The energy density of thin-film lithium batteries(TFLBs)is predominantly determined by the average voltage and specific capacity,however,the mechanism of regulating the voltage plateaus of the film electrodes is not w...The energy density of thin-film lithium batteries(TFLBs)is predominantly determined by the average voltage and specific capacity,however,the mechanism of regulating the voltage plateaus of the film electrodes is not well understood.In this study,three boride films(Co–B,Fe–B,and Co–Fe–B alloys)with different thick-nesses were fabricated to enhance the specific capacity and voltage stability of TFLBs.By analyzing the cycling performance,redox peak evolution,and capacitive contribution,the thickness-dependent lithiation behavior of the thin/thick films was elucidated.Theoretical simulations and electrochemical analysis were conducted to investigate how the lithiation behaviors affected the voltage profiles of the film electrodes.In addition,the various-thickness CoB films were compared in all-solid-state TFLBs,demonstrating the universality and practicability of this simple regulation strategy to develop high-performance energy storage devices.展开更多
With its high theoretical capacity,lithium(Li)metal is recognized as the most potential anode for realizing a high-performance energy storage system.A series of questions(severe safety hazard,low Coulombic efficiency,...With its high theoretical capacity,lithium(Li)metal is recognized as the most potential anode for realizing a high-performance energy storage system.A series of questions(severe safety hazard,low Coulombic efficiency,short lifetime,etc.)induced by uncontrollable dendrites growth,unstable solid electrolyte interface layer,and large volume change,make practical application of Li-metal anodes still a threshold.Due to their highly appealing properties,carbon-based materials as hosts to composite with Li metal have been passionately investigated for improving the performance of Li-metal batteries.This review displays an overview of the critical role of carbon-based hosts for improving the comprehensive performance of Li-metal anodes.Based on correlated mainstream models,the main failure mechanism of Li-metal anodes is introduced.The advantages and strategies of carbon-based hosts to address the corresponding challenges are generalized.The unique function,existing limitation,and recent research progress of key carbon-based host materials for Li-metal anodes are reviewed.Finally,a conclusion and an outlook for future research of carbon-based hosts are presented.This review is dedicated to summarizing the advances of carbon-based materials hosts in recent years and providing a reference for the further development of carbonbased hosts for advanced Li-metal anodes.展开更多
To study the mechanism of formation and inhibition of Ce conversion films on Al 2024-T3 alloy, scanning microreference electrode technique (SMRE) is used to probe the potential map on Al 2024-T3 in CeCl 3 solution, t...To study the mechanism of formation and inhibition of Ce conversion films on Al 2024-T3 alloy, scanning microreference electrode technique (SMRE) is used to probe the potential map on Al 2024-T3 in CeCl 3 solution, the localized corrosion of Al alloy decreases with immersion time and disappears finally, which results from the competition of Cl - aggression and Ce 3+ inhibition on alloy surface. The results of X-ray photoelectron spectroscopy (XPS) indicate that the Ce conversion films consist of Al 2O 3, CeO 2 and Ce 2O 3(Ce(OH) 3), and CeO 2/Ce 2O 3 ratio decreases with the immersion time. When a critical pH for Ce(OH) 3 formation was reached, Ce(OH) 3 will precipitate on the micro cathodic area on alloy surface. Consequently, H 2O 2, the product of the catholic reaction will oxidize a part of Ce(OH) 3 to CeO 2, which appears a better corrosion resistance for Al alloys.展开更多
Lithium cobalt oxide(LCO)is the dominating cathode materials for lithium-ion batteries(LIBs)deployed in consumer electronic devices for its superior volumetric energy density and electrochemical performances.The const...Lithium cobalt oxide(LCO)is the dominating cathode materials for lithium-ion batteries(LIBs)deployed in consumer electronic devices for its superior volumetric energy density and electrochemical performances.The constantly increasing demands of higher energy density urge to develop high-voltage LCO via a variety of strategies.However,the corresponding modification mechanism,especially the influence of the long-and short-range structural transitions at high-voltage on electrochemical performance,is still not well understood and needs further exploration.Based on ss-NMR,in-situ X-ray diffraction,and electrochemical performance results,it is revealed that the H3 to H1-3 phase transition dictates the structural reversibility and stability of LCO,thereby determining the electrochemical performance.The introduction of La and Al ions could postpone the appearance of H1-3 phase and induce various types of local environments to alleviate the volume variation at the atomic level,leading to better reversibility of the H1-3 phase and smaller lattice strain,and significantly improved cycle performance.Such a comprehensive long-range,local,and electronic structure characterization enables an in-depth understanding of the structural evolution of LCO,providing a guiding principle for developing high-voltage LCO for high energy density LIBs.展开更多
