Trifunctional robust electrocatalysts based on 3D Fe/N-doped carbon nanocubes encapsulating Co4N nanoparticles for efficient battery-powered water electrolyzers

Herein,we have designed a highly active and robust trifunctional electrocatalyst derived from Prussian blue analogs,where Co_(4)N nanoparticles are encapsulated by Fe embedded in N-doped carbon nanocubes to synthesize hierarchically structured Co_(4)N@Fe/N-C for rechargeable zinc-air batteries and overall water-splitting electrolyzers.As confirmed by theoretical and experimental results,the high intrinsic oxygen reduction reaction,oxygen evolution reaction,and hydrogen evolution reaction activities of Co_(4)N@Fe/N-C were attributed to the formation of the heterointerface and the modulated local electronic structure.Moreover,Co_(4)N@Fe/N-C induced improvement in these trifunctional electrocatalytic activities owing to the hierarchical hollow nanocube structure,uniform distribution of Co_(4)N,and conductive encapsulation by Fe/N-C.Thus,the rechargeable zinc-air battery with Co_(4)N@Fe/N-C delivers a high specific capacity of 789.9 mAh g^(-1) and stable voltage profiles over 500 cycles.Furthermore,the overall water electrolyzer with Co_(4)N@Fe/N-C achieved better durability and rate performance than that with the Pt/C and IrO2 catalysts,delivering a high Faradaic efficiency of 96.4%.Along with the great potential of the integrated water electrolyzer powered by a zinc-air battery for practical applications,therefore,the mechanistic understanding and active site identification provide valuable insights into the rational design of advanced multifunctional electrocatalysts for energy storage and conversion.

MXene-based hybrid materials for electrochemical and photoelectrochemical H_(2) generation

The conversion of solar energy to produce clean hydrogen fuel through water splitting is an emerging strategy for efficiently storing solar energy in the form of solar fuel.This aligns with the increasing global demand for the development of an ideal energy alternative to fossil fuels that does not emit greenhouse gases.Electrochemical(EC) and photoelectrochemical(PEC) water splitting technologies have garnered significant attention worldwide for advanced hydrogen solar fuel production in recent decades.To achieve sustainable green H_(2) production,it is essential to create efficient catalyst materials that are low-cost and can replace expensive noble metal-based catalysts.These characteristics make them an ideal catalyst material for the process.Two-dimensional MXenes with M_(n+1)X_(n) structure have been identified as a promising option for EC and PEC water splitting due to their superior hydrophilicity,metal-like conductivity,large surface area,and adjustable surface chemistry.Here,we present a summary of recent advancements in the synthesis and performance enhancement methods for MXene hybrid materials in hydrogen production through EC and PEC water splitting.Furthermore,we examine the challenges and insights associated with the rational design of MXene-based hybrid materials to facilitate efficient water splitting for sustainable solar fuel production.

Self-Assembled Wire Arrays and ITO Contacts for Silicon Nanowire Solar Cell Applications

Self-assembly of silicon nanowire(SiNW)arrays is studied using SF_(6)/0_(2)plasma treatment.The self-assembly method can be applied to single-and poly-crystalline Si substrates.Plasma conditions can control the length and diameter of the SiNW arrays.Lower reflectance of the wire arrays over the wavelength range 200-1100nm is obtained.The conducting transparent indium-tin-oxide(ITO)electrode can be fully coated on the self-assembled SiNW arrays by sputtering.The ITO-coated SiNW solar cells show the same low surface light reflectance and a higher carrier collection efficiency than SiNW solar cells without ITO coating.An efficiency enhancement of around 3 times for ITO coated SiNW solar cells is demonstrated via experiments.

Electrochemical and structural evolution of structured V_(2)O_(5) microspheres during Li-ion intercalation

With the development of stable alkali metal anodes,V_(2)O_(5) is gaining traction as a cathode material due to its high theoretical capacity and the ability to intercalate Li,Na and K ions.Herein,we report a method for synthesizing structured orthorhombic V_(2)O_(5) microspheres and investigate Li intercalation/deintercalation into this material.For industry adoption,the electrochemical behavior of V_(2)O_(5) as well as structural and phase transformation attributing to Li intercalation reaction must be further investigated.Our synthesized V_(2)O_(5) microspheres consisted of small primary particles that were strongly joined together and exhibited good cycle stability and rate capability,triggered by reversible volume change and rapid Li ion diffusion.In addition,the reversibility of phase transformation(a,e,d,c and xLixV_(2)O_(5))and valence state evolution(5+,4+,and 3.5+)during intercalation/de-intercalation were studied via in-situ X-ray powder diffraction and X-ray absorption near edge structure analyses.

