By employing metal oxides as oxygen carriers,chemical looping demonstrates its effectiveness in transferring oxygen between reduction and oxidation environments to partially oxidize fuels into syngas and convert CO_(2...By employing metal oxides as oxygen carriers,chemical looping demonstrates its effectiveness in transferring oxygen between reduction and oxidation environments to partially oxidize fuels into syngas and convert CO_(2) into CO.Generally,NiFe_(2_)O_(4) oxygen carriers have demonstrated remarkable efficiency in chemical looping CO_(2) conversion.Nevertheless,the intricate process of atomic migration and evolution within the internal structure of bimetallic oxygen carriers during continuous high‐temperature redox cycling remains unclear.Consequently,the lack of a fundamental understanding of the complex ionic migration and oxygen transfer associated with energy conversion processes hampers the design of high‐performance oxygen carriers.Thus,in this study,we employed in situ characterization techniques and theoretical calculations to investigate the ion migration behavior and structural evolution in the bulk of NiFe_(2_)O_(4) oxygen carriers during H_(2) reduction and CO_(2)/lab air oxidation cycles.We discovered that during the H_(2) reduction step,lattice oxygen rapidly migrates to vacancy layers to replenish consumed active oxygen species,while Ni leaches from the material and migrates to the surface.During the CO_(2) splitting step,Ni migrates toward the core of the bimetallic oxygen carrier,forming Fe–Ni alloys.During the air oxidation step,Fe–Ni migrates outward,creating a hollow structure owing to the Kirkendall effect triggered by the swift transfer of lattice oxygen.The metal atom migration paths depend on the oxygen transfer rates.These discoveries highlight the significance of regulating the release–recovery rate of lattice oxygen to uphold the structures and reactivity of oxygen carriers.This work offers a comprehensive understanding of the oxidation/reduction‐driven atomic interdiffusion behavior of bimetallic oxygen carriers.展开更多
Due to ever-increasing concerns about safety issues in using Li ionic batteries,solid electrolytes have extensively explored.The Li-rich antiperovskite Li_(3)OBr has been considered as a promising solid electrolyte ca...Due to ever-increasing concerns about safety issues in using Li ionic batteries,solid electrolytes have extensively explored.The Li-rich antiperovskite Li_(3)OBr has been considered as a promising solid electrolyte candidate,but it still suffers challenges to achieve a high ionic conductivity owing to the high intrinsic symmetry of the crystal lattice.Herein,we presented a design strategy that introduces various point defects and grain boundaries to break the high lattice symmetry of Li_(3)OBr crystal,and their effect and microscopic mechanism of promoting the migration of Li-ion were explored theoretically.It has been found that Li_(i)are the dominant defects responsible for the fast Li-ion diffusion in bulk Li_(3)OBr and its surface,but they are easily trapped by the grain boundaries,leading to the annihilating of the Frenkel defect pair V'_(Li)+Li_(i),and thus limits the V'_(Li)diffusion at the grain boundaries.The V_(Br)defect near the grain boundaries can effectively drive V'_(Li)across the grain boundary,thereby converting the carrier of Li^(+)migration from Li,in the bulk and surface to V'_(Li)at the grain boundary,and thus improving the ionic conductivity in the whole Li_(3)OBr crystal.This work provides a comprehensive insight into the Li^(+)transport and conduction mechanism in the Li_(3)OBr electrolyte.It opens a new way of improving the conductivity for all-solid-state Li electrolyte material through the defect design.展开更多
Solid polymer electrolytes have been considered as the promising candidates to improve the safety and stability of high-energy lithium metal batteries.However,the practical applications of solid polymer electrolytes a...Solid polymer electrolytes have been considered as the promising candidates to improve the safety and stability of high-energy lithium metal batteries.However,the practical applications of solid polymer electrolytes are still limited by the low ionic conductivity,poor interfacial contact with electrodes,narrow electrochemical window and weak mechanical strength.Here,a series of novel block copolymer electrolytes with three-dimensional networks are designed by cross-linked copolymerization of the polyethylene glycol soft segments and hexamethylene diisocyanate trimer hard segments.Their ionic migration performances and