The sodium potassium citrato oxotungstate(VI) dimer, Na 4K 2〔W 2O 5\|(cit) 2〕·11H 2O (H 4cit = citric acid) was obtained by the reaction of sodium tungstate(VI) and excess potassium citrate monobasic (KH 3cit) ...The sodium potassium citrato oxotungstate(VI) dimer, Na 4K 2〔W 2O 5\|(cit) 2〕·11H 2O (H 4cit = citric acid) was obtained by the reaction of sodium tungstate(VI) and excess potassium citrate monobasic (KH 3cit) in neutral solution. The crystal data for the title compound: monoclinic, C 12 H 30 K 2Na 4W 2O 30 , M r =1192.21, space group P2 1/n, a=17.427(4), b=10.022(2), c=18.637(3) , β=92.62(1)°, V=3252(2) 3, Z=4, D c =2.435 g/cm 3, μ( Mo Kα )=76.38 cm -1 , F( 000)=2288. The structure was refined to R =0.0434 for 6327 independent observed reflections with I>3σ(I) . The complex anion contains a quasi centrosymmetric (O 2W)O b(WO 2) core with a bent bridging oxo group 〔W-O b-W 175.0(4)°〕. Each citrate as tridentate ligand coordinates to a tungsten atom through the alkoxy, α carboxyl, and one β carboxyl group, while the other β carboxyl group remains uncoordinated. Principal dimensions are: W-O b 1.883(6) , (W=O t)av 1.715(6) , W-O (alkoxy) 1.959(6) , W-O ( α carboxy) 2.176(6) and W-O ( β carboxy) 2.231(6) . The tungsten atom is located in a distorted octahedron environment.展开更多
Precursor decomposition was used for the preparation of VTeO/SBA-15 catalyst for the selective oxidation of propane to acrolein. The catalyst shows a better performance compared with those prepared by conventional imp...Precursor decomposition was used for the preparation of VTeO/SBA-15 catalyst for the selective oxidation of propane to acrolein. The catalyst shows a better performance compared with those prepared by conventional impregnant method. A yield of 9.3% of acrolein was achieved with 2% V loadings at 500 ℃. XRD, N2-adsorption, H2-TPR, Py-IR and XPS measurements were used to unclose the relationship between the structure and performance of the catalyst.展开更多
In situ cross-linking encapsulation has been demonstrated to be an efficient strategy for enhancing the humidity stability of perovskite solar cells(PSCs).In this study,a novel cross-linkable fullerene derivative,name...In situ cross-linking encapsulation has been demonstrated to be an efficient strategy for enhancing the humidity stability of perovskite solar cells(PSCs).In this study,a novel cross-linkable fullerene derivative,namely1-(p-benzoate-(p-methylvinylbenzene)-indolino[2,3][60]fullerene(FPPS),was readily synthesized from commercially available building blocks in two steps.This FPPS was employed as an interfacial modifier on perovskite surfaces in inverted planar p-i-n PSCs.Owing to the fast interfacial charge extraction and efficient trap passivation,PSCs based on the cross-linked FPPS(C-FPPS)exhibited excellent performance.The PSCs had a top-performing power conversion efficiency(PCE)of 17.82%with negligible hysteresis,compared to the control devices without C-PFFS(16.99%).Moreover,the strong water resistance of the C-FPPS interfacial layer distinctly enhances the ambient stability of PSC devices,exhibiting a t80(the time required to reach 80%of the initial PCE)of 300 h under high-humidity conditions.This significantly surpasses the control devices,whose t80 was only 130 h.These results demonstrate that cross-linkable fullerene derivatives can be promising interfacial materials for designing high-efficiency,hysteresis-free,air-stable PSCs.展开更多
MCM 41 molecular sieve supported Rh PPh 3 catalysts were prepared by the in situ assembling of the metal complex from smaller moieties of Rh(acac)(CO) 2 and ligand of PPh 3. The resulted vip/host materials(Rh PPh 3/...MCM 41 molecular sieve supported Rh PPh 3 catalysts were prepared by the in situ assembling of the metal complex from smaller moieties of Rh(acac)(CO) 2 and ligand of PPh 3. The resulted vip/host materials(Rh PPh 3/MCM 41) were characterized by X ray powder diffraction, FTIR and 31 P( 1H) NMR, and served as catalysts for propene hydroformylation. The results showed negligible change in MCM 41 framework after propene hydroformylation at 393 K. Higher hydroformylation activities were obtained on Rh PPh 3/MCM 41 catalysts compared to that on Rh PPh 3/SiO 2.展开更多
The active sites of samarium orthovanadate(SmVO_(4))were studied by means of ESR,NO TPD and temperature programmed ^(18) O_(2) isotope exchange(TPIE)methods.The results of ESR and NO TPD confirm the presence of V ^(4+...The active sites of samarium orthovanadate(SmVO_(4))were studied by means of ESR,NO TPD and temperature programmed ^(18) O_(2) isotope exchange(TPIE)methods.The results of ESR and NO TPD confirm the presence of V ^(4+) in the catalyst.The TPIE revealed that the ^(18)O_(2) isotope exchange was carried out through a single exchange procedure.The V^(4+)species associated with oxygen vacancies are the sites for O_(2) activation.展开更多
Four FeCO states with 3d4s and 3d3d electrons spinpaired or spinunpaired were examined to investigate the influences of pairing versus unpairing mechanisms upon the bonding and interaction in FeCO.The calculation resu...Four FeCO states with 3d4s and 3d3d electrons spinpaired or spinunpaired were examined to investigate the influences of pairing versus unpairing mechanisms upon the bonding and interaction in FeCO.The calculation results show that the FeCO bonding and interaction are determined by a balance between the bonding stabilization and the exchange stabilization with 3d4s electron spinpairing or without it.The 3d3d electron spinpairing versus unpairing has a surprised effect on the FeCO bonding properties even though the 3d orbitals are usually considered as non bonding ones.展开更多
