Water splitting is important to the conversion and storage of renewable energy,but slow kinetics of the oxygen evolution reaction(OER)greatly limits its utility.Here,under visible light illumination,the p-n WO_(3)/SnS...Water splitting is important to the conversion and storage of renewable energy,but slow kinetics of the oxygen evolution reaction(OER)greatly limits its utility.Here,under visible light illumination,the p-n WO_(3)/SnSe_(2)(WS)heterojunction significantly activates OER catalysis of CoFe-layered double hydroxide(CF)/carbon nanotubes(CNTs).Specifically,the catalyst achieves an overpotential of 224 mV at 10 mA cm^(-2)and a small Tafel slope of 47 mV dec^(-1),superior to RuO_(2)and most previously reported transition metal-based OER catalysts.The p-n WS heterojunction shows strong light absorption to produce photogenerated carriers.The photogenerated holes are trapped by CF to suppresses the charge recombination and facilitate charge transfer,which accelerates OER kinetics and boost the activity for the OER.This work highlights the possibility of using heterojunctions to activate OER catalysis and advances the design of energy-efficient catalysts for water oxidation systems using solar energy.展开更多
The large volumetric variations experienced by metal selenides within conversion reaction result in inferior rate capability and cycling stability,ultimately hindering the achievement of superior electrochemical perfo...The large volumetric variations experienced by metal selenides within conversion reaction result in inferior rate capability and cycling stability,ultimately hindering the achievement of superior electrochemical performance.Herein,metallic Cu_(2)Se encapsulated with N-doped carbon(Cu_(2)Se@NC)was prepared using Cu_(2)O nanocubes as templates through a combination of dopamine polymerization and hightemperature selenization.The unique nanocubic structure and uniform N-doped carbon coating could shorten the ion transport distance,accelerate electron/charge diffusion,and suppress volume variation,ultimately ensuring Cu_(2)Se@NC with excellent electrochemical performance in sodium ion batteries(SIBs)and potassium ion batteries(PIBs).The composite exhibited excellent rate performance(187.7 mA h g^(-1)at 50 A g^(-1)in SIBs and 179.4 mA h g^(-1)at 5 A g^(-1)in PIBs)and cyclic stability(246,8 mA h g^(-1)at 10 A g^(-1)in SIBs over 2500 cycles).The reaction mechanism of intercalation combined with conversion in both SIBs and PIBs was disclosed by in situ X-ray diffraction(XRD)and ex situ transmission electron microscope(TEM).In particular,the final products in PIBs of K_(2)Se and K_(2)Se_(3)species were determined after discharging,which is different from that in SIBs with the final species of Na_(2)Se.The density functional theory calculation showed that carbon induces strong coupling and charge interactions with Cu_(2)Se,leading to the introduction of built-in electric field on heterojunction to improve electron mobility.Significantly,the theoretical calculations discovered that the underlying cause for the relatively superior rate capability in SIBs to that in PIBs is the agile Na~+diffusion with low energy barrier and moderate adsorption energy.These findings offer theoretical support for in-depth understanding of the performance differences of Cu-based materials in different ion storage systems.展开更多
The design of sulfur hosts with high conductivity,large specific surface area,strong adsorption and electrocatalytic ability is crucial to advance high performance lithium-sulfur batteries.Herein,a novel ultrathin san...The design of sulfur hosts with high conductivity,large specific surface area,strong adsorption and electrocatalytic ability is crucial to advance high performance lithium-sulfur batteries.Herein,a novel ultrathin sandwich-type Ni-doped MoS_(2)/reduced graphene oxide(denote as Ni-doped MoS_(2)/rGO) hybrid is developed as a sulfur host through a simple one-step hydrothermal route.The two-dimensional layered structure Ni-doped MoS_(2)/rGO hybrid with heterostructure and heteroatom architecture defects not only plays a key role in adsorption of lithium polysulfide but also catalyzes on redox kinetics of sulfur and polysulfide species.Meanwhile,it can contribute to the large specific surface area for Li_(2) S/S_8 deposition,fast Li-ion and electron transportation,thus enhancing the electrocatalytic properties,as confirmed firstly by cyclic voltammetry(CV) results.Due to the adsorption-catalytic synergistic effect,the Ni-doped MoS_(2)/rGO cathode exhibits high specific capacity(1343.6 mA h g^(-1) at 0.2 C,921.6 mA h g^(-1) at 1 C),high coulombic efficiency and an outstanding cycle stability(with the low attenuation rate of 0.077% per cycle over 140 cycles at 0.5 C and 0.11% per cycle over 400 cycles at 1 C,respectively).This work proposes some inspiration for exploring the construction of advanced lithium-sulfur batteries through the rational design defects of atomic structure and electronic states of MoS_(2) as sulfur host.展开更多
Homogeneous and heterogeneous types of catalysis are frequently considered as separate disciplines or even opposed to each other.In the present work,a new type of mixed het-ero-/homogeneous catalysis was demonstrated ...Homogeneous and heterogeneous types of catalysis are frequently considered as separate disciplines or even opposed to each other.In the present work,a new type of mixed het-ero-/homogeneous catalysis was demonstrated for the case of selective alkylarene oxidation by molecular oxygen.The proposed catalytic system consists of two widely available components:N-hydroxyphthalimide(NHPI,a homogeneous organocatalyst for free-radical chain reactions)and nanosized TiO_(2)(heterogeneous UV-active photoredox catalyst).The interaction of NHPI with TiO_(2) allows for a shift from UV to visible light photoredox activity and generation of phthalimide-N-oxyl(PINO)radicals that diffuse into the solution where NHPI/PINO-catalyzed free-radical chain reaction can proceed without the additional light input providing a fundamental increase in energy efficiency.The NHPI/TiO_(2) ratio controls the selectivity of oxidation affording preferential formation of hydroperoxide or ketone from alkylarene.展开更多
Water electrolysis is considered as one most promising technique for hydrogen production.The high efficiency electrocatalyst is the key to accelerating the sluggish kinetics of the hydrogen evolution reaction(HER) in ...Water electrolysis is considered as one most promising technique for hydrogen production.The high efficiency electrocatalyst is the key to accelerating the sluggish kinetics of the hydrogen evolution reaction(HER) in alkaline media.In this work,an efficient HER electrocatalyst with hetero-interfacial metal-metal oxide structure was constructed through a redox solid phase reaction(SPR) strategy.During the annealing process under Ar atmosphere,RuO_(2) and WS_(2)in RuO_(2)/WS_(2)precursor were converted to Ru nanoparticles(NPs) and WO3in situ,where tiny Ru NPs and oxygen vacancies were uniformly distributed onto the newly formed WO3nanosheets.Different characterization techniques were adopted to confirm the successful formation of Ru/WO_(3)electrocatalyst(RWOC).The optimized RWOC sample annealed at 400℃ exhibited the low overpotential value of 13 mV at a current density of 10 mA cm^(-2)and strong durability under the alkaline condition.Density functional theoretical calculations further revealed that the promoted adsorption/desorption rate of reaction intermediates and the accelerated kinetics of HER process were deduced to the synergistic effect between Ru and WO_(3)in electrocatalyst.This work provides a feasible method to fabricate highly efficient HER electrocatalysts.展开更多