Redox Charge Transfer Kinetics and Reversibility of VO_(2) in Aqueous and Non-Aqueous Electrolytes of Na-Ion Storage

The deep understanding about the electrochemical behavior of the nanostructured electrode in electrolytes provides crucial insights for the rational design of electrode for sodium(Na)-ion storage system(NIS).Here,we report redox charge transfer kinetics and reversibility of VO_(2)(B) nanorod electrodes in both aqueous and organic electrolytes for NIS.The assynthesized VO_(2)(B) nanorods show the reversible redox reaction with the higher specific and rate capacitances at high current density in aqueous electrolytes than in organic electrolytes.Temperature-dependent impedance measurements demonstrate the more facile interfacial charge transfer of Na ions into VO_(2)(B) nanorods in aqueous electrolytes.The reversible evolution in oxidation state and chemical composition of VO_(2)(B) nanorods is observed in aqueous electrolytes,as confirmed by ex situ XRD and ex situ X-ray photoelectron spectroscopy analyses.Given by the facile and reversible pseudocapacitive feature,the electrochemical performances of VO_(2)(B) nanorods are further improved by constructing the hierarchical structure of the reduced graphene oxide-VO_(2) composite for aqueous Na+ion storage.

LiTFSI salt concentration effect to digest lithium polysulfides for high-loading sulfur electrodes

Sulfur utilization improvement and control of dissolved lithium polysulfide(LiPS;Li_(2)S x,2<x≤8)are cru-cial aspects of the development of lithium-sulfur(Li-S)batteries,especially in high-loading sulfur elec-trodes and low electrolyte/sulfur(E/S)ratios.The sluggish reaction in the low E/S ratio induces poor LiPS solubility and unstable Li_(2)S electrodeposition,resulting in limited sulfur utilization,especially under high-loading sulfur electrode.In this study,we report on salt concentration effects that improve sulfur utilization with a high-loading cathode(6 mgs ulfurcm^(-2)),a high sulfur content(80 wt%)and a low E/S ratio(5 m L gs ulfur^(-1)).On the basis of the rapid LiPS dissolving in a low concentration electrolyte,we estab-lished that the quantity of Li_(2)S electrodeposition from a high Li+diffusion coefficient,referring to the reduction of LiPS precipitation,was significantly enhanced by a faster kinetic.These results demonstrate the importance of kinetic factors for the rate capability and cycle life stability of Li-S battery electrolytes through high Li_(2)S deposition under high-loading sulfur electrode.

Single-Phase Ternary Compounds with a Disordered Lattice and Liquid Metal Phase for High-Performance Li-Ion Battery Anodes

Si is considered as the promising anode materials for lithium-ion batteries(LIBs)owing to their high capacities of 4200 mAh g-1and natural abundancy.However,severe electrode pulverization and poor electronic and Li-ionic conductivities hinder their practical applications.To resolve the afore-mentioned problems,we first demonstrate a cation-mixed disordered lattice and unique Li storage mechanism of single-phase ternary GaSiP_(2)compound,where the liquid metallic Ga and highly reactive P are incorporated into Si through a ball milling method.As confirmed by experimental and theoretical analyses,the introduced Ga and P enables to achieve the stronger resistance against volume variation and metallic conductivity,respectively,while the cation-mixed lattice provides the faster Li-ionic diffusion capability than those of the parent GaP and Si phases.The resulting GaSiP_(2)electrodes delivered the high specific capacity of 1615 mAh g-1and high initial Coulombic efficiency of 91%,while the graphite-modified GaSiP_(2)(GaSiP_(2)@C)achieved 83%of capacity retention after 900 cycles and high-rate capacity of 800 at 10,000 mA g-1.Furthermore,the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)//Ga SiP_(2)@C full cells achieved the high specific capacity of 1049 mAh g-1after 100 cycles,paving a way for the rational design of high-performance LIB anode materials.