Silver nanoparticles with average diameter of 10 ± 3 nm were synthesized within the sieves of poly（N-isopropylacrylamide-2-hydroxyethylmethacrylate-acrylic acid）（p（NIPAAm-HEMA-AAc））polymer microgels. Free r...Silver nanoparticles with average diameter of 10 ± 3 nm were synthesized within the sieves of poly（N-isopropylacrylamide-2-hydroxyethylmethacrylate-acrylic acid）（p（NIPAAm-HEMA-AAc））polymer microgels. Free radial emulsion polymerization was employed for synthesis of p（NIPAAm-HEMA-AAc） polymer microgels. Silver nanoparticles were introduced within the microgels sphere by in situ reduction method. Microgels and hybrid microgels were characterized by Fourier transform infrared spectroscopy, ultra violet-visible spectroscopy,transmission electron microscopy and dynamic light scattering measurements. Catalytic activity of Ag-p（NIPAAm-HEMA-AAc） hybrid microgels was studied using catalytic reduction of 4-nitrophenol（4-NP） as a model reaction in aqueous media. The influence of sodium borohydride（Na BH4） concentration, catalyst dose and 4-NP concentration on catalytic reduction of 4-NP was investigated. A linear relationship was found between catalyst dose and apparent rate constant（kapp）. The mechanism of catalysis by hybrid microgels was explored for further development in this area. The deep analysis of catalytic process reveals that the unique combination of NIPAAm, HEMA and AAc does not only stabilize silver nanoparticles in polymer network but it also enhances the mass transport of hydrophilic substrate like 4-NP from outside to inside the polymer network.展开更多
The electronic structure of the perovskite LaCoO3 at room temperature structure （293 K） was calculated by using PBE, PBE＋U and HSE. Different spin configurations have been considered. Our calculations showed that t...The electronic structure of the perovskite LaCoO3 at room temperature structure （293 K） was calculated by using PBE, PBE＋U and HSE. Different spin configurations have been considered. Our calculations showed that the choice of the Hubbard U parameter in DFT＋U and mixing factor α in HSE significantly influenced the band gap as well as relative energies. For the spin exited states, the optimal value for U and α were 3.0 eV and 0.05, respectively. Our calculation also emphasized that when U〉5.0 eV, PBE＋U would lead to unreasonable electronic structure and energy order.展开更多
The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd‑based catalysts that were co‑modified with organic and inorganic ligands.It was demonstrated that the catalysts c...The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd‑based catalysts that were co‑modified with organic and inorganic ligands.It was demonstrated that the catalysts contained Pd species in mixed valence states,with high valence Pd at the metal‑support interface and zero valence Pd at the metal surface.While the strong coordination of triphenylphosphine(PPh3)to Pd0 on the Pd surface prevents the adsorption of halogenated nitroaromatics and thus dehalogenation,the coordination of sodium metavanadate(NaVO3)to high‑valence Pd sites at the interface helps to activate H2 in a heterolytic pathway for the selective hydrogenation of nitro‑groups.The excellent catalytic performance of the interfacial active sites enables the selective hydrogenation of a wide range of halogenated nitroaromatics.展开更多
Anion exchange membrane fuel cells(AEMFCs)are considered a more affordable technology compared to proton exchange membrane fuel cells(PEMFCs),but the performance and durability of AEMFCs are still not competent with P...Anion exchange membrane fuel cells(AEMFCs)are considered a more affordable technology compared to proton exchange membrane fuel cells(PEMFCs),but the performance and durability of AEMFCs are still not competent with PEMFCs owing to the more challenging water management,which severely hinders its development and real-life applications.In this study,we introduce the strategy to boost the performance and stability of the membrane electrode assembly(MEA)of AEMFCs by regulating the hydrophilicity of the anode and cathode ionomers.Two poly(biphenyl alkylene)ionomers with different hydrophilicity are synthesized and used to fabricate MEAs with asymmetric or symmetric ionomer configurations in the anodic and cathodic catalyst layers(CLs)for AEMFCs.Molecular dynamics(MD)simulations have revealed different diffusion rates of water in the hydrophobic anode and the hydrophilic cathode,which show the potential of this design to improve water management in AEMFCs,The effectiveness of this design is also confirmed by experimental results that the MEA with this asymmetric configuration exhibits the highest power and current densities of 1.58 W cm^(-2)or 5.58 A cm^(-2),respectively,among all configurations.Furthermore,this configuration also enhances the durability,with the MEA showing a voltage decay rate of only 313.1μV h^(-1)after 500 h of in-situ durability test at 0.2 A cm^(-2).This study provides new insights into the rational design of more efficient water management in MEA for high-performance AEMFCs.展开更多
The controlled incorporation of heptagons into helicene frameworks offers a promising approach to modulate their structural and electronic properties.This study demonstrates the synthesis of two heptagonembedded oxa-h...The controlled incorporation of heptagons into helicene frameworks offers a promising approach to modulate their structural and electronic properties.This study demonstrates the synthesis of two heptagonembedded oxa-helicenes:one with a single heptagon(5)and another with two heptagons(6),achieved through controlled oxidative cyclization of a triple oxa-helicene(4).UV-vis absorption and emission spectra revealed red-shifts and slight increases in Stokes shifts from 4 to 6,attributed toπ-system extension and greater structural relaxation in the excited state.5 and 6 exhibited fluorescence quantum yields 2-3times higher than 4.Chiral separation and thermal stability analyses showed a significant decrease in enantiomeric stability for 5 and 6 compared to 4,due to planarization effects induced by heptagon incorporation.The chiroptical properties were also investigated,revealing reduced optical dissymmetry factors after heptagon embedding.展开更多
