasets shows that the recognition accuracy of the carboxylated chitosan-doped PEDOT:PSS memristor array can reach 93%. This work provides a path to facilitate the performance of metal ion-based memristors in artificial synapses.

Efficient Regulation of Polysulfides by MoS2 /MoO3 Heterostructures for High-Performance Li-S Batteries.

The notorious shuttle effect and sluggish conversion of polysulfides seriously hinder the practical application of Lithium-sulfur (Li-S) batteries. In this study, a novel architecture of MoS2 /MoO3 heterostructure uniformly distributed on carbon nanotubes (MoS2 /MoO3 @CNT) is designed and introduced into Li-S batteries via decorating commercial separator to regulate the redox reactions of polysulfides. Systematic experiments and theoretical calculations showed that the heterostructure not only provides sufficient surface affinity to capture polysulfides and acts as an active catalyst to promote the conversion of polysulfides, but also the highly conductive CNT enables rapid electron/ion migration. As a result, Li-S batteries with the MoS2 /MoO3 @CNT-PP separator deliver an impressive reversible capacity (1015 mAh g-1 at 0.2 A g-1 after 100 cycles), excellent rate capacity (873 mAh g-1 at 5 A g-1 ), and low self-discharge capacity loss (94.6% capacity retention after 7 days of standing). Moreover, even at an elevated temperature of 70 °C, it still exhibits high-capacity retention (800 mAh g-1 at 1 A g-1 after 100 cycles). Encouragingly, when the sulfur load is increased to 8.7 mg cm-2 , the high reversible areal capacity of 6.61 mAh cm-2 can be stably maintained after 100 cycles, indicating a high potential for practical application.

Transition Metal d-band Center Tuning by Interfacial Engineering to Accelerate Polysulfides Conversion for Robust Lithium-Sulfur Batteries.

Although lithium-sulfur batteries (LSBs) promise high theoretical energy density and potential cost effectiveness, their applications are severely impeded by the shuttling and sluggish redox kinetics of lithium polysulfides (LiPSs). In this context, a Co9 S8 @MoS2 heterostructure is sophisticatedly designed as an efficient catalytic host to boost the sulfur reduction reaction/evolution reaction (SRR/SER) kinetics and suppresses the LiPSs shuttling in LSBs. The results indicate that the electronic structure is manipulated in the Co9 S8 @MoS2 heterostructure, where the built-in electric fields (BIEFs) within the heterointerfaces enable the sufficient adsorption sites to accelerate the ionic diffusion/charge transfer kinetics for LiPSs redox, thus enhancing the sulfur conversion. By tuning the electronic structure, the metal d-band of Co9 S8 @MoS2 heterostructure plays an important role in adsorbing and catalyzing the conversion of LiPSs, thus promoting the reaction kinetics of the corresponding LSBs. This work unlocks the potential of heterostructures as promising catalysts to the design of high-energy and stabilized LSBs.

Improved Comprehensive Photovoltaic Performance and Mechanisms by Additive Engineering of Ti3C2Tx MXene into CsPbI2Br.

CsPbI2Br is promising in the application of perovskite solar cells (PSCs) owing to its reasonable bandgap and good thermal stability. However, the reported power conversion efficiency (PCE) of the CsPbI2Br solar cells is still much lower than that of the organic-inorganic hybrid PSCs, mainly due to relatively poor CsPbI2Br crystal quality. Herein, additive engineering to the photoactive layer of CsPbI2Br using the Ti3C2Tx MXene nanosheets is reported. Thanks to the improved crystallinity/reduced defect density, together with the formation of the Schottky junction between the MXene nanosheets and CsPbI2Br, enhanced separation and transfer of the photogenerated electron-hole pairs can be achieved for optimal MXene addition. A simple device configuration of ITO/SnO2/Ti3C2Tx-added CsPbI2Br/P3HT/Ag can thus deliver a significantly boosted PCE of 15.10%, i.e., a ∼16.69% relative increment compared with that (12.94%) of the control device without adding MXene. In addition, the enhanced humidity resistance is achieved for the MXene-added CsPbI2Br layers.

High-Performance Osmotic Power Generators Based on the 1D/2D Hybrid Nanochannel System.

Extracting clean energy by converting the salinity gradient between river and sea into energy is an effective way to reduce the global pollution and carbon emissions. Reverse electrodialysis (RED) is of great importance to realize the energy conversion assisting the ion-selective membrane. However, its higher ion resistance and lower conversion efficiency results in the undesirable power conversion performance. Here, we demonstrate a 1D/2D hybrid nanochannel system to achieve high osmotic energy conversion and output power. This heterogeneous structure is composed of two structures, in which the subnanometer nanochannels in graphene oxide membrane (GOM) can serve as a selective layer and reduce the ion diffusion energy barrier, while the nanochannel in the polymer can introduce asymmetry to enhance ionic rectification and conversion efficiency. This heterogeneous membrane exhibits excellent cation selectivity and enhanced ionic current rectification (ICR) performance. The application of the GOM/PET hybrid nanochannel system in osmotic energy harvesting is evaluated, and the output power can reach up to 118.2 pW with the energy conversion efficiency of 40.3%. Theoretical calculation indicates that the 1D/2D hybrid system can effectively take the advantage of excellent cation selectivity of 2D lamellar nanochannels to improve its RED performance significantly.