Water electrolysis using proton-exchange membranes is one of the most promising technologies for carbon-neutral and sustainable energy production.Generally,the overall efficiency of water splitting is limited by the o...Water electrolysis using proton-exchange membranes is one of the most promising technologies for carbon-neutral and sustainable energy production.Generally,the overall efficiency of water splitting is limited by the oxygen evolution reaction(OER).Nevertheless,a trade-off between activity and stability exists for most electrocatalytic materials in strong acids and oxidizing media,and the development of efficient and stable catalytic materials has been an important focus of research.In this view,gaining in-depth insights into the OER system,particularly the interactions between reaction intermediates and active sites,is significantly important.To this end,this review introduces the fundamentals of the OER over Ru-based materials,including the conventional adsorbate evolution mechanism,lattice oxygen oxidation mechanism,and oxide path mechanism.Moreover,the up-to-date progress of representative modifications for improving OER performance is further discussed with reference to specific mechanisms,such as tuning of geometric,electronic structures,incorporation of proton acceptors,and optimization of metal-oxygen covalency.Finally,some valuable insights into the challenges and opportunities for OER electrocatalysts are provided with the aim to promote the development of next-generation catalysts with high activity and excellent stability.展开更多
The defect-free structure of Mo-based materials is a“double-edged sword”,which endows the material with excellent stability,but limits its chemical versatility and application in electrochemical hydrogen evolution r...The defect-free structure of Mo-based materials is a“double-edged sword”,which endows the material with excellent stability,but limits its chemical versatility and application in electrochemical hydrogen evolution reaction(HER).Carbon doping engineering is an attractive strategy to effectively improve the performance of Mo-based catalyst and maintain their stability.Herein,we report a cross-linked porous carbon-doped MoO_(2)(C–MoO_(2))-based catalyst Ru/C–MoO_(2) for electrochemical HER,which is prepared by the convenient redox solid-phase reaction(SPR)of porous RuO_(2)/Mo_(2)C composite precursor.Theoretical studies reveal that due to the presence of carbon atoms,the electronic structure of C–MoO_(2) has been properly adjusted,and the loaded small Ru nanoparticles provide a fast water dissociation rate and moderate H adsorption strength.In electrochemical studies under a pH-universal environment,Ru/C–MoO_(2) electrocatalyst exhibits a low overpotential at a current density of 10 mA cm^(-2) and has a low Tafel slope.Meanwhile,Ru/C-MoO_(2) has excellent stability for more than 100 h at an initial current density of 100 mA cm^(-2).展开更多
Access to fresh water,its availability,and its quality are a global challenge to humanity,largely due to human activities in the environment.Thus,global water security has been jeopardized,requiring urgent remediation...Access to fresh water,its availability,and its quality are a global challenge to humanity,largely due to human activities in the environment.Thus,global water security has been jeopardized,requiring urgent remediation to safeguard our very existence.Hence,a novel and facilely engineered zirconium and polyethylenimine adsorbent based on tiger nut residue (TNR) was prepared,and its adsorptive capabilities towards a model dyestuff and nutrient were invested through a batch adsorption method.The developed adsorbent,zirconium-polyethylenimine-engineered tiger nut residue (TNR@PEI–Zr) was characterised by scanning electron microscopy,Fourier-transform infrared spectroscopy,X-ray diffraction analysis,and X-ray photoelectron spectroscopy to understand its morphology and surface chemistry and predict its adsorption mechanism.TNR@PEI–Zr had a p H point of zero charge (pH_(zpc)) of 6.7.The introduction of salts inhibited the removal efficiency of Alizarin red (AR) and phosphate (PO_(4)^(3–)) in the order of HCO_(3)^(-)>SO_(4)^(2–)>Cl^(-).Increasing temperatures (293–313 K) favoured the adsorption process at pH 3.The Langmuir model suited the adsorption processes of both AR and PO_(4)^(3–),implying homogenous and monolayer removal of pollutants with a maximal capacity of 537.8 mg·g^(-1)and 100.5 mg·g^(-1)at a dose of 0.01 g,respectively.The rate-determining steps of AR and PO_(4)^(3–)followed a pseudo-secondorder kinetic model and were thermodynamically spontaneous with an increase in randomness at the solid-solution interface.The adsorbent’s recyclability was notable and outperformed most adsorbents in terms of removal efficiency.TNR@PEI–Zr was found to be stable,and its use in practical wastewater decontamination was effective,ecologically acceptable and free of secondary pollution problems.展开更多
The adverse effects of eutrophication have prompted the use of various remediation techniques for phosphate(PO_(4)^(3-))removal owing to it being the major causative agent.Herein,the influence of different solvents an...The adverse effects of eutrophication have prompted the use of various remediation techniques for phosphate(PO_(4)^(3-))removal owing to it being the major causative agent.Herein,the influence of different solvents and ratios of 2-aminoterepthalicacid on the efficiency of magnetic biomass metal-organic framework composites based on the in situ growth of NH_(2)-MIL-101(Fe)onto magnetized peanut husks towards PO_(4)^(3-)removal was assessed via the adsorption technique.The magnetic biocomposite labelled as MPN@NH2-MIL-101(Fe)exhibited the best efficiency owing to its mesoporous structures and presence of abundant oxygen and nitrogen possessing functional groups.Adsorption results confirmed MPN@NH2-MIL-101(Fe)to have a high adsorption capacity of(14.0±0.3)mg·L^(-1)at a PO43-concentration of 20 mg·L^(-1)with an associated high stability within pH 2-10.The adsorption kinetics for the process was well described by both Elovich and pseudo-second-order kinetic models and was mediated by both internal diffusion and liquid film diffusion.The Temkin and Freundlich models fitted the equilibrium data well signifying occurrence of both physical and chemical adsorption on a heterogeneous surface.It is concluded that MPN@NH2-MIL-101(Fe)is a promising adsorbent for the effective removal of phosphate from a water body.展开更多