interface compatibilities with Li metal anode have been optimized delicately by tailoring the ratio of these functional units.The optimized block copolymer electrolyte has shown an amorphous crystalline structure,a high ionic conductivity of ~5.7×10^(-4)S cm^(-1),high lithium ion transference number(~0.49),wide electrochemical window up to ~4.65 V(vs.Li+/Li) and favorable mechanical strength at 55℃.Furthermore,the enhanced interface compatibility can well support the normal operations of lithium metal batteries using both LiFePO4 and LiNi0.8Co0.15Al0.05O2 cathodes.This study not only paves a new way to develop solid polymer electrolyte with optimizing functional units,but also provides a polymer electrolyte design strategy for the application demand of lithium metal battery.展开更多
In this study, neutral salt spray accelerated corrosion test of copper–aluminium composite under 0–125 A DC current was carried out under 5% concentration. The effect of corrosion behaviour on copper–aluminium comp...In this study, neutral salt spray accelerated corrosion test of copper–aluminium composite under 0–125 A DC current was carried out under 5% concentration. The effect of corrosion behaviour on copper–aluminium composite by DC current was carried out by a scanning electron microscope(SEM) with energy-dispersive spectroscopy(EDS), X-ray diffraction(XRD) patterns, X-ray photoelectron spectroscopy(XPS), weight-loss method and electrochemical analysis. The results show that the current can accelerate the corrosion rate. Meanwhile, the current temperature effect can reduce the corrosion rate. The current caused directional migration of ions resulting in different corrosion products on positive and negative poles of specimen, and the corrosion degree on the positive pole was more serious. The galvanic corrosion mechanism at the copper–aluminium interface is different from the pitting corrosion mechanism far away from the interface, and the latter is more affected by DC current.展开更多
Two-dimensional(2D) alternating cation(ACI) perovskite surface defects,especially dominant iodine vacancies(V_Ⅰ) and undercoordinated Pb^(2+),limit the performance of perovskite solar cells(PVSCs).To address the issu...Two-dimensional(2D) alternating cation(ACI) perovskite surface defects,especially dominant iodine vacancies(V_Ⅰ) and undercoordinated Pb^(2+),limit the performance of perovskite solar cells(PVSCs).To address the issue,1-butyl-3-methylimidazolium trifluoro-methane-sulfonate(BMIMOTF) and its iodide counterpart(BMIMI) are utilized to modify the perovskite surface respectively.We find that BMIMI can change the perovskite surface,whereas BMIMOTF shows a nondestructive and more effective defect passivation,giving significantly reduced defect density and suppressed charge-carrier nonradiative recombination.This mainly attributes to the marked passivation efficacy of OTF-anion on V_Ⅰ and undercoordinated Pb^(2+),rather than BMIMI^(+) cation.Benefiting from the rational surface-modification of BMMIMOTF,the films exhibit an optimized energy level alignment,enhanced hydrophobicity and suppressed ion migration.Consequently,the BMIMOTF-modified devices achieve an impressive efficiency of 21.38% with a record open-circuit voltage of 1.195 V,which is among the best efficiencies reported for 2D PVSCs,and display greatly enhanced humidity and thermal stability.展开更多
Polymerization is a valid strategy to solve the dissolution issue of organic electrode materials in aprotic electrolytes.However,conventional polymers usually with amorphous structures and morphology’s influence on e...Polymerization is a valid strategy to solve the dissolution issue of organic electrode materials in aprotic electrolytes.However,conventional polymers usually with amorphous structures and morphology’s influence on electrochemistry have rarely been studied.Herein,a hollow tubular poly phenyl pyrene-4,5,9,10-tetraone(T-PPh-PTO)organic cathode material was designed and synthesized based on the concentration-gradient of the precursor(PTO-Br2)and asymmetrical internal diffusion during the reaction.The unique hollow structure endowed T-PPh-PTO with a short Li+diffusion path accompanied by a high diffusion Li+coefficient(D≈10−8 cm^(2)·s^(−1)).Thus,T-PPh-PTO presented a capacitance-dominated redox pseudocapacitance action with an outstanding rate performance(173 mAh·g^(−1)at 2 A·g^(−1))and high cycle stability(capacity retention ratio is 91.7%after 2,000 cycles).Our study leads to further developments in designing unique organic structures for energy storage.展开更多