MXene ink hosting zinc anode for high performance aqueous zinc metal batteries

Despite the safety,low cost,and high theoretical capacity(820 mA h g^(-1))of Zn metal anodes,the practical application of aqueous Zn metal batteries remains a critical challenge due to the Zn dendrite growth,corrosion,and hydrogen evolution reaction.Herein,we demonstrate the MXene ink hosting Zn metal anodes(MX@Zn)for high-performance and patternable Zn metal full batteries.The as-designed MX@Zn electrode is more facile and reversible than bare Zn and CC@Zn,as verified by better cyclic stability and lower overpotentials of symmetric cells with the plating capacity of 0.05 mA h cm^(-2)at 0.1 m A cm^(-2)and of 1 m A h cm^(-2)at 1 m A cm^(-2).The MX@Zn|MnO_(2)full cells deliver a high specific capacity of 281.9 m A h g^(-1),91.5%of the theoretical capacity,achieving 50%capacity retention from 60 mA g^(-1)to 300 mA g^(-1)and 79.7%of initial capacity after 200 cycles.Moreover,the patterned devices based on the MX@Zn electrode achieve high energy and power densities of 348.57 Wh kg^(-1)and 1556 W kg^(-1),respectively,along with a capacity retention of 64%and Coulombic efficiency of 99%over 500 cycles.The high performance of MX@Zn is attributed to the high electrical conductivity and hydrophilicity of MXene and rapid ion diffusion through the 3D interconnected porous channels.

A conformal titanyl phosphate amorphous overlayer for enhancing photoelectrochemical hydrogen peroxide production

Photoelectrochemical(PEC)H_(2)O_(2)production through water oxidation reaction(WOR)is a promising strategy,however,designing highly efficient and selective photoanode materials remains challenging due to competitive reaction pathways.Here,for highly enhanced PEC H_(2)O_(2)production,we present a conformal amorphous titanyl phosphate(a-TP)overlayer on nanoparticulate TiO_(2)surfaces,achieved via lysozyme-molded in-situ surface reforming.The a-TP overlayer modulates surface adsorption energies for reaction intermediates,favoring WOR for H_(2)O_(2)production over the competing O_(2)evolution reaction.Our density functional theory calculations reveal that a-TP/TiO_(2)exhibits a substantial energy uphill for the O·*formation pathway,which disfavors O_(2)evolution but promotes H_(2)O_(2)production.Additionally,the a-TP overlayer strengthens the built-in electric field,resulting in favorable kinetics.Consequently,a-TP/TiO_(2)exhibits 3.7-fold higher Faraday efficiency(FE)of 63%at 1.76 V vs.reversible hydrogen electrode(RHE)under 1 sun illumination,compared to bare TiO_(2)(17%),representing the highest FE among TiO_(2)-based WOR H_(2)O_(2)production systems.Employing the a-TP overlayer constitutes a promising strategy for controlling reaction pathways and achieving efficient solar-to-chemical energy conversion.

High Na-ion conductivity andmechanical integrity of anion-exchanged polymeric hydrogel electrolytes for flexible sodium ion hybrid energy storage

The polymeric gel electrolytes are attractive owing to their higher ionic conductivities than those of dry polymer electrolytes and lowered water activity for enlarged potential window.However,the ionic conductivity and mechanical strength of the Na-ion conducting polymeric gel electrolytes are limited by below 20 mS cm−1 and 2.2 MPa.Herein,we demonstrate Na-ion conducting and flexible polymeric hydrogel electrolytes of the chemically coupled poly(diallyldimethylammonium chloride)-dextrin-N,N′-methylene-bisacrylamide film immersed in NaClO_(4) solution(ex-DDA-Dex+NaClO_(4))for flexible sodium-ion hybrid capacitors(f-NIHC).In particular,the anion exchange reaction and synergistic interaction of ex-DDA-Dex with the optimum ClO_(4)−enable to greatly improve the ionic conductivity up to 27.63 mS cm−1 at 25◦C and electrochemical stability window up to 2.6 V,whereas the double networking structure leads to achieve both the mechanical strength(7.48 MPa)and softness of hydrogel electrolytes.Therefore,the f-NIHCs with the ex-DDA-Dex+NaClO_(4) achieved high specific and high-rate capacities of 192.04 F g^(−1)at 500 mA g^(−1)and 116.06 F g^(−1)at 10000 mA g^(−1),respectively,delivering a large energy density of 120.03Wh kg^(−1)at 906Wkg^(−1)and long cyclability of 70%over 500 cycles as well as demonstrating functional operation under mechanical stresses.