Degradation of materials is one of the most critical aging mechanisms affecting the performance of lithium batteries.Among the various approaches to investigate battery aging,phase-field modelling(PFM)has emerged as a...Degradation of materials is one of the most critical aging mechanisms affecting the performance of lithium batteries.Among the various approaches to investigate battery aging,phase-field modelling(PFM)has emerged as a widely used numerical method for simulating the evolution of the phase interface as a function of space and time during material phase transition process.Moreover,PFM coupled with multi-physics analyses is particularly well-suited for investigating the mesoscale microstructural evolution of materials,providing quantitative understandings of aging and failure mechanisms in lithium batteries.In this paper,we comprehensively overview the state-of-art applications of PFM in the research of degradation and failure processes in lithium batteries,particularly focusing on the theoretical framework and development of the PFMs for lithium deposition/dissolution,phase separation,and crack propagation.Furthermore,we summarize the existing challenges and prospect some future developments in PFMs,aiming to offer new insights into the advancement of PFM and ultimately enhance the development of lithium batteries.展开更多
In fulfillment of the national science-and-technology development agenda, the Department of Chemical Sciences of the National Natural Science Foundation of China (NSFC) convened the Strategic Symposium on the Fifteent...In fulfillment of the national science-and-technology development agenda, the Department of Chemical Sciences of the National Natural Science Foundation of China (NSFC) convened the Strategic Symposium on the Fifteenth FiveYear (20262030) Development Plan for Electrochemistry held in Xiamen on 29 August, 2025-the culminating year of the Fourteenth Five-Year (2021-2025) Development Plan. More than forty leading experts in the field of electrochemistry participated with spanning nine thematic fronts: Interfacial Electrocatalysis, Interfacial Electrochemistry for Energy Storage, Bioelectrochemistry, Electrochemistry of Hydrogen Energy, Electrochemical Micro-/Nano-Manufacturing, Operando Electrochemical Characterization, Electro-Thermal Coupling Catalysis, Theoretical and Computational Electrochemistry,and Electrochemical Synthesis. The forum assembled China's foremost electrochemical expertise to blueprint high-quality disciplinary growth for the coming five-year period, thereby serving overarching national strategic needs and sharpening the international competitiveness of Chinese electrochemistry.This paper is presented to highlight the strategic needs and priority areas for the next five years (2026-2030) based on this symposium. The development status of basic research and applied basic research in China's electrochemistry field is systematically reviewed. The in-depth analyses of the existing problems and key challenges in the research and development of electrochemistry related fields are outlined, and the frontier research areas and development trends in the next 5-10 years by integrating national major strategic needs are discussed, which will further promote the academic community to reach a clearer consensus. The proposed strategic roadmap is intended to accelerate a sharpened community consensus, propel the discipline toward high-quality advancement, and furnish a critical reference for building China into a world-leading science and technology power.展开更多
Ethyl-(2,2,2-trifluoroethyl)carbonate(ETFEC)is investigated as a solvent component in high-voltage electrolytes for LiNi0.5Mn1.5O4(LNMO).Our results show that the self-discharge behavior and the high temperature cycle...Ethyl-(2,2,2-trifluoroethyl)carbonate(ETFEC)is investigated as a solvent component in high-voltage electrolytes for LiNi0.5Mn1.5O4(LNMO).Our results show that the self-discharge behavior and the high temperature cycle performance can be significantly improved by the addition of 10%ETFEC into the normal carbonate electrolytes,e.g.,the capacity retention improved from 65.3%to 77.1%after 200 cycles at 60℃.The main reason can be ascribed to the high stability of ETFEC which prevents large oxidation of the electrolyte on the cathode surface.In addition,we also explore the feasibility of electrolytes using single fluoriated-solvents with and without additives.Our results show that the cycle performance of LNMO material can be greatly improved in 1 MLiPF6+pure ETFEC-solvent system with 2 wt%ethylene carbonate(EC)or ethylene sulfate(DTD).The capacity retention of the LNMO materials is 93%after 300 cycles,even better than that of carbonate-based electrolytes.It is shown that the additives are oxidized on the surface of LNMO particles and contribute to the formation of cathode/electrolyte interphase(CEI)films.This composite CEI film plays a crucial role in suppressing the serious decomposition of the electrolyte at high voltage.展开更多
Lithium(Li) metal is considered as the most promising anode material for the next-generation high performance Li batteries.However,the uncontrollable dendritic growth impedes its commercial application.Herein,we desig...Lithium(Li) metal is considered as the most promising anode material for the next-generation high performance Li batteries.However,the uncontrollable dendritic growth impedes its commercial application.Herein,we design a 3 D Si@carbon nanofibers(CNFs)@ZnO-ZnO-Cu skeleton(SCZ) for guiding the homogeneous bottom-growth of Li metal.The top LixSi@CNFs and bottom LiyZn@CNFs layers could form conductivity and overpotential gradient to avoid the "top-growth" of Li metal.Moreover,the top lithiophilic LixSi@CNFs layer could regulate the nucleation and deposition of Li-ions even if the lithium dendrites grow out of the skeleton under high capacity Li deposition(30 mAh cm^(-2)).As a result,the SCZ-Li||LiFePO_(4) full cell delivers a high capacity of ~104 mAh g^(-1)(~94.82% capacity retention) after 2000 cycles at 5 C, elucidating the potential application of the 3 D double-gradient Li metal composite anode.展开更多
基金supported by National Natural Science Foundation of China(Grant Nos.52101273 and U22A20118)Natural Science Foundation of Fujian Province of China(Grant No.2022J01042)Fundamental Research Funds for Central Universities of China(Grant No.20720242002).