Sodium-ion battery is a potential application system for large-scale energy storage due to the advantage of higher nature abundance and lower production cost of sodium-based materials.However,there exist inevitably th...Sodium-ion battery is a potential application system for large-scale energy storage due to the advantage of higher nature abundance and lower production cost of sodium-based materials.However,there exist inevitably the safety problems such as flammability due to the use of the same type of organic liquid electrolyte with lithium-ion battery.Gel polymer electrolytes are being considered as an effective solution to replace conventional organic liquid electrolytes for building safer sodium-ion batteries.In this review paper,the authors present a comprehensive overview of the research progress in electrochemical and physical properties of the gel polymer electrolyte-based sodium batteries.The gel polymer electrolytes based on different polymer hosts namely poly(ethylene oxide),poly(acrylonitrile),poly(methyl methacrylate),poly(vinylidene fluoride),poly(vinylidene fluoride-hexafluoro propylene),and other new polymer networks are summarized.The ionic conductivity,ion transference number,electrochemical window,thermal stability,mechanical property,and interfacial issue with electrodes of gel polymer electrolytes,and the corresponding influence factors are described in detail.Furthermore,the ion transport pathway and ion conduction mechanism are analyzed and discussed.In addition,the advanced gel polymer electrolyte systems including flame-retardant polymer electrolytes,composite gel polymer electrolytes,copolymerization,single-ion conducting polymer electrolytes,etc.with more superior and functional performance are classified and summarized.Finally,the application prospects,development opportunities,remaining challenges,and possible solutions are discussed.展开更多
Developing highly active and robust oxygen evolution reaction(OER)electrocatalysts is still a critical challenge for water electrolyzers and metal-air batteries.Realizing the dynamic evolution of the intermediate and ...Developing highly active and robust oxygen evolution reaction(OER)electrocatalysts is still a critical challenge for water electrolyzers and metal-air batteries.Realizing the dynamic evolution of the intermediate and charge transfer during OER and developing a clear OER mechanism is crucial to design high-performance OER catalysts.Recently in Nature,Xue and colleagues revealed a new OER mechanism,coupled oxygen evolution mechanism(COM),which involves a switchable metal and oxygen redox under light irradiation in nickel oxyhydroxide-based materials.This newly developed mechanism requires a reversible geometric conversion between octahedron(NiO_(6))and square planar(NiO_(4))to achieve electronic states with both“metal redox”and“oxygen redox”during OER.The asymmetric structure endows NR-NiOOH with a nonoverlapping region between the dz^(2) orbitals and a_(1g)^(*)bands,which facilitate the geometric conversion and enact the COM pathway.As a result,NR-NiOOH exhibited better OER activity and stability than the traditional NiOOH.展开更多
Exploring the desired anode materials to address the issues of poor structural stability tardy redox kinetics caused by large potassium ionic radius are fatal for the realization of large-scale applications of potassi...Exploring the desired anode materials to address the issues of poor structural stability tardy redox kinetics caused by large potassium ionic radius are fatal for the realization of large-scale applications of potassium-ion batteries.In this work,the feasibility to achieve promoted K^(+)storage by constructing the model of CoS_(2)enfolded in carbon was verified by the density functional theory calculations.And the results predicted a faster electron/potassium ion transport kinetics than bare CoS_(2)by increasing electron carrier density and narrowing diffusion barrier.Therefore,an interfacial engineering strategy was applied and implemented to synthesize the CoS_(2)nanoparticles enveloped in the S-doped carbon(CoS_(2)/SC)under this inspiration.The as-prepared CoS_(2)/SC composite exhibited a prominent rate capability and long cycling lifespan,delivering the high capacity of 375 mA h g^(-1)at 0.2 A g^(-1)at the 100th cycle and 273 mA h g^(-1)at 2 A g^(-1)over 300 cycles.The in/ex situ characterizations unraveled the converse mechanism of CoS_(2)/SC in K^(+)storage,showing an eventually reversible phase transformation of K_(x)CoS_(2)Co↔within the electrochemical reactions.展开更多
Safe, green and efficient industrial production has always been the pursuit of the chemical industry. Since thermal energy is the driving force for most of chemical reactions, an ideal reaction tank would have the cap...Safe, green and efficient industrial production has always been the pursuit of the chemical industry. Since thermal energy is the driving force for most of chemical reactions, an ideal reaction tank would have the capacity to automatically regulate heat conduction rate. In detail, this reaction tank should endow an ability that resists the heat loss when the reaction temperature is lower than the target, while accelerating the heat dissipation when the system is overheated. In this case, this smart reactor can not only minimize energy consumption but also reduce safety risks.Hollow structures are known to reduce heat conductivity. Particularly, the hollow structure with multishells can provide more interfaces and thus further inhibit heat transmission, which would be more favorable for heat isolation. Step forward, by coupling HoMSs with temperature-sensitive polymer, a smart heat isolation material has been fabricated in this work. It performs as a good heat isolator at a relatively lower temperature. A heat insulation effect of 6.5℃ can be achieved for the TSPU/3S–TiO_(2)HoMSs with a thickness of 1 mm under the temperature field of 50℃.The thermal conductivity of composite material would be raised under overheating conditions. Furthermore, this composite displays an unusual two-stage phase transformation during heating. Benefiting from the unique multishelled structure, energy is found to be gradually guided into the hollow structure and stored inside. This localized heat accumulation enables the composite to be a potential coating material for intelligent thermal-regulator and site-defined micro-reactor.展开更多
In this paper,we have developed a decarboxylative amination of carboxylic acids with nitroarenes for the synthesis of secondary amines.The protocol is performed at mild conditions without the use of noble metals as ca...In this paper,we have developed a decarboxylative amination of carboxylic acids with nitroarenes for the synthesis of secondary amines.The protocol is performed at mild conditions without the use of noble metals as catalysts.A wide range of structurally diverse secondary amines could be obtained in good yields(up to 94%)with good functional group tolerance.This transformation shows good to excellent selectivity,avoiding the generation of over alkylated byproducts.展开更多
Metal selenides owing to their high theoretical capacity and good conductivity are considered as one of the potential candidates for the anode materials of sodium-ion batteries(SIBs).However,their practical applicatio...Metal selenides owing to their high theoretical capacity and good conductivity are considered as one of the potential candidates for the anode materials of sodium-ion batteries(SIBs).However,their practical applications are greatly restricted by the poor cycling performances and complicated synthesis methods.In this work,a sandwich-like Sn Se2/reduced graphene oxide(r GO)composite with a small amount of r GO(7.3%)is synthesized by a simple one-pot solvothermal technique.The as-synthesized Sn Se2/r GO shows improved initial coulombic efficiency(ICE)of 73.7%,high capacity of 402.0 m Ah g-1 after 150 cycles at 0.1 A g-1 with a retention of 86.2%and outstanding rate performances.The abundant Sn-O-C bonds of synthesized material not only accelerate the charge transfer at the interface but also enhance the mechanical strength to accommodate volume variation and prevent active material loss during cycling.Moreover,the compact structure leads to thin solid electrolyte interface(SEI)so that high initial coulombic efficiency was obtained.Furthermore,full cells are assembled to test its potential application.This work offers a simple method to synthesize Sn Se2/r GO as a candidate anode for SIBs.展开更多