Synergetic effects of a front ITO nanocylinder array and a back square Al array to enhance light absorption for organic solar cells.

Efficient light management is critical to obtain high performance for organic solar cells (OSCs), which aims to solve the contradiction between limited carrier extraction and light absorption for the normally employed photoactive layers generally having both short exciton diffusion lengths and low extinction coefficients. In this study, we introduce a simple and efficient light management structure consisting of a front indium tin oxide nanocylinder (ITO-NC) array and a back square Al array. Thanks to the synergetic effects of antireflection and light scattering induced by the ITO-NC array, together with the secondary scattering and localized surface plasmon resonance because of the square Al array, remarkably enhanced light absorption in a broad spectral range can be achieved. Taking the most investigated photoactive layer of the P3HT:PC61BM blend as an example, simulation results reveal that, compared with the planar control device of the ITO/PEDOT:PSS/P3HT:PC61BM(80nm)/ZnO/Al, the short-circuit current density and power conversion efficiency can be enhanced by 36.58% and 38.38% after incorporating the light management structure with the optimal structural parameters. Furthermore, good omnidirectional light management can be achieved for the proposed device structure. Given the excellent performance and simple structure, we believe that this study would provide a meaningful exploration of developing light management structures applicable for thin film-based optoelectronic devices.

Sheet-Like Stacking SnS2/rGO Heterostructures as Ultrastable Anodes for Lithium-Ion Batteries.

SnS2-based materials have attracted considerable attention in energy storage and conversion owing to their high lithium activity and theoretical capacity. However, the practical application is severely limited by the low coulombic efficiency and short cycle life due to irreversible side reactions, low conductivity, and serious pulverization in the discharge/charge process. In this study, sheet-like stacking SnS2/reduced graphene oxide (rGO) heterostructures were developed using a facile solvothermal method. It was found that the composites between SnS2 nanoplates and rGO nanosheets are closely coupled through van der Waals interactions, providing efficient electron/ion paths to ensure high electrical conductivity and sufficient buffer space to alleviate volume expansion. Therefore, the SnS2/rGO heterostructure anode can obtain a high capacity of 840 mA h g-1 after 120 cycles at a current density of 200 mA g-1 and maintain a capacity of 450 mA h g-1 after 1000 cycles at 1000 mA g-1. In situ X-ray diffraction tests showed that SnS2/rGO undergoes typical initial intercalation, conversion, and subsequent alloying reactions during the first discharge, and most of the reactions are dealloying/alloying in the subsequent cycles. The galvanostatic intermittent titration technique showed that the diffusion of lithium ions in the SnS2/rGO heterostructures is faster in the intercalation and conversion reactions than in the alloying reactions. These observations help to clarify the reaction mechanism and ion diffusion behavior in the SnS2 anode materials, thus providing valuable insights for improving the energy efficiency of lithium-ion batteries.

Ion-Selective Covalent Organic Framework Membranes as a Catalytic Polysulfide Trap to Arrest the Redox Shuttle Effect in Lithium-Sulfur Batteries.

In the wake of shaping the energy future through materials innovation, lithium-sulfur batteries (LSBs) are top-of-the-line energy storage system attributed to their high theoretical energy density and specific capacity inclusive of low material costs. Despite their strengths, LSBs suffer from the cross-over of soluble polysulfide redox species to the anode, entailing fast capacity fading and inferior cycling stability. Adding to the concern, the insulating character of polysulfides lends to sluggish reaction kinetics. To address these challenges, we construct optimized polysulfide blockers-cum-conversion catalysts by accommodating the battery separator with covalent organic framework@Graphene (COF@G) composites. We settle on a crystalline TAPP-ETTB COF in the interest of its nitrogen-enriched scaffold with a regular pore geometry, providing ample lithiophilic sites for strong chemisorption and catalytic effect to polysulfides. On another front, graphene enables high electron mobility, boosting the sulfur redox kinetics. Consequently, a lithium-sulfur battery with a TAPP-ETTB COF@G-based separator demonstrates a high reversible capacity of 1489.8 mA h g-1 at 0.2 A g-1 after the first cycle and good cyclic performance (920 mA h g-1 after 400 cycles) together with excellent rate performance (827.7 mA h g-1 at 2 A g-1). The scope and opportunities to harness the designability and synthetic structural control in crystalline organic materials is a promising domain at the interface of sustainable materials, energy storage, and Li-S chemistry.