文摘The energy density of thin-film lithium batteries(TFLBs)is predominantly determined by the average voltage and specific capacity,however,the mechanism of regulating the voltage plateaus of the film electrodes is not well understood.In this study,three boride films(Co–B,Fe–B,and Co–Fe–B alloys)with different thick-nesses were fabricated to enhance the specific capacity and voltage stability of TFLBs.By analyzing the cycling performance,redox peak evolution,and capacitive contribution,the thickness-dependent lithiation behavior of the thin/thick films was elucidated.Theoretical simulations and electrochemical analysis were conducted to investigate how the lithiation behaviors affected the voltage profiles of the film electrodes.In addition,the various-thickness CoB films were compared in all-solid-state TFLBs,demonstrating the universality and practicability of this simple regulation strategy to develop high-performance energy storage devices.
基金The author sincerely thanks the financial supports from the National Natural Science Foundation of China(Grant Nos.51871188,51701169,and 51931006)National Key R&D Program of China(Grant No.2016YFA0202602)+1 种基金the Natural Science Foundation of Fujian Province of China(Grant No.2019J06003)the“Double‐First Class”Foundation of Materials and Intelligent Manufacturing Discipline of Xiamen University.
文摘With its high theoretical capacity,lithium(Li)metal is recognized as the most potential anode for realizing a high-performance energy storage system.A series of questions(severe safety hazard,low Coulombic efficiency,short lifetime,etc.)induced by uncontrollable dendrites growth,unstable solid electrolyte interface layer,and large volume change,make practical application of Li-metal anodes still a threshold.Due to their highly appealing properties,carbon-based materials as hosts to composite with Li metal have been passionately investigated for improving the performance of Li-metal batteries.This review displays an overview of the critical role of carbon-based hosts for improving the comprehensive performance of Li-metal anodes.Based on correlated mainstream models,the main failure mechanism of Li-metal anodes is introduced.The advantages and strategies of carbon-based hosts to address the corresponding challenges are generalized.The unique function,existing limitation,and recent research progress of key carbon-based host materials for Li-metal anodes are reviewed.Finally,a conclusion and an outlook for future research of carbon-based hosts are presented.This review is dedicated to summarizing the advances of carbon-based materials hosts in recent years and providing a reference for the further development of carbonbased hosts for advanced Li-metal anodes.
文摘To study the mechanism of formation and inhibition of Ce conversion films on Al 2024-T3 alloy, scanning microreference electrode technique (SMRE) is used to probe the potential map on Al 2024-T3 in CeCl 3 solution, the localized corrosion of Al alloy decreases with immersion time and disappears finally, which results from the competition of Cl - aggression and Ce 3+ inhibition on alloy surface. The results of X-ray photoelectron spectroscopy (XPS) indicate that the Ce conversion films consist of Al 2O 3, CeO 2 and Ce 2O 3(Ce(OH) 3), and CeO 2/Ce 2O 3 ratio decreases with the immersion time. When a critical pH for Ce(OH) 3 formation was reached, Ce(OH) 3 will precipitate on the micro cathodic area on alloy surface. Consequently, H 2O 2, the product of the catholic reaction will oxidize a part of Ce(OH) 3 to CeO 2, which appears a better corrosion resistance for Al alloys.
基金funded by the National Natural Science Foundation of China(grant no.21761132030,21935009)National Key Research and Development Program of China(grant no.2016YFB0901502,2018YFB0905400)Collaboration project between Ningde City&Xiamen University(2017c002)。
文摘Lithium cobalt oxide(LCO)is the dominating cathode materials for lithium-ion batteries(LIBs)deployed in consumer electronic devices for its superior volumetric energy density and electrochemical performances.The constantly increasing demands of higher energy density urge to develop high-voltage LCO via a variety of strategies.However,the corresponding modification mechanism,especially the influence of the long-and short-range structural transitions at high-voltage on electrochemical performance,is still not well understood and needs further exploration.Based on ss-NMR,in-situ X-ray diffraction,and electrochemical performance results,it is revealed that the H3 to H1-3 phase transition dictates the structural reversibility and stability of LCO,thereby determining the electrochemical performance.The introduction of La and Al ions could postpone the appearance of H1-3 phase and induce various types of local environments to alleviate the volume variation at the atomic level,leading to better reversibility of the H1-3 phase and smaller lattice strain,and significantly improved cycle performance.Such a comprehensive long-range,local,and electronic structure characterization enables an in-depth understanding of the structural evolution of LCO,providing a guiding principle for developing high-voltage LCO for high energy density LIBs.