Li-O_(2) batteries provide an attractive and potential strategy for energy conversion and storage with high specific energy densities.However,large over-potential in oxygen evolution reactions (OER) caused by the deco...Li-O_(2) batteries provide an attractive and potential strategy for energy conversion and storage with high specific energy densities.However,large over-potential in oxygen evolution reactions (OER) caused by the decomposition obstacles of Li_(2)O_(2) seriously impedes its electrochemical performances.Herein,a novel N,O,S and F co-doping vesicular carbon was prepared by self-template pyrolysis method and used in LiO_(2) battery to tune the nucleation and decomposition of Li_(2)O_(2).The introduction of F in the carbon matrix with suitable content can regulate the adsorption of intermediates,through which the morphology of Li_(2)O_(2) can be controlled to film,favorable to its decomposition in charge process.The cathode based on the optimized F doped carbon vesicle exhibits improved electrochemical performances including a low over-potential,large capacity and a long-term stability.Density functional theory (DFT) results show that F and C in C–F bond hasve a strong interaction to Li and O in Li_(2)O_(2),respectively,which can enhance the transfer of electrons from Li_(2)O_(2) to the carbon matrix to generate hole polaron and thus accelerate the delithiation and decomposition of Li_(2)O_(2).This work provides a new sight into understanding the mechanism of nucleation and decomposition of Li_(2)O_(2) for the development of high-performance Li-O_(2) batteries.展开更多
The irreversible consumption of sodium in the initial several cycles greatly led to the attenuation of capacity,which caused the low initial coulombic efficiency(ICE)and obvious poor cycle stability.Presodiation can e...The irreversible consumption of sodium in the initial several cycles greatly led to the attenuation of capacity,which caused the low initial coulombic efficiency(ICE)and obvious poor cycle stability.Presodiation can effectively improve the electrochemical performance by compensating the capacity loss in the initial cycle.Here,carbon-coated sodium-pretreated iron disulfide(NaFeS_(2)@C)has been synthesized through conventional chemical method and used in sodium metal battery as a cathode material.The calculated density of states(DOS)of NaFeS2@C is higher,which implies enhanced electron mobility and improved cycle reversibility.Because of the highly reversible conversion reaction and the compensation of irreversible capacity loss during the initial cycle,the Na/NaFeS_(2)@C battery achieves ultrahigh initial coulombic efficiency(96.7%)and remarkable capacity(751 mA·h·g^(-1) at 0.1 A·g^(-1)).In addition,highly reversible electrochemical reactions and ultra-thin NaF-rich solid electrolyte interphase(SEI)also benefit for the electrochemical performance,even at high current density of 100 A·g^(-1),it still exhibits a reversible capacity of 136 mA·h·g^(-1),and 343 mA·h·g^(-1) after 2500 cycles at 5.0 A·g^(-1).This work aims to bring up new insights to improve the ICE and stability of sodium metal batteries.展开更多
Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-pot...Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-potential cathodes failing to apply in full cells.Herein,vinylene carbonate(VC)as an additive into NaCF_(3) SO_(3)-Diglyme(DGM)could make sodium-ion full cells applicable without preactivation of cathode and anode.The assembled FeS@C||Na3 V2(PO_(4))_(3)@C full cell with this electrolyte exhibits long term cycling stability and high capacity retention.The deduced reason is additive VC,whose HOMO level value is close to that of DGM,not only change the solvent sheath structure of Na^(+),but also is synergistically oxidized with DGM to form integrity and consecutive cathode electrolyte interphase on Na3 V2(PO_(4))_(3)@C cathode,which could effectively improve the oxidative stability of electrolyte and prevent the electrolyte decomposition.This work displays a new way to optimize the sodium-ion full cell seasily with bright practical application potential.展开更多
Fe-based sulfates are ideal cathode candidates for sodium-ion batteries(SIBs) owing to their high operating voltage and low cost but suffer from the nature of poor power performance. Herein, a hierarchical porous Na2F...Fe-based sulfates are ideal cathode candidates for sodium-ion batteries(SIBs) owing to their high operating voltage and low cost but suffer from the nature of poor power performance. Herein, a hierarchical porous Na2Fe(SO4)2@reduced graphene oxide/carbon dot(Na2Fe(SO4)2@rGO/C) with low carbon content(4.12 wt%) was synthesized via a facile homogeneous strategy benefiting for engineering application,which delivers excellent sodium storage performance(high voltage plateau of 3.75 V, 85 m Ah g-1 and330 Wh kg-1 at 0.05 C;5805 W kg-1 at 10 C) and high Na+diffusion coefficient(1.19 × 10-12 cm2 s-1).Moreover, the midpoint voltage of assembled full cell could reach 3.0 V. The electron transfer and reaction kinetics are effectively boosted since the nanoscale Na2Fe(SO4)2 is supported by a robust crosslinked carbon matrix with rGO sheets and carbon dots. The slight rGO sheets sufficiently enhance the electron transfer like a current collecter and restrain the aggregation, as well as ensure smooth ion channels. Meanwhile, the carbon dots in the whole space connect with Na2Fe(SO4)2 and help rGO to promote the conductivity of the electrode. Ex-situ X-ray powder diffraction and X-ray photoelectron spectrometry analysis confirm the high reversibility of this sodiation/desodiation process.展开更多
As anode materials for high-performance sodium-ion batteries and potassium-ion batteries,bimetallic selenides have attracted great concern due to their relatively high electrical conductivity and electrochemical activ...As anode materials for high-performance sodium-ion batteries and potassium-ion batteries,bimetallic selenides have attracted great concern due to their relatively high electrical conductivity and electrochemical activity.However,the formidable challenge in the reaction process is the large volume change,leading to the structural collapse of material,and eventually the decline in electrochemical performance.Herein,a composite of hierarchical CoSe_(2)–MoSe_(2) tubes anchored on reduced graphene oxide nanosheets(CoSe_(2)–MoSe_(2)/rGO)is designed by an in situ hydrothermal selenization treatment.Benefiting from the synergistic effects between CoSe_(2) and MoSe_(2),unique hierarchical structure,and effective reduced graphene oxide coating,the CoSe_(2)–MoSe_(2)/rGO exhibited improved reaction kinetics and structural stability,and thus good electrochemical properties.A combination mechanism of intercalation and conversion of CoSe_(2)–MoSe_(2)/rGO by forming NaxCoSe_(2) and Mo_(15)Se_(19) as intermediate states is put forward on the basis of in situ and ex situ XRD analyses.展开更多
基金the National Natural Science Foundation of China(No.41807213)the Hydrogeo-logical Survey Project of Huangshui River(No.DD20190331).