Perspective on High-Energy Carbon-Based Supercapacitors

Supercapacitors based on carbon materials have advantages such as high power density,fast charging/discharging capability,and long lifetime stability,playing a vital role in the field of electrochemical energy storage technologies.To further expand the practical applications of carbon-based supercapacitors,their energy density,which is essentially determined by the specific capacitance and operating voltage,should be improved.This review provides fundamental knowledge on achieving high energy density of supercapacitors.We first address the relationship of the features of carbon materials,such as the surface area,pore size distribution,and surface functional groups,with their electrochemical performances,such as the gravimetric and volumetric capacitance,surface pseudocapacitance,and operating voltage.Then,we discuss the properties of electrolytes from nonaqueous and aqueous to hybrid one from the thermodynamic and kinetic aspects,and present their effects on capacitance and operating voltage.Finally,we illustrate different cell design strategies and their basic principles for increasing operating voltage.We also highlight the recent advances related to these fields and provide our insight into high-energy supercapacitors.

Pushing the Band Gap Envelope of Quasi-Type II Heterostructured Nanocrystals to Blue:ZnSe/ZnSe_(1-X)Te_(X)/ZnSe Spherical Quantum Wells

Quasi-type II heterostructured nanocrystals(NCs)have been of particular interest due to their great potential for controlling the interplay of charge carriers.However,the lack of material choices for quasi-type II NCs restricts the accessible emission wavelength from red to near-infrared(NIR),which hinders their use in light-emitting applications that demand a wide range of visible colors.Herein,we demonstrate a new class of quasi-type II nanoemitters formulated in ZnSe/ZnSe_(1-X)Te_(X)/ZnSe seed/spherical quantum well/shell heterostructures(SQWs)whose emission wavelength ranges from blue to orange.In a given geometry,ZnSe_(1-X)Te_(X) emissive layers grown between the ZnSe seed and the shell layer are strained to fit into the surrounding media,and thus,the lattice mismatch between ZnSe_(1-X)Te_(X) and ZnSe is effectively alleviated.In addition,composition of the ZnSe_(1-X)Te_(X) emissive layer and the dimension of the ZnSe shell layer are engineered to tailor the distribution and energy of electron and hole wave functions.Benefitting from the capabilities to tune the charge carriers on demand and to form defectfree heterojunctions,ZnSe/ZnSe_(1-X)Te_(X)/ZnSe/ZnS NCs show near-unity photoluminescence quantum yield(PLQY>90%)in a broad range of emission wavelengths(peak PL from 450nm to 600 nm).Finally,we exemplify dichromatic white NC-based light-emitting diodes(NC-LEDs)employing the mixed layer of blue-and yellow-emitting ZnSe/ZnSe_(1-X)TeX/ZnSe/ZnS SQW NCs.

Tetradentate Pt(Ⅱ)complex as a singlet exciton sensitizing host for highly efficient green fluorescent organic light-emitting diodes

Efficient green fluorescent organic light-emitting diodes were designed with a phosphorescent metal complex as a singlet exciton sensitizing host(SESH)for achieving high efficiency and low efficiency roll-off through exciton and polaron management.Tetradentate Pt(Ⅱ)complex(Pt-Trz)possessing a tetradentate ligand with a bulky blocking group not only suppresses the severe formation of excimer or dimer itself but also transfers radiative excitons to fluorescent dopant effectively.The SESH assisted fluorescence(SESHF)device with Pt-Trz as the host exhibits the maximum external quantum efficiency of 13.3%and a lower efficiency roll-off compared with exciplex host device which is a general approach for harvesting triplet excitons.Numerical exciton dynamics modeling unravels that the SESHF device effectively utilizes triplet excitons in the host by intersystem crossing and resonance energy transfer from the triplet state of the host to the singlet state of the terminal emitter.Bimolecular quenching rates of the SESHF device are reduced by 11 times for triplet-triplet annihilation and 1.8 times for tripletpolaron annihilation compared with the exciplex device,which demonstrates that Pt-Trz could be a platform to be used as an efficient host for fluorophores.

Hybrid windshield-glass heater for commercial vehicles fabricated via enhanced electrostatic interactions among a substrate, silver nanowires, and an over-coating layer

We introduce a transparent windshield-glass heater produced via transparent electrodes using silver nanowire （AgNW） networks for conventional use in the automobile industry. A high-quality conducting hybrid film is deposited on a plasma-treated glass substrate by spraying AgNWs, immersing the sprayed product in positively charged adhesive polymer solution, and then spraying negatively charged graphene oxide （GO） and a silane layer as an over-coating layer （OCL）.The results of heating tests conducted after adhesion tests show that the sheet resistance changes with the application of polymer glue. Surprisingly, the transmittance of the film with the GO OCL is higher than that of the film without the GO OCL. Heating and defrosting tests are carefully conducted via infrared （IR） monitoring. Adhesive-polymer-treated and GO-protected AgNW transparent glass heaters exhibit the best performance with low sheet resistance; thus, through strong electrostatic interaction among the substrate, adhesive layer, and OCL, our AgNW hybrid glass heater can reach the target temperature with a standard vehicle voltage of 12 V in a short period of time.

