查看更多>>摘要：With the continuing boost in the demand for energy storage,there is an increasing requirement for bat-teries to be capable of operation in extreme environmental conditions.Sodium-ion batteries(SIBs)have emerged as a highly promising energy storage solution due to their promising performance over a wide range of temperatures and the abundance of sodium resources in the earth's crust.Compared to lithium-ion batteries(LIBs),although sodium ions possess a larger ionic radius,they are more easily desolvated than lithium ions.Furthermore,SIBs have a smaller Stokes radius than lithium ions,resulting in improved sodium-ion mobility in the electrolyte.Nevertheless,SIBs demonstrate a significant decrease in perfor-mance at low temperatures(LT),which constrains their operation in harsh weather conditions.Despite the increasing interest in SIBs,there is a notable scarcity of research focusing specifically on their mech-anism under LT conditions.This review explores recent research that considers the thermal tolerance of SIBs from an inner chemistry process perspective,spanning a wide temperature spectrum(-70 to 100 ℃),particularly at LT conditions.In addition,the enhancement of electrochemical performance in LT SIBs is based on improvements in reaction kinetics and cycling stability achieved through the utiliza-tion of effective electrode materials and electrolyte components.Furthermore,the safety concerns asso-ciated with SIBs are addressed and effective strategies are proposed for mitigating these issues.Finally,prospects conducted to extend the environmental frontiers of commercial SIBs are discussed mainly from three viewpoints including innovations in materials,development and research of relevant theoretical mechanisms,and intelligent safety management system establishment for larger-scale energy storage SIBs.
查看更多>>摘要：The global concerns of energy crisis and climate change,primarily caused by carbon dioxide(CO2),are of utmost importance.Recently,the electrocatalytic CO2 reduction reaction(CO2RR)to high value-added multi-carbon(C2+)products driven by renewable electricity has emerged as a highly promising solution to alleviate energy shortages and achieve carbon neutrality.Among these C2+products,ethylene(C2H4)holds particular importance in the petrochemical industry.Accordingly,this review aims to establish a connection between the fundamentals of electrocatalytic CO2 reduction reaction to ethylene(CO2RR-to-C2H4)in laboratory-scale research(lab)and its potential applications in industrial-level fabrication(fab).The review begins by summarizing the fundamental aspects,including the design strategies of high-performance Cu-based electrocatalysts and advanced electrolyzer devices.Subsequently,innovative and value-added techniques are presented to address the inherent challenges encountered during the implementations of CO2RR-to-C2H4 in industrial scenarios.Additionally,case studies of the techno-economic analysis of the CO2RR-to-C2H4 process are discussed,taking into factors such as cost-effectiveness,scalability,and market potential.The review concludes by outlining the perspectives and challenges associated with scaling up the CO2RR-to-C2H4 process.The insights presented in this review are expected to make a valuable contribution in advancing the CO2RR-to-C2H4 process from lab to fab.
查看更多>>摘要：The development of efficient single-atom catalysts(SACs)for the oxygen reduction reaction(ORR)remains a formidable challenge,primarily due to the symmetric charge distribution of metal single-atom sites(M-N4).To address such issue,herein,Fe-Nx sites coupled synergistic catalysts fabrication strategy is presented to break the uniform electronic distribution,thus enhancing the intrinsic catalytic activity.Precisely,atomically dispersed Fe-Nx sites supported on N/S-doped mesoporous carbon(NSC)coupled with FeS@C core-shell nanoparticles(FAS-NSC@950)is synthesized by a facile hydrothermal reaction and subsequent pyrolysis.Due to the presence of an in situ-grown conductive graphitic layer(shell),the FeS nanoparticles(core)effectively adjust the electronic structure of single-atom Fe sites and facilitate the ORR kinetics via short/long-range coupling interactions.Consequently,FAS-NSC@950 displays a more positive half-wave potential(E1/2)of 0.871 V with a significantly boosted ORR kinetics(Tafel slope=52.2 mV dec-1),outpacing the commercial Pt/C(E1/2=0.84 V and Tafel slope=54.6 mV dec-1).As a bifunctional electrocatalyst,it displays a smaller bifunctional activity parameter(△E)of 0.673 V,surpassing the Pt/C-RuO2 combination(△E=0.724 V).Besides,the FAS-NSC@950-based zinc-air battery(ZAB)displays superior power density,specific capacity,and long-term cycling performance to the Pt/C-Ir/C-based ZAB.This work significantly contributes to the field by offering a promising strat-egy to enhance the catalytic activity of SACs for ORR,with potential implications for energy conversion and storage technologies.