文摘Water splitting is important to the conversion and storage of renewable energy,but slow kinetics of the oxygen evolution reaction(OER)greatly limits its utility.Here,under visible light illumination,the p-n WO_(3)/SnSe_(2)(WS)heterojunction significantly activates OER catalysis of CoFe-layered double hydroxide(CF)/carbon nanotubes(CNTs).Specifically,the catalyst achieves an overpotential of 224 mV at 10 mA cm^(-2)and a small Tafel slope of 47 mV dec^(-1),superior to RuO_(2)and most previously reported transition metal-based OER catalysts.The p-n WS heterojunction shows strong light absorption to produce photogenerated carriers.The photogenerated holes are trapped by CF to suppresses the charge recombination and facilitate charge transfer,which accelerates OER kinetics and boost the activity for the OER.This work highlights the possibility of using heterojunctions to activate OER catalysis and advances the design of energy-efficient catalysts for water oxidation systems using solar energy.
基金The Natural Science Foundation of Henan Province(222300420083)the Opening Foundation of State Key Laboratory of Chemistry and Utilization of Carbon-based Energy Resource of Xinjiang University(KFKT2021004)。
文摘The large volumetric variations experienced by metal selenides within conversion reaction result in inferior rate capability and cycling stability,ultimately hindering the achievement of superior electrochemical performance.Herein,metallic Cu_(2)Se encapsulated with N-doped carbon(Cu_(2)Se@NC)was prepared using Cu_(2)O nanocubes as templates through a combination of dopamine polymerization and hightemperature selenization.The unique nanocubic structure and uniform N-doped carbon coating could shorten the ion transport distance,accelerate electron/charge diffusion,and suppress volume variation,ultimately ensuring Cu_(2)Se@NC with excellent electrochemical performance in sodium ion batteries(SIBs)and potassium ion batteries(PIBs).The composite exhibited excellent rate performance(187.7 mA h g^(-1)at 50 A g^(-1)in SIBs and 179.4 mA h g^(-1)at 5 A g^(-1)in PIBs)and cyclic stability(246,8 mA h g^(-1)at 10 A g^(-1)in SIBs over 2500 cycles).The reaction mechanism of intercalation combined with conversion in both SIBs and PIBs was disclosed by in situ X-ray diffraction(XRD)and ex situ transmission electron microscope(TEM).In particular,the final products in PIBs of K_(2)Se and K_(2)Se_(3)species were determined after discharging,which is different from that in SIBs with the final species of Na_(2)Se.The density functional theory calculation showed that carbon induces strong coupling and charge interactions with Cu_(2)Se,leading to the introduction of built-in electric field on heterojunction to improve electron mobility.Significantly,the theoretical calculations discovered that the underlying cause for the relatively superior rate capability in SIBs to that in PIBs is the agile Na~+diffusion with low energy barrier and moderate adsorption energy.These findings offer theoretical support for in-depth understanding of the performance differences of Cu-based materials in different ion storage systems.
基金support from the National Natural Science Foundation of China (No. 21373189)the Natural Science Foundation of Henan Province (No. 182300410278)。
文摘The design of sulfur hosts with high conductivity,large specific surface area,strong adsorption and electrocatalytic ability is crucial to advance high performance lithium-sulfur batteries.Herein,a novel ultrathin sandwich-type Ni-doped MoS_(2)/reduced graphene oxide(denote as Ni-doped MoS_(2)/rGO) hybrid is developed as a sulfur host through a simple one-step hydrothermal route.The two-dimensional layered structure Ni-doped MoS_(2)/rGO hybrid with heterostructure and heteroatom architecture defects not only plays a key role in adsorption of lithium polysulfide but also catalyzes on redox kinetics of sulfur and polysulfide species.Meanwhile,it can contribute to the large specific surface area for Li_(2) S/S_8 deposition,fast Li-ion and electron transportation,thus enhancing the electrocatalytic properties,as confirmed firstly by cyclic voltammetry(CV) results.Due to the adsorption-catalytic synergistic effect,the Ni-doped MoS_(2)/rGO cathode exhibits high specific capacity(1343.6 mA h g^(-1) at 0.2 C,921.6 mA h g^(-1) at 1 C),high coulombic efficiency and an outstanding cycle stability(with the low attenuation rate of 0.077% per cycle over 140 cycles at 0.5 C and 0.11% per cycle over 400 cycles at 1 C,respectively).This work proposes some inspiration for exploring the construction of advanced lithium-sulfur batteries through the rational design defects of atomic structure and electronic states of MoS_(2) as sulfur host.
文摘Homogeneous and heterogeneous types of catalysis are frequently considered as separate disciplines or even opposed to each other.In the present work,a new type of mixed het-ero-/homogeneous catalysis was demonstrated for the case of selective alkylarene oxidation by molecular oxygen.The proposed catalytic system consists of two widely available components:N-hydroxyphthalimide(NHPI,a homogeneous organocatalyst for free-radical chain reactions)and nanosized TiO_(2)(heterogeneous UV-active photoredox catalyst).The interaction of NHPI with TiO_(2) allows for a shift from UV to visible light photoredox activity and generation of phthalimide-N-oxyl(PINO)radicals that diffuse into the solution where NHPI/PINO-catalyzed free-radical chain reaction can proceed without the additional light input providing a fundamental increase in energy efficiency.The NHPI/TiO_(2) ratio controls the selectivity of oxidation affording preferential formation of hydroperoxide or ketone from alkylarene.
基金supported by the grants from the Research Grants Council of the Hong Kong Special Administrative Region,China (Project No. 16205721)Guangdong Basic and Applied Basic Research Foundation (Project No.2021A1515011815)Poly U Start-up Fund (Project No. 1-BDC4)。
文摘Water electrolysis is considered as one most promising technique for hydrogen production.The high efficiency electrocatalyst is the key to accelerating the sluggish kinetics of the hydrogen evolution reaction(HER) in alkaline media.In this work,an efficient HER electrocatalyst with hetero-interfacial metal-metal oxide structure was constructed through a redox solid phase reaction(SPR) strategy.During the annealing process under Ar atmosphere,RuO_(2) and WS_(2)in RuO_(2)/WS_(2)precursor were converted to Ru nanoparticles(NPs) and WO3in situ,where tiny Ru NPs and oxygen vacancies were uniformly distributed onto the newly formed WO3nanosheets.Different characterization techniques were adopted to confirm the successful formation of Ru/WO_(3)electrocatalyst(RWOC).The optimized RWOC sample annealed at 400℃ exhibited the low overpotential value of 13 mV at a current density of 10 mA cm^(-2)and strong durability under the alkaline condition.Density functional theoretical calculations further revealed that the promoted adsorption/desorption rate of reaction intermediates and the accelerated kinetics of HER process were deduced to the synergistic effect between Ru and WO_(3)in electrocatalyst.This work provides a feasible method to fabricate highly efficient HER electrocatalysts.