Resistive Switching Memristor: On the Direct Observation of Physical Nature of Parameter Variability.

Ion-based memristive switching has attracted widespread attention from industries owing to its outstanding advantages in storage and neuromorphic computing. Major issues for achieving brain-inspired computation of highly functional memory in redox-based ion devices are relatively large variability in their operating parameters and limited cycling endurance. In some devices, volatile and nonvolatile operations often replace each other without changing operating conditions. To address these issues, it is important to observe directly what is happening in repeated operations. Herein, we use a planar device that enables direct capturing of microscopic behaviors in the nucleation and growth of metal whiskers under repeated switching to verify the microscopic origin of the large parameter variability. We report direct observations that reveal the physical origin for the large cycle-to-cycle and device-to-device variability in memristive switching, which was achieved using planar polymer atomic switches with a gap >1 µm. We find that the deposition location of metal atoms is closely related to the crystallinity of the ion transport layer (solid polymer electrolyte, SPE). The filament variability (shape, position, quantity, etc.) during different cycles and devices is indeed the main reason for the observed variability in the operating characteristics. The results shed unique light on the complexity of the operation of the ion device, that is, the evolution of the dielectric layer and metal filament must be considered.

Sandwich-like SnS2/graphene multilayers for efficient lithium/sodium storage.

2D materials have attracted extensive attention in energy storage and conversion due to their excellent electrochemical performances. Herein, we report utilization of monolayer SnS2 sheets within SnS2/graphene multilayers for efficient lithium and sodium storage. SnS2/graphene multilayers are synthesized through a solution-phase direct assembly method by electrostatic interaction between monolayer SnS2 and PDDA (polydimethyl diallyl ammonium chloride)-graphene nanosheets. It has been shown that the SnS2/graphene multilayer electrode has a large pseudocapacity contribution for enhanced lithium and sodium storage. Typical batteries deliver a stable reversible capacity of ∼160 mA h g-1 at 2 A g-1 after 2000 cycles for lithium and a stable reversible capacity of ∼142 mA h g-1 at 1 A g-1 after 1000 cycles for sodium. The excellent electrochemical performances of SnS2/graphene multilayers are attributed to the synergistic effect between the monolayer SnS2 sheets and the PDDA-graphene nanosheets. The multilayer structure assembled by different monolayer nanosheets is promising for the further development of 2D materials for energy storage and conversion.

MXenes for Solar Cells.

Application of two-dimensional MXene materials in photovoltaics has attracted increasing attention since the first report in 2018 due to their metallic electrical conductivity, high carrier mobility, excellent transparency, tunable work function and superior mechanical property. In this review, all developments and applications of the Ti3C2Tx MXene (here, it is noteworthy that there are still no reports on other MXenes' application in photovoltaics by far) as additive, electrode and hole/electron transport layer in solar cells are detailedly summarized, and meanwhile, the problems existing in the related studies are also discussed. In view of these problems, some suggestions are given for pushing exploration of the MXenes' application in solar cells. It is believed that this review can provide a comprehensive and deep understanding into the research status and, moreover, helps widen a new situation for the study of MXenes in photovoltaics.

Improvement of the Optoelectrical Properties of a Transparent Conductive Polymer via the Introduction of ITO Nanoparticles and Its Application in Crystalline Silicon/Organic Heterojunction Solar Cells.

Compared with conventional transparent conductive indium tin oxide (ITO) films, poly(3,4-ethylenedioxythiophene):poly (styrenesulfonic acid) (PEDOT:PSS) as a conductive polymer material has been diffusely applied in organic optoelectronic devices. However, its optoelectrical properties need to be further improved. Therefore, a simple and universal approach with introducing ITO nanoparticles (NPs) was proposed to improve the optoelectrical properties of PEDOT:PSS thin films. The results show that the vertical conductivity (σDC⊥) and average transmittance (from 300 to 1200 nm) of PEDOT:PSS films were enhanced about 26.8 and 6.3%, respectively. Crystalline silicon (c-Si)/organic heterojunction solar cells (HSCs) with PEDOT:PSS/ITO NP hybrid films were fabricated and performances led to further improvement. The spatial distributions of relative electrical field intensity and the carrier generation rate of the HSCs under the standard AM 1.5 G condition were simulated, which were in good agreement with the experimental conclusions.

High photosensitivity light-controlled planar ZnO artificial synapse for neuromorphic computing.