Indolo[3,2,1-jk]carbazole-derived planar electron transport materials realizing high efficiency in green phosphorescent organic light-emitting diodes

Two novel electron transporting materials(ETMs),2-(4,6-diphenyl-1,3,5-triazin-2-yl)indolo[3,2,1-jk]-carbazole(DPTrz-ICz)and 5,11-bis(4,6-diphenyl-1,3,5-triazin-2-yl)-2-phenylindolo[3,2,1-jk]carbazole(2DPTrz-ICz),were developed based on the indolo[3,2,1-jk]carbazole(ICz)core,combined with 2,4-diphenyl-1,3,5-triazine(DPTrz).The introduced ICz core in ETM exhibited enhanced intermolecular charge transport properties owing to its planar and rigid geometry and high triplet energy,demonstrating the potential of designing ETM.Consequently,2DPTrz-ICz,featuring high triplet energy of 2.84 eV,effectively prevented triplet exciton quenching and showed increased electron mobility owing to the activation of intermolecular hopping charge transfer facilitated by stacking architecture.The two materials were utilized as ETMs in green phosphorescent organic light-emitting diodes.2DPTrz-ICz exhibited a superior external quantum efficiency of 21.5%,higher than that of the spirobifluorene-derived ETM.

Crystal reconstruction of V_(2)O_(3)/carbon heterointerfaces via anodic hydration for ultrafast and reversible Mg-ion battery cathodes

Magnesium-ion batteries(MIBs)have promising applications because of their high theoretical capacity and the natural abundance of magnesium Mg.However,the kinetic performance and cyclic stability of cathode materials are limited by the strong interactions between Mg ions and the crystal lattice.Here,we demonstrate the unique Mg^(2+)-ion storage mechanism of a hierarchical accordion-like vanadium oxide/carbon heterointerface(V_(2)O_(3)@C),where the V_(2)O_(3) crystalline structure is reconstructed into a MgV_(3)O_(7)·H_(2)O phase through an anodic hydration reaction upon first cycle,for the improved kinetic and cyclic performances.As verified by in situ/ex situ spectroscopic and electrochemical analyses,the fast charge transfer kinetics of the V_(2)O_(3)@C cathode were due to the crystal-reconstruction and chemically coupled heterointerface.The V_(2)O_(3)@C demonstrated an ultrahigh rate capacity of 130.4 mAh g^(-1)at 50000 mA g^(-1)and 1000 cycles,achieving a Coulombic efficiency of 99.6%.The high capacity of 381.0 mA h g^(-1)can be attributed to the reversible Mg^(2+)-ion intercalation mechanism observed in the MgV_(3)O_(7)·H_(2)O phase using a 0.3 M Mg(TFSI)2/ACN(H_(2)O)electrolyte.Additionally,within the voltage range of 2.25 V versus Mg/Mg^(2+),the V_(2)O_(3)@C exhibited a capacity of 245.1 mAh g^(-1)when evaluated with magnesium metal in a 0.3 M Mg(TFSI)^(2+)0.25 M MgCl_(2)/DME electrolyte.These research findings have important implications for understanding the relationship between the Mg-ion storage mechanism and reconstructed crystal phase of vanadium oxides as well as the heterointerface reconstruction for the rational design of MIB cathode materials.

Quasiparticle interference and impurity resonances on WTe2

Using scanning tunneling microscopy/spectroscopy(STM/STS),we examine quasiparticle scattering and interference properties at the surface of WTe2.WTe2,layered transition metal dichalcogenide,is predicted to be a type-ll Weyl semimetal.The Weyl fermion states in WTe2 emerge as topologically protected touching points of electron and hole pockets,and Fermi arcs connecting them can be visible in the spectral function on the surface.To probe the properties of surface states,we have conducted low-temperature STM/STS(at 2.7 K)on the surfaces of WTe2 single crystals.We visualize the surface states of WTe2 with atomic scale resolution.Clear surface states emerging from the bulk electron pocket have been identified and their connection with the bulk electronic states shows good agreement with calculations.We show the interesting double resonance peaks in the local density of states appearing at localized impurities.The low-energy resonant peak occurs near the Weyl point above the Fermi energy and it may be mixed with the surface state of Weyl points,which makes it difficult to observe the topological nature of the Weyl semimetal WTe2.