基金partly supported by the National Natural Science Foundation of China(NSFCs,52202050,52122308,21905253,51973200)the China Postdoctoral Science Foundation(2022TQ0286)the Natural Science Foundation of Henan(202300410372)。
文摘Water electrolysis using proton-exchange membranes is one of the most promising technologies for carbon-neutral and sustainable energy production.Generally,the overall efficiency of water splitting is limited by the oxygen evolution reaction(OER).Nevertheless,a trade-off between activity and stability exists for most electrocatalytic materials in strong acids and oxidizing media,and the development of efficient and stable catalytic materials has been an important focus of research.In this view,gaining in-depth insights into the OER system,particularly the interactions between reaction intermediates and active sites,is significantly important.To this end,this review introduces the fundamentals of the OER over Ru-based materials,including the conventional adsorbate evolution mechanism,lattice oxygen oxidation mechanism,and oxide path mechanism.Moreover,the up-to-date progress of representative modifications for improving OER performance is further discussed with reference to specific mechanisms,such as tuning of geometric,electronic structures,incorporation of proton acceptors,and optimization of metal-oxygen covalency.Finally,some valuable insights into the challenges and opportunities for OER electrocatalysts are provided with the aim to promote the development of next-generation catalysts with high activity and excellent stability.
基金This work was financially supported by the National Natural Science Foundation of China (52122308,21905253,51973200)the Natural Science Foundation of Henan (202300410372).
文摘The defect-free structure of Mo-based materials is a“double-edged sword”,which endows the material with excellent stability,but limits its chemical versatility and application in electrochemical hydrogen evolution reaction(HER).Carbon doping engineering is an attractive strategy to effectively improve the performance of Mo-based catalyst and maintain their stability.Herein,we report a cross-linked porous carbon-doped MoO_(2)(C–MoO_(2))-based catalyst Ru/C–MoO_(2) for electrochemical HER,which is prepared by the convenient redox solid-phase reaction(SPR)of porous RuO_(2)/Mo_(2)C composite precursor.Theoretical studies reveal that due to the presence of carbon atoms,the electronic structure of C–MoO_(2) has been properly adjusted,and the loaded small Ru nanoparticles provide a fast water dissociation rate and moderate H adsorption strength.In electrochemical studies under a pH-universal environment,Ru/C–MoO_(2) electrocatalyst exhibits a low overpotential at a current density of 10 mA cm^(-2) and has a low Tafel slope.Meanwhile,Ru/C-MoO_(2) has excellent stability for more than 100 h at an initial current density of 100 mA cm^(-2).
文摘Access to fresh water,its availability,and its quality are a global challenge to humanity,largely due to human activities in the environment.Thus,global water security has been jeopardized,requiring urgent remediation to safeguard our very existence.Hence,a novel and facilely engineered zirconium and polyethylenimine adsorbent based on tiger nut residue (TNR) was prepared,and its adsorptive capabilities towards a model dyestuff and nutrient were invested through a batch adsorption method.The developed adsorbent,zirconium-polyethylenimine-engineered tiger nut residue (TNR@PEI–Zr) was characterised by scanning electron microscopy,Fourier-transform infrared spectroscopy,X-ray diffraction analysis,and X-ray photoelectron spectroscopy to understand its morphology and surface chemistry and predict its adsorption mechanism.TNR@PEI–Zr had a p H point of zero charge (pH_(zpc)) of 6.7.The introduction of salts inhibited the removal efficiency of Alizarin red (AR) and phosphate (PO_(4)^(3–)) in the order of HCO_(3)^(-)>SO_(4)^(2–)>Cl^(-).Increasing temperatures (293–313 K) favoured the adsorption process at pH 3.The Langmuir model suited the adsorption processes of both AR and PO_(4)^(3–),implying homogenous and monolayer removal of pollutants with a maximal capacity of 537.8 mg·g^(-1)and 100.5 mg·g^(-1)at a dose of 0.01 g,respectively.The rate-determining steps of AR and PO_(4)^(3–)followed a pseudo-secondorder kinetic model and were thermodynamically spontaneous with an increase in randomness at the solid-solution interface.The adsorbent’s recyclability was notable and outperformed most adsorbents in terms of removal efficiency.TNR@PEI–Zr was found to be stable,and its use in practical wastewater decontamination was effective,ecologically acceptable and free of secondary pollution problems.
基金supported by the National Key Research and Development Program of China (2018YFD0401402–04)Zhongyuan Scholars Foundation (202101510005).
文摘The adverse effects of eutrophication have prompted the use of various remediation techniques for phosphate(PO_(4)^(3-))removal owing to it being the major causative agent.Herein,the influence of different solvents and ratios of 2-aminoterepthalicacid on the efficiency of magnetic biomass metal-organic framework composites based on the in situ growth of NH_(2)-MIL-101(Fe)onto magnetized peanut husks towards PO_(4)^(3-)removal was assessed via the adsorption technique.The magnetic biocomposite labelled as MPN@NH2-MIL-101(Fe)exhibited the best efficiency owing to its mesoporous structures and presence of abundant oxygen and nitrogen possessing functional groups.Adsorption results confirmed MPN@NH2-MIL-101(Fe)to have a high adsorption capacity of(14.0±0.3)mg·L^(-1)at a PO43-concentration of 20 mg·L^(-1)with an associated high stability within pH 2-10.The adsorption kinetics for the process was well described by both Elovich and pseudo-second-order kinetic models and was mediated by both internal diffusion and liquid film diffusion.The Temkin and Freundlich models fitted the equilibrium data well signifying occurrence of both physical and chemical adsorption on a heterogeneous surface.It is concluded that MPN@NH2-MIL-101(Fe)is a promising adsorbent for the effective removal of phosphate from a water body.