查看更多>>摘要：The development of aqueous zinc ion battery cathode materials with high capacity and high magnifica-tion is still a challenge.Herein,porous vanadium oxide/carbon(p-VOx@C,mainly VO2 with a small amount of V2O3)core/shell microspheres with oxygen vacancies are facilely fabricated by using a vanadium-based metal-organic framework(MIL-100(V))as a sacrificial template.This unique structure can improve the conductivity of the VOx,accelerate electrolyte diffusion,and suppress structural collapse during circulation.Subsequently,H2O molecules are introduced into the interlayer of VOx through a highly efficient in-situ electrochemical activation process,facilitating the intercalation and diffusion of zinc ions.After the activation,an optimal sample exhibits a high specific capacity of 464.3 mA h g-1 at 0.2 A g-1 and 395.2 mA h g-1 at 10 A g-1,indicating excellent rate performance.Moreover,the optimal sample maintains a capacity retention of about 89.3％after 2500 cycles at 10 A g-1.Density functional theory calculation demonstrates that the presence of oxygen vacancies and intercalated water molecules can significantly reduce the diffusion barrier for zinc ions.In addition,it is proved that the storage of zinc ions in the cathode is achieved by reversible intercalation/extraction during the charge and discharge process through various ex-situ analysis technologies.This work demonstrates that the p-VOx@C has great potential for applications in aqueous ZIBs after electrochemical activation.
查看更多>>摘要：Designing efficient and long-lasting non-metal electrocatalysts is an urgent task for addressing the issue of kinetic hysteresis in electrochemical oxidation reactions.The bimetallic hydroxides,catalyzing the oxygen evolution reaction(OER),have significant research potential because hydroxide reconstruction to generate an active phase is a remarkable advantage.Herein,the complete reconstruction of ultrathin CoNi(OH)2 nanosheets was achieved by embedding Ag nanoparticles into the hydroxide to induce a spon-taneous redox reaction(SRR),forming heterojunction Ag@CoNi(OH)2 for bifunctional hydrolysis.Theoretical calculations and in situ Raman and ex situ characterizations revealed that the inductive effect of the Ag cation redistributed the charge to promote phase transformation to highly activate Ag-modified hydroxides.The Co-Ni dual sites in Co/NiOOH serve as novel active sites for optimizing the intermediates,thereby weakening the barrier formed by OOH*.Ag@CoNi(OH)2 required a potential of 1.55 V to drive water splitting at a current density of 10 mA cm-2,with nearly 98.6％Faraday efficiency.Through ion induction and triggering of electron regulation in the OER via the synergistic action of the heterogeneous interface and surface reconstruction,this strategic design can overcome the limited capacity of bimetallic hydroxides and bridge the gap between the basic theory and industrialization of water decomposition.
查看更多>>摘要：Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs)is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi0.7-xSmxSr0.3FeO3-δ perovskites as highly-active catalysts for LT-SOFCs.Sm doping can significantly enhance the electrocatalytic activity and chemical stability of cathode.At 600 ℃,Bi0.675Sm0.025Sr0.3FeO3-δ(BSSF25)cathode has been found to be the optimum composition with a polar-ization resistance of 0.098 Q cm2,which is only around 22.8％of Bi0.7Sr0.3FeO3-δ(BSF).A full cell utilizing BSSF25 displays an exceptional output density of 790 mW cm-2,which can operate continuously over 100 h without obvious degradation.The remarkable electrochemical performance observed can be attrib-uted to the improved O2 transport kinetics,superior surface oxygen adsorption capacity,as well as O 2p band centers in close proximity to the Fermi level.Moreover,larger average bonding energy(ABE)and the presence of highly acidic Bi,Sm,and Fe ions restrict the adsorption of CO2 on the cathode surface,resulting in excellent CO2 resistivity.This work provides valuable guidance for systematic design of effi-cient and durable catalysts for LT-SOFCs.