A light-controlled artificial synapse, which mimics the human brain has been considered to be one of the ideal candidates for the fundamental physical architecture of a neuromorphic computing system owing to the possible abilities of high bandwidth and low power calculation. However, the low photosensitivity of synapse devices can affect the accuracy of recognition and classification in neuromorphic computing tasks. In this work, a planar light-controlled artificial synapse having high photosensitivity (Ion/Ioff > 1000) with a high photocurrent and a low dark current is realized based on a ZnO thin film grown by radiofrequency sputtering. The synaptic functions of the human brain such as sensory memory, short-term memory, long-term memory, duration-time-dependent-plasticity, light-intensity-dependent-plasticity, learning-experience behavior, neural facilitation, and spike-timing-dependent plasticity are successfully emulated using persistent photoconductivity characteristic of a ZnO thin film. Furthermore, the high classification accuracy of 90%, 92%, and 86% after 40 epochs for file type datasets, small digits, and large digit is realized with a three-layer neural network based on backpropagation where the numerical weights in the network layer are mapped directly to the conductance states of the experimental synapse devices. Finally, characterization and analysis reveal that oxygen vacancy defects and chemisorbed oxygen on the surface of the ZnO film are the main factors that determine the performance of the device.

A highly stable and sensitive ethanol sensor based on Ru-decorated 1D WO3 nanowires.

Decorating materials with noble metal catalysts is an effective method for optimizing the sensing performance of sensors based on tungsten trioxide (WO3) nanowires. Ruthenium (Ru) exhibits excellent catalytic activity for oxygen adsorption/desorption and chemical reactions between gases and adsorbed oxygen. Herein, small Ru nanoparticles were uniformly distributed on the surface of one-dimensional WO3 nanowires. The nanowires were prepared by the electrospinning method through an ultraviolet (UV) irradiation process, and decoration with Ru did not change their morphology. A sensor based on 4% Ru nanowires (NWs) shows the highest response (∼120) to 100 ppm ethanol, which was increased around 47 times, and the lowest ethanol detection limit (221 ppb) at a lower temperature (200 °C) displays outstanding repeatability and stability even after 45 days or in higher-humidity conditions. Moreover, it also has faster response-recovery features. The improvement in the sensing performance was attributed to the stable morphology of the nanowires, the sensitization effect of Ru, the catalytic effect of RuO2 and the optimal atomic utilization efficiency. This work offers an effective and promising strategy for promoting the ethanol sensing performance of WO3.

Controlled Growth of Fine Multifilaments in Polymer-Based Memristive Devices Via the Conduction Control.

Solid polymer electrolyte (SPE) is one of the choices for many ionic devices, including organic transistors, ion batteries, memristors, and more. However, uncontrollable conductive filament formation seriously affects the performance of the device. In this paper, the PEDOT:PSS was doped to improve the electronic and ionic conductivity of amorphous polymer electrolyte poly(vinylpyrrolidone) (PVP), realizing the transition of the filaments growth from cathode to anode in atomic switch memristors. Based on the difference in ion and electron mobility and scanning electron microscope observation, the in situ reductions of metal ions inside the dielectric layer can effectively prevent the formation of uncontrollable filaments. The formation of uniformly distributed metal particles in the dielectric layer is similar to co-sputter doping technology, which enables the device to exhibit excellent performance, such as smaller set/reset bias distribution, endurance, and retention. Obviously, this innovative way improves the conductive mechanism of ionic devices.

Cr-Doped Urchin-Like WO3 Hollow Spheres: The Cooperative Modulation of Crystal Growth and Energy-Band Structure for High-Sensitive Acetone Detection.

Acetone is a biomarker in the exhaled breath of diabetic patients; sensitive and selective detection of acetone in human exhaled breath plays an important role in noninvasive diagnosis. Tungsten oxide (especially for γ-WO3) is a promising material for the detection of breath acetone. It is generally believed that the stable metastable phase of WO3 (ε-WO3) is the main reason for the improved response to acetone detection. In this work, pure and Cr-doped urchin-like WO3 hollow spheres were synthesized by a facile hydrothermal approach. Analyses of the resulting materials via X-ray photoelectron spectroscopy (XPS) and Raman confirmed that they are mainly composed by γ-WO3. The gas sensing performances of pure and Cr-doped WO3 to acetone were systematically tested. Results show that the sensor based on pure WO3 annealed at 450 °C has a high response of 20.32 toward 100 ppm acetone at a working temperature of 250 °C. After doped with Cr, the response was increased 3.5 times higher than the pure WO3 sensor. The pure and Cr-doped WO3 sensors both exhibit a tiny response to other gases, low detection limits (ppb-level) and an excellent repeatability. The improvement of gas sensing properties could be attributed to an optimized morphology of Cr-doped WO3 by regulating the crystal growth and reducing the assembled nanowires' diameter. The increasing number of oxygen vacancy and the introduction of impurity energy level with trap effect after Cr doping would lead to the wider depletion layer as well as a better gas sensing performance. This work will contribute to the development of new WO3 acetone sensors with a novel morphology and will explain the increased response after Cr doping from a new perspective.