基金supported by the National Natural Science Foundation of China(Nos.21771164,U1804129)the Natural Science Foundation of Henan Province(No.222300420525)the Zhongyuan Youth Talent Support Program of Henan Province
文摘Sodium-ion battery is a potential application system for large-scale energy storage due to the advantage of higher nature abundance and lower production cost of sodium-based materials.However,there exist inevitably the safety problems such as flammability due to the use of the same type of organic liquid electrolyte with lithium-ion battery.Gel polymer electrolytes are being considered as an effective solution to replace conventional organic liquid electrolytes for building safer sodium-ion batteries.In this review paper,the authors present a comprehensive overview of the research progress in electrochemical and physical properties of the gel polymer electrolyte-based sodium batteries.The gel polymer electrolytes based on different polymer hosts namely poly(ethylene oxide),poly(acrylonitrile),poly(methyl methacrylate),poly(vinylidene fluoride),poly(vinylidene fluoride-hexafluoro propylene),and other new polymer networks are summarized.The ionic conductivity,ion transference number,electrochemical window,thermal stability,mechanical property,and interfacial issue with electrodes of gel polymer electrolytes,and the corresponding influence factors are described in detail.Furthermore,the ion transport pathway and ion conduction mechanism are analyzed and discussed.In addition,the advanced gel polymer electrolyte systems including flame-retardant polymer electrolytes,composite gel polymer electrolytes,copolymerization,single-ion conducting polymer electrolytes,etc.with more superior and functional performance are classified and summarized.Finally,the application prospects,development opportunities,remaining challenges,and possible solutions are discussed.
基金supported by the National Natural Science Foundation of China(52122308,21905253,51973200).
文摘Developing highly active and robust oxygen evolution reaction(OER)electrocatalysts is still a critical challenge for water electrolyzers and metal-air batteries.Realizing the dynamic evolution of the intermediate and charge transfer during OER and developing a clear OER mechanism is crucial to design high-performance OER catalysts.Recently in Nature,Xue and colleagues revealed a new OER mechanism,coupled oxygen evolution mechanism(COM),which involves a switchable metal and oxygen redox under light irradiation in nickel oxyhydroxide-based materials.This newly developed mechanism requires a reversible geometric conversion between octahedron(NiO_(6))and square planar(NiO_(4))to achieve electronic states with both“metal redox”and“oxygen redox”during OER.The asymmetric structure endows NR-NiOOH with a nonoverlapping region between the dz^(2) orbitals and a_(1g)^(*)bands,which facilitate the geometric conversion and enact the COM pathway.As a result,NR-NiOOH exhibited better OER activity and stability than the traditional NiOOH.
基金The National Natural Science Foundation of China(Grant No.21701144)Opening Foundation of State Key Laboratory of Chemistry and Utilization of Carbon-based Energy Resource of Xinjiang University(Grant No.KFKT2021004)are gratefully acknowledged.
文摘Exploring the desired anode materials to address the issues of poor structural stability tardy redox kinetics caused by large potassium ionic radius are fatal for the realization of large-scale applications of potassium-ion batteries.In this work,the feasibility to achieve promoted K^(+)storage by constructing the model of CoS_(2)enfolded in carbon was verified by the density functional theory calculations.And the results predicted a faster electron/potassium ion transport kinetics than bare CoS_(2)by increasing electron carrier density and narrowing diffusion barrier.Therefore,an interfacial engineering strategy was applied and implemented to synthesize the CoS_(2)nanoparticles enveloped in the S-doped carbon(CoS_(2)/SC)under this inspiration.The as-prepared CoS_(2)/SC composite exhibited a prominent rate capability and long cycling lifespan,delivering the high capacity of 375 mA h g^(-1)at 0.2 A g^(-1)at the 100th cycle and 273 mA h g^(-1)at 2 A g^(-1)over 300 cycles.The in/ex situ characterizations unraveled the converse mechanism of CoS_(2)/SC in K^(+)storage,showing an eventually reversible phase transformation of K_(x)CoS_(2)Co↔within the electrochemical reactions.
基金financially supported by the National Natural Science Foundation of China (Nos.21931012,21971244,92163209,and 52174387)the Education Department of Henan Province (No.20A430024)。
文摘Safe, green and efficient industrial production has always been the pursuit of the chemical industry. Since thermal energy is the driving force for most of chemical reactions, an ideal reaction tank would have the capacity to automatically regulate heat conduction rate. In detail, this reaction tank should endow an ability that resists the heat loss when the reaction temperature is lower than the target, while accelerating the heat dissipation when the system is overheated. In this case, this smart reactor can not only minimize energy consumption but also reduce safety risks.Hollow structures are known to reduce heat conductivity. Particularly, the hollow structure with multishells can provide more interfaces and thus further inhibit heat transmission, which would be more favorable for heat isolation. Step forward, by coupling HoMSs with temperature-sensitive polymer, a smart heat isolation material has been fabricated in this work. It performs as a good heat isolator at a relatively lower temperature. A heat insulation effect of 6.5℃ can be achieved for the TSPU/3S–TiO_(2)HoMSs with a thickness of 1 mm under the temperature field of 50℃.The thermal conductivity of composite material would be raised under overheating conditions. Furthermore, this composite displays an unusual two-stage phase transformation during heating. Benefiting from the unique multishelled structure, energy is found to be gradually guided into the hollow structure and stored inside. This localized heat accumulation enables the composite to be a potential coating material for intelligent thermal-regulator and site-defined micro-reactor.
基金National Key Research and Development Program of China(2022YFA1503200,2021YFC2101901)the National Natural Science Foundation of China(22122103,22101130,22001117,21971108,22271144)Fundamental Research Funds for the Central Universities(020514380304,020514380252,020514380272)for financial support.
文摘In this paper,we have developed a decarboxylative amination of carboxylic acids with nitroarenes for the synthesis of secondary amines.The protocol is performed at mild conditions without the use of noble metals as catalysts.A wide range of structurally diverse secondary amines could be obtained in good yields(up to 94%)with good functional group tolerance.This transformation shows good to excellent selectivity,avoiding the generation of over alkylated byproducts.
基金supported by the National Natural Science Foundation of China(Nos.21771164,U1804129,21773215)。
文摘Metal selenides owing to their high theoretical capacity and good conductivity are considered as one of the potential candidates for the anode materials of sodium-ion batteries(SIBs).However,their practical applications are greatly restricted by the poor cycling performances and complicated synthesis methods.In this work,a sandwich-like Sn Se2/reduced graphene oxide(r GO)composite with a small amount of r GO(7.3%)is synthesized by a simple one-pot solvothermal technique.The as-synthesized Sn Se2/r GO shows improved initial coulombic efficiency(ICE)of 73.7%,high capacity of 402.0 m Ah g-1 after 150 cycles at 0.1 A g-1 with a retention of 86.2%and outstanding rate performances.The abundant Sn-O-C bonds of synthesized material not only accelerate the charge transfer at the interface but also enhance the mechanical strength to accommodate volume variation and prevent active material loss during cycling.Moreover,the compact structure leads to thin solid electrolyte interface(SEI)so that high initial coulombic efficiency was obtained.Furthermore,full cells are assembled to test its potential application.This work offers a simple method to synthesize Sn Se2/r GO as a candidate anode for SIBs.