文摘The sodium potassium citrato oxotungstate(VI) dimer, Na 4K 2〔W 2O 5\|(cit) 2〕·11H 2O (H 4cit = citric acid) was obtained by the reaction of sodium tungstate(VI) and excess potassium citrate monobasic (KH 3cit) in neutral solution. The crystal data for the title compound: monoclinic, C 12 H 30 K 2Na 4W 2O 30 , M r =1192.21, space group P2 1/n, a=17.427(4), b=10.022(2), c=18.637(3) , β=92.62(1)°, V=3252(2) 3, Z=4, D c =2.435 g/cm 3, μ( Mo Kα )=76.38 cm -1 , F( 000)=2288. The structure was refined to R =0.0434 for 6327 independent observed reflections with I>3σ(I) . The complex anion contains a quasi centrosymmetric (O 2W)O b(WO 2) core with a bent bridging oxo group 〔W-O b-W 175.0(4)°〕. Each citrate as tridentate ligand coordinates to a tungsten atom through the alkoxy, α carboxyl, and one β carboxyl group, while the other β carboxyl group remains uncoordinated. Principal dimensions are: W-O b 1.883(6) , (W=O t)av 1.715(6) , W-O (alkoxy) 1.959(6) , W-O ( α carboxy) 2.176(6) and W-O ( β carboxy) 2.231(6) . The tungsten atom is located in a distorted octahedron environment.
基金Supported by the Ministry of Science and Technology of China(No. 2005CB221408)the National Natural Science Founda-tion of China(Nos. 20423002, 20571061)Key Scientific Project of Fujian Province, China(No. 2005HZ01-3)
文摘Precursor decomposition was used for the preparation of VTeO/SBA-15 catalyst for the selective oxidation of propane to acrolein. The catalyst shows a better performance compared with those prepared by conventional impregnant method. A yield of 9.3% of acrolein was achieved with 2% V loadings at 500 ℃. XRD, N2-adsorption, H2-TPR, Py-IR and XPS measurements were used to unclose the relationship between the structure and performance of the catalyst.
基金the National Natural Science Foundation of China(Nos.21721001,51572231 and 51502252)the Natural Science Foundation of Fujian Province of China(No.2016J01264)。
文摘In situ cross-linking encapsulation has been demonstrated to be an efficient strategy for enhancing the humidity stability of perovskite solar cells(PSCs).In this study,a novel cross-linkable fullerene derivative,namely1-(p-benzoate-(p-methylvinylbenzene)-indolino[2,3][60]fullerene(FPPS),was readily synthesized from commercially available building blocks in two steps.This FPPS was employed as an interfacial modifier on perovskite surfaces in inverted planar p-i-n PSCs.Owing to the fast interfacial charge extraction and efficient trap passivation,PSCs based on the cross-linked FPPS(C-FPPS)exhibited excellent performance.The PSCs had a top-performing power conversion efficiency(PCE)of 17.82%with negligible hysteresis,compared to the control devices without C-PFFS(16.99%).Moreover,the strong water resistance of the C-FPPS interfacial layer distinctly enhances the ambient stability of PSC devices,exhibiting a t80(the time required to reach 80%of the initial PCE)of 300 h under high-humidity conditions.This significantly surpasses the control devices,whose t80 was only 130 h.These results demonstrate that cross-linkable fullerene derivatives can be promising interfacial materials for designing high-efficiency,hysteresis-free,air-stable PSCs.
基金Supported by the National Natural Science Foundation of China(Nos.2 98730 372 0 0 2 30 0 1and2 0 0 2 10 0 2 ) State KeyProject for Fundamental Research(No.G2 0 0 0 0 4 80 8) and the Ministry of Education of China
文摘MCM 41 molecular sieve supported Rh PPh 3 catalysts were prepared by the in situ assembling of the metal complex from smaller moieties of Rh(acac)(CO) 2 and ligand of PPh 3. The resulted vip/host materials(Rh PPh 3/MCM 41) were characterized by X ray powder diffraction, FTIR and 31 P( 1H) NMR, and served as catalysts for propene hydroformylation. The results showed negligible change in MCM 41 framework after propene hydroformylation at 393 K. Higher hydroformylation activities were obtained on Rh PPh 3/MCM 41 catalysts compared to that on Rh PPh 3/SiO 2.
文摘The active sites of samarium orthovanadate(SmVO_(4))were studied by means of ESR,NO TPD and temperature programmed ^(18) O_(2) isotope exchange(TPIE)methods.The results of ESR and NO TPD confirm the presence of V ^(4+) in the catalyst.The TPIE revealed that the ^(18)O_(2) isotope exchange was carried out through a single exchange procedure.The V^(4+)species associated with oxygen vacancies are the sites for O_(2) activation.
文摘Four FeCO states with 3d4s and 3d3d electrons spinpaired or spinunpaired were examined to investigate the influences of pairing versus unpairing mechanisms upon the bonding and interaction in FeCO.The calculation results show that the FeCO bonding and interaction are determined by a balance between the bonding stabilization and the exchange stabilization with 3d4s electron spinpairing or without it.The 3d3d electron spinpairing versus unpairing has a surprised effect on the FeCO bonding properties even though the 3d orbitals are usually considered as non bonding ones.