查看更多>>摘要：M-N-C(M=Fe,Co,Ni,etc.)catalyst owns high catalytic activity in the oxygen catalytic reaction which is the most likely to replace the Pt-based catalysts.But it is still a challenge to further increase the active site density.This article constructs the high-efficiency FeMn-N/S-C-1000 catalyst to realize ORR/OER bifunctional catalysis by hetero-atom,bimetal(Fe,Mn)doped simultaneously strategy.When evaluated it as bi-functional electro-catalysts,FeMn-N/S-C-1000 exhibits excellent catalytic activity(E1/2=0.924 V,Ej=10=1.617 V)in alkaline media,outperforms conventional Pt/C,RuO2 and most non-precious-metal cat-alysts reported recently.Such outstanding performance is owing to N,S co-coordinated with metal to form multi-types of single atom,dual atom active sites to carry out bi-catalysis.Importantly,nitrite poi-son test provides the proof that the active sites of FeMn-N/S-C are more than that of single-atom catalysts to promote catalytic reactions directly.To better understand the local structure of Fe and Mn active sites,XAS and DFT were employed to reveal that FeMn-N5/S-C site plays the key role during catalysis.Notably,the FeMn-N/S-C-1000 based low-temperature rechargeable flexible Zn-air also exhibits superior dis-charge performance and extraordinary durability at-40 ℃.This work will provide a new idea to design diatomic catalysts applied in low-temperature rechargeable batteries.
查看更多>>摘要：Highly-efficient oxidation of 5-hydroxymethylfurfural(HMF)to 2,5-furandicarboxylic acid(FDCA)at low temperature with air as the oxidant is still challenging.Herein,inspired by the respiratory electron trans-port chain(ETC)of living cells mediated by electron carriers,we constructed artificial ETCs and trans-formed liquid flow fuel cells(LFFCs)to flexible reactors for efficient oxidation of HMF to produce FDCA under mild conditions.This LFFC reactor employed an electrodeposition modified nickel foam as an anode to promote HMF oxidation and(VO2)2SO4 as a cathode electron carrier to facilitate the electron transfer to air.The reaction rate could be easily controlled by selecting the anode catalyst,adjusting the external loading and changing the cathodic electron carrier or oxidants.A maximal power density of 44.9 mW cm-2 at room temperature was achieved,while for FDCA production,short-circuit condition was preferred to achieve quick transfer of electrons.For a single batch operation with 0.1 M initial HMF,FDCA yield reached 97.1％.By fed-batch operation,FDCA concentration reached 144.5 g L-1 with a total yield of 96％.Ni2+/Ni3+redox couple was the active species mediating the electron transfer,while both experimental and DFT calculation results indicated that HMFCA pathway was the preferred reaction mechanism.
查看更多>>摘要：Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely used to study the reaction mechanism of the hydrogen evolution reaction(HER),but the cal-culation results need to be supported by experimental results and direct evidence to confirm the mech-anistic insights.In this review,we discuss the fundamental principles of the in situ spectroscopic strategy and a theoretical model for a mechanistic understanding of the HER.In addition,we investigate recent studies by in situ Fourier transform infrared(FTIR),Raman spectroscopy,and X-ray absorption spec-troscopy(XAS)and cover new findings that occur at the catalyst-electrolyte interface during HER.These spectroscopic strategies provide practical ways to elucidate catalyst phase,reaction intermediate,catalyst-electrolyte interface,intermediate binding energy,metal valency state,and coordination envi-ronment during HER.
查看更多>>摘要：Sodium-ion batteries(SIBs)and hybrid capacitors(SIHCs)have garnered significant attention in energy storage due to their inherent advantages,including high energy density,cost-effectiveness,and enhanced safety.However,developing high-performance anode materials to improve sodium storage performance still remains a major challenge.Here,a facile one-pot method has been developed to fabricate a hybrid of MoSeTe nanosheets implanted within the N,F co-doped honeycomb carbon skeleton(MoSeTe/N,F@C).Experimental results demonstrate that the incorporation of large-sized Te atoms into MoSeTe nanosheets enlarges the layer spacing and creates abundant anion vacancies,which effectively facilitate the inser-tion/extraction of Na+and provide numerous ion adsorption sites for rapid surface capacitive behavior.Additionally,the heteroatoms N,F co-doped honeycomb carbon skeleton with a highly conductive net-work can restrain the volume expansion and boost reaction kinetics within the electrode.As anticipated,the MoSeTe/N,F@C anode exhibits high reversible capacities along with exceptional cycle stability.When coupled with Na3V2(PO4)3@C(NVPF@C)to form SIB full cells,the anode delivers a reversible specific capacity of 126 mA h g-1 after 100 cycles at 0.1 A g-1.Furthermore,when combined with AC to form SIHC full cells,the anode demonstrates excellent cycling stability with a reversible specific capacity of 50 mA h g-1 keeping over 3700 cycles at 1.0 A g-1.In situ XRD,ex situ TEM characterization,and theo-retical calculations(DFT)further confirm the reversibility of sodium storage in MoSeTe/N,F@C anode materials during electrochemical reactions,highlighting their potential for widespread practical applica-tion.This work provides new insights into the promising utilization of advanced transition metal dichalcogenides as anode materials for Na+-based energy storage devices.
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