基金financially supported by the National Natural Science Foundation of China(Grant No.21701145)the China Postdoctoral Science Foundation(Grant Nos.2017M610459,2018T110739)。
文摘Li-O_(2) batteries provide an attractive and potential strategy for energy conversion and storage with high specific energy densities.However,large over-potential in oxygen evolution reactions (OER) caused by the decomposition obstacles of Li_(2)O_(2) seriously impedes its electrochemical performances.Herein,a novel N,O,S and F co-doping vesicular carbon was prepared by self-template pyrolysis method and used in LiO_(2) battery to tune the nucleation and decomposition of Li_(2)O_(2).The introduction of F in the carbon matrix with suitable content can regulate the adsorption of intermediates,through which the morphology of Li_(2)O_(2) can be controlled to film,favorable to its decomposition in charge process.The cathode based on the optimized F doped carbon vesicle exhibits improved electrochemical performances including a low over-potential,large capacity and a long-term stability.Density functional theory (DFT) results show that F and C in C–F bond hasve a strong interaction to Li and O in Li_(2)O_(2),respectively,which can enhance the transfer of electrons from Li_(2)O_(2) to the carbon matrix to generate hole polaron and thus accelerate the delithiation and decomposition of Li_(2)O_(2).This work provides a new sight into understanding the mechanism of nucleation and decomposition of Li_(2)O_(2) for the development of high-performance Li-O_(2) batteries.
基金the National Natural Science Foundation of China(Nos.U1804129,21771164)2020 College Student Innovation and Entrepreneurship Training Program(202010459004)Zhongyuan Youth Talent Support Program of Henan Province and Zhengzhou University Youth Innovation Program.
文摘The irreversible consumption of sodium in the initial several cycles greatly led to the attenuation of capacity,which caused the low initial coulombic efficiency(ICE)and obvious poor cycle stability.Presodiation can effectively improve the electrochemical performance by compensating the capacity loss in the initial cycle.Here,carbon-coated sodium-pretreated iron disulfide(NaFeS_(2)@C)has been synthesized through conventional chemical method and used in sodium metal battery as a cathode material.The calculated density of states(DOS)of NaFeS2@C is higher,which implies enhanced electron mobility and improved cycle reversibility.Because of the highly reversible conversion reaction and the compensation of irreversible capacity loss during the initial cycle,the Na/NaFeS_(2)@C battery achieves ultrahigh initial coulombic efficiency(96.7%)and remarkable capacity(751 mA·h·g^(-1) at 0.1 A·g^(-1)).In addition,highly reversible electrochemical reactions and ultra-thin NaF-rich solid electrolyte interphase(SEI)also benefit for the electrochemical performance,even at high current density of 100 A·g^(-1),it still exhibits a reversible capacity of 136 mA·h·g^(-1),and 343 mA·h·g^(-1) after 2500 cycles at 5.0 A·g^(-1).This work aims to bring up new insights to improve the ICE and stability of sodium metal batteries.
基金supported by the National Natural Science Foundation of China(Nos.U1804129,21771164,21671205,U1804126)Zhongyuan Youth Talent Support Program of Henan ProvinceZhengzhou University Youth Innovation Program。
文摘Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-potential cathodes failing to apply in full cells.Herein,vinylene carbonate(VC)as an additive into NaCF_(3) SO_(3)-Diglyme(DGM)could make sodium-ion full cells applicable without preactivation of cathode and anode.The assembled FeS@C||Na3 V2(PO_(4))_(3)@C full cell with this electrolyte exhibits long term cycling stability and high capacity retention.The deduced reason is additive VC,whose HOMO level value is close to that of DGM,not only change the solvent sheath structure of Na^(+),but also is synergistically oxidized with DGM to form integrity and consecutive cathode electrolyte interphase on Na3 V2(PO_(4))_(3)@C cathode,which could effectively improve the oxidative stability of electrolyte and prevent the electrolyte decomposition.This work displays a new way to optimize the sodium-ion full cell seasily with bright practical application potential.
基金the National Natural Science Foundation of China(Nos.21771164,U1804129 and 21671205)Postdoctoral Research Grant in Henan Province(001702055)+1 种基金Center of Advanced Analysis&Gene Sequencing of Zhengzhou Universitythe Zhongyuan Youth Talent support program in Henan province。
文摘Fe-based sulfates are ideal cathode candidates for sodium-ion batteries(SIBs) owing to their high operating voltage and low cost but suffer from the nature of poor power performance. Herein, a hierarchical porous Na2Fe(SO4)2@reduced graphene oxide/carbon dot(Na2Fe(SO4)2@rGO/C) with low carbon content(4.12 wt%) was synthesized via a facile homogeneous strategy benefiting for engineering application,which delivers excellent sodium storage performance(high voltage plateau of 3.75 V, 85 m Ah g-1 and330 Wh kg-1 at 0.05 C;5805 W kg-1 at 10 C) and high Na+diffusion coefficient(1.19 × 10-12 cm2 s-1).Moreover, the midpoint voltage of assembled full cell could reach 3.0 V. The electron transfer and reaction kinetics are effectively boosted since the nanoscale Na2Fe(SO4)2 is supported by a robust crosslinked carbon matrix with rGO sheets and carbon dots. The slight rGO sheets sufficiently enhance the electron transfer like a current collecter and restrain the aggregation, as well as ensure smooth ion channels. Meanwhile, the carbon dots in the whole space connect with Na2Fe(SO4)2 and help rGO to promote the conductivity of the electrode. Ex-situ X-ray powder diffraction and X-ray photoelectron spectrometry analysis confirm the high reversibility of this sodiation/desodiation process.
基金supported by the National Natural Science Foundation of China(Grant No.21701144)。
文摘As anode materials for high-performance sodium-ion batteries and potassium-ion batteries,bimetallic selenides have attracted great concern due to their relatively high electrical conductivity and electrochemical activity.However,the formidable challenge in the reaction process is the large volume change,leading to the structural collapse of material,and eventually the decline in electrochemical performance.Herein,a composite of hierarchical CoSe_(2)–MoSe_(2) tubes anchored on reduced graphene oxide nanosheets(CoSe_(2)–MoSe_(2)/rGO)is designed by an in situ hydrothermal selenization treatment.Benefiting from the synergistic effects between CoSe_(2) and MoSe_(2),unique hierarchical structure,and effective reduced graphene oxide coating,the CoSe_(2)–MoSe_(2)/rGO exhibited improved reaction kinetics and structural stability,and thus good electrochemical properties.A combination mechanism of intercalation and conversion of CoSe_(2)–MoSe_(2)/rGO by forming NaxCoSe_(2) and Mo_(15)Se_(19) as intermediate states is put forward on the basis of in situ and ex situ XRD analyses.