基金financial support for research from Higher Education Commission Pakistan under National Research Program for Universities(NRPU)(No.20-3995/WRPU/R&D/HEC/14/1212)Research Centre for Advanced Materials Science - King Khalid University, Saudi Arabia for support
文摘Silver nanoparticles with average diameter of 10 ± 3 nm were synthesized within the sieves of poly（N-isopropylacrylamide-2-hydroxyethylmethacrylate-acrylic acid）（p（NIPAAm-HEMA-AAc））polymer microgels. Free radial emulsion polymerization was employed for synthesis of p（NIPAAm-HEMA-AAc） polymer microgels. Silver nanoparticles were introduced within the microgels sphere by in situ reduction method. Microgels and hybrid microgels were characterized by Fourier transform infrared spectroscopy, ultra violet-visible spectroscopy,transmission electron microscopy and dynamic light scattering measurements. Catalytic activity of Ag-p（NIPAAm-HEMA-AAc） hybrid microgels was studied using catalytic reduction of 4-nitrophenol（4-NP） as a model reaction in aqueous media. The influence of sodium borohydride（Na BH4） concentration, catalyst dose and 4-NP concentration on catalytic reduction of 4-NP was investigated. A linear relationship was found between catalyst dose and apparent rate constant（kapp）. The mechanism of catalysis by hybrid microgels was explored for further development in this area. The deep analysis of catalytic process reveals that the unique combination of NIPAAm, HEMA and AAc does not only stabilize silver nanoparticles in polymer network but it also enhances the mass transport of hydrophilic substrate like 4-NP from outside to inside the polymer network.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.21033006, No.21133004, and No.21373167） and the Ministry of Science and Technology （No.2010CB732303）.
文摘The electronic structure of the perovskite LaCoO3 at room temperature structure （293 K） was calculated by using PBE, PBE＋U and HSE. Different spin configurations have been considered. Our calculations showed that the choice of the Hubbard U parameter in DFT＋U and mixing factor α in HSE significantly influenced the band gap as well as relative energies. For the spin exited states, the optimal value for U and α were 3.0 eV and 0.05, respectively. Our calculation also emphasized that when U〉5.0 eV, PBE＋U would lead to unreasonable electronic structure and energy order.
文摘The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd‑based catalysts that were co‑modified with organic and inorganic ligands.It was demonstrated that the catalysts contained Pd species in mixed valence states,with high valence Pd at the metal‑support interface and zero valence Pd at the metal surface.While the strong coordination of triphenylphosphine(PPh3)to Pd0 on the Pd surface prevents the adsorption of halogenated nitroaromatics and thus dehalogenation,the coordination of sodium metavanadate(NaVO3)to high‑valence Pd sites at the interface helps to activate H2 in a heterolytic pathway for the selective hydrogenation of nitro‑groups.The excellent catalytic performance of the interfacial active sites enables the selective hydrogenation of a wide range of halogenated nitroaromatics.
基金supported by the National Key R&D Program of China(No.2023YFB4004700)。
文摘Anion exchange membrane fuel cells(AEMFCs)are considered a more affordable technology compared to proton exchange membrane fuel cells(PEMFCs),but the performance and durability of AEMFCs are still not competent with PEMFCs owing to the more challenging water management,which severely hinders its development and real-life applications.In this study,we introduce the strategy to boost the performance and stability of the membrane electrode assembly(MEA)of AEMFCs by regulating the hydrophilicity of the anode and cathode ionomers.Two poly(biphenyl alkylene)ionomers with different hydrophilicity are synthesized and used to fabricate MEAs with asymmetric or symmetric ionomer configurations in the anodic and cathodic catalyst layers(CLs)for AEMFCs.Molecular dynamics(MD)simulations have revealed different diffusion rates of water in the hydrophobic anode and the hydrophilic cathode,which show the potential of this design to improve water management in AEMFCs,The effectiveness of this design is also confirmed by experimental results that the MEA with this asymmetric configuration exhibits the highest power and current densities of 1.58 W cm^(-2)or 5.58 A cm^(-2),respectively,among all configurations.Furthermore,this configuration also enhances the durability,with the MEA showing a voltage decay rate of only 313.1μV h^(-1)after 500 h of in-situ durability test at 0.2 A cm^(-2).This study provides new insights into the rational design of more efficient water management in MEA for high-performance AEMFCs.
基金financially supported by the Ministry of Science and Technology of China(No.2017YFA0204902)the National Natural Science Foundation of China(Nos.21901217,22101241)。
文摘The controlled incorporation of heptagons into helicene frameworks offers a promising approach to modulate their structural and electronic properties.This study demonstrates the synthesis of two heptagonembedded oxa-helicenes:one with a single heptagon(5)and another with two heptagons(6),achieved through controlled oxidative cyclization of a triple oxa-helicene(4).UV-vis absorption and emission spectra revealed red-shifts and slight increases in Stokes shifts from 4 to 6,attributed toπ-system extension and greater structural relaxation in the excited state.5 and 6 exhibited fluorescence quantum yields 2-3times higher than 4.Chiral separation and thermal stability analyses showed a significant decrease in enantiomeric stability for 5 and 6 compared to 4,due to planarization effects induced by heptagon incorporation.The chiroptical properties were also investigated,revealing reduced optical dissymmetry factors after heptagon embedding.
基金financially supported by the National Key R&D Program of China(2021YFB2401800)。
文摘Degradation of materials is one of the most critical aging mechanisms affecting the performance of lithium batteries.Among the various approaches to investigate battery aging,phase-field modelling(PFM)has emerged as a widely used numerical method for simulating the evolution of the phase interface as a function of space and time during material phase transition process.Moreover,PFM coupled with multi-physics analyses is particularly well-suited for investigating the mesoscale microstructural evolution of materials,providing quantitative understandings of aging and failure mechanisms in lithium batteries.In this paper,we comprehensively overview the state-of-art applications of PFM in the research of degradation and failure processes in lithium batteries,particularly focusing on the theoretical framework and development of the PFMs for lithium deposition/dissolution,phase separation,and crack propagation.Furthermore,we summarize the existing challenges and prospect some future developments in PFMs,aiming to offer new insights into the advancement of PFM and ultimately enhance the development of lithium batteries.
文摘In fulfillment of the national science-and-technology development agenda, the Department of Chemical Sciences of the National Natural Science Foundation of China (NSFC) convened the Strategic Symposium on the Fifteenth FiveYear (20262030) Development Plan for Electrochemistry held in Xiamen on 29 August, 2025-the culminating year of the Fourteenth Five-Year (2021-2025) Development Plan. More than forty leading experts in the field of electrochemistry participated with spanning nine thematic fronts: Interfacial Electrocatalysis, Interfacial Electrochemistry for Energy Storage, Bioelectrochemistry, Electrochemistry of Hydrogen Energy, Electrochemical Micro-/Nano-Manufacturing, Operando Electrochemical Characterization, Electro-Thermal Coupling Catalysis, Theoretical and Computational Electrochemistry,and Electrochemical Synthesis. The forum assembled China's foremost electrochemical expertise to blueprint high-quality disciplinary growth for the coming five-year period, thereby serving overarching national strategic needs and sharpening the international competitiveness of Chinese electrochemistry.This paper is presented to highlight the strategic needs and priority areas for the next five years (2026-2030) based on this symposium. The development status of basic research and applied basic research in China's electrochemistry field is systematically reviewed. The in-depth analyses of the existing problems and key challenges in the research and development of electrochemistry related fields are outlined, and the frontier research areas and development trends in the next 5-10 years by integrating national major strategic needs are discussed, which will further promote the academic community to reach a clearer consensus. The proposed strategic roadmap is intended to accelerate a sharpened community consensus, propel the discipline toward high-quality advancement, and furnish a critical reference for building China into a world-leading science and technology power.
基金financially supported by National Key Research and Development Program of China(Grant no.2018YFB010440)the National Natural Science Foundation of China(Grant nos.21761132030,21621091).
文摘Ethyl-(2,2,2-trifluoroethyl)carbonate(ETFEC)is investigated as a solvent component in high-voltage electrolytes for LiNi0.5Mn1.5O4(LNMO).Our results show that the self-discharge behavior and the high temperature cycle performance can be significantly improved by the addition of 10%ETFEC into the normal carbonate electrolytes,e.g.,the capacity retention improved from 65.3%to 77.1%after 200 cycles at 60℃.The main reason can be ascribed to the high stability of ETFEC which prevents large oxidation of the electrolyte on the cathode surface.In addition,we also explore the feasibility of electrolytes using single fluoriated-solvents with and without additives.Our results show that the cycle performance of LNMO material can be greatly improved in 1 MLiPF6+pure ETFEC-solvent system with 2 wt%ethylene carbonate(EC)or ethylene sulfate(DTD).The capacity retention of the LNMO materials is 93%after 300 cycles,even better than that of carbonate-based electrolytes.It is shown that the additives are oxidized on the surface of LNMO particles and contribute to the formation of cathode/electrolyte interphase(CEI)films.This composite CEI film plays a crucial role in suppressing the serious decomposition of the electrolyte at high voltage.
基金financial support from the National Natural Science Foundation of China(Grant Nos.51701169,51871188 and 51931006)the National Key R&D Program of China(Grant No.2016YFA0202602)+1 种基金the Natural Science Foundation of Fujian Province of China(No.2019J06003)the "Double-First Class" Foundation of Materials and Intelligent Manufacturing Discipline of Xiamen University。
文摘Lithium(Li) metal is considered as the most promising anode material for the next-generation high performance Li batteries.However,the uncontrollable dendritic growth impedes its commercial application.Herein,we design a 3 D Si@carbon nanofibers(CNFs)@ZnO-ZnO-Cu skeleton(SCZ) for guiding the homogeneous bottom-growth of Li metal.The top LixSi@CNFs and bottom LiyZn@CNFs layers could form conductivity and overpotential gradient to avoid the "top-growth" of Li metal.Moreover,the top lithiophilic LixSi@CNFs layer could regulate the nucleation and deposition of Li-ions even if the lithium dendrites grow out of the skeleton under high capacity Li deposition(30 mAh cm^(-2)).As a result,the SCZ-Li||LiFePO_(4) full cell delivers a high capacity of ~104 mAh g^(-1)(~94.82% capacity retention) after 2000 cycles at 5 C, elucidating the potential application of the 3 D double-gradient Li metal composite anode.