基金National Natural Science Foundation of China,Grant/Award Numbers:52076209,52006224,52106285,22179027Foundation and Applied Foundation Research of Guangdong Province,Grant/Award Number:2022B1515020045+1 种基金Natural Science Foundation of Guangxi Province,Grant/Award Number:2021GXNSFAA075036Young Talent Support Project of Guangzhou Association for Science and Technology,Grant/Award Number:QT‐2023‐042。
文摘By employing metal oxides as oxygen carriers,chemical looping demonstrates its effectiveness in transferring oxygen between reduction and oxidation environments to partially oxidize fuels into syngas and convert CO_(2) into CO.Generally,NiFe_(2_)O_(4) oxygen carriers have demonstrated remarkable efficiency in chemical looping CO_(2) conversion.Nevertheless,the intricate process of atomic migration and evolution within the internal structure of bimetallic oxygen carriers during continuous high‐temperature redox cycling remains unclear.Consequently,the lack of a fundamental understanding of the complex ionic migration and oxygen transfer associated with energy conversion processes hampers the design of high‐performance oxygen carriers.Thus,in this study,we employed in situ characterization techniques and theoretical calculations to investigate the ion migration behavior and structural evolution in the bulk of NiFe_(2_)O_(4) oxygen carriers during H_(2) reduction and CO_(2)/lab air oxidation cycles.We discovered that during the H_(2) reduction step,lattice oxygen rapidly migrates to vacancy layers to replenish consumed active oxygen species,while Ni leaches from the material and migrates to the surface.During the CO_(2) splitting step,Ni migrates toward the core of the bimetallic oxygen carrier,forming Fe–Ni alloys.During the air oxidation step,Fe–Ni migrates outward,creating a hollow structure owing to the Kirkendall effect triggered by the swift transfer of lattice oxygen.The metal atom migration paths depend on the oxygen transfer rates.These discoveries highlight the significance of regulating the release–recovery rate of lattice oxygen to uphold the structures and reactivity of oxygen carriers.This work offers a comprehensive understanding of the oxidation/reduction‐driven atomic interdiffusion behavior of bimetallic oxygen carriers.
基金supported by grants from the National Science Foundation of Shandong Province(no.ZR2020ZD35)the Young Talent Cultivation Program of the State Key Laboratory of Crystal Materials,Shandong University
文摘Due to ever-increasing concerns about safety issues in using Li ionic batteries,solid electrolytes have extensively explored.The Li-rich antiperovskite Li_(3)OBr has been considered as a promising solid electrolyte candidate,but it still suffers challenges to achieve a high ionic conductivity owing to the high intrinsic symmetry of the crystal lattice.Herein,we presented a design strategy that introduces various point defects and grain boundaries to break the high lattice symmetry of Li_(3)OBr crystal,and their effect and microscopic mechanism of promoting the migration of Li-ion were explored theoretically.It has been found that Li_(i)are the dominant defects responsible for the fast Li-ion diffusion in bulk Li_(3)OBr and its surface,but they are easily trapped by the grain boundaries,leading to the annihilating of the Frenkel defect pair V'_(Li)+Li_(i),and thus limits the V'_(Li)diffusion at the grain boundaries.The V_(Br)defect near the grain boundaries can effectively drive V'_(Li)across the grain boundary,thereby converting the carrier of Li^(+)migration from Li,in the bulk and surface to V'_(Li)at the grain boundary,and thus improving the ionic conductivity in the whole Li_(3)OBr crystal.This work provides a comprehensive insight into the Li^(+)transport and conduction mechanism in the Li_(3)OBr electrolyte.It opens a new way of improving the conductivity for all-solid-state Li electrolyte material through the defect design.
基金supported financially by the National Key R&D Program of China (Grant No. 2018YFB0104300)Beijing Natural Science Foundation (JQ19003, KZ201910005002 and L182009)+1 种基金National Natural Science Foundation of China (Grants 21875007, 51622202, and 21974007)the Project of Youth Talent Plan of Beijing Municipal Education Commission (CIT&TCD201804013)。
文摘Solid polymer electrolytes have been considered as the promising candidates to improve the safety and stability of high-energy lithium metal batteries.However,the practical applications of solid polymer electrolytes are still limited by the low ionic conductivity,poor interfacial contact with electrodes,narrow electrochemical window and weak mechanical strength.Here,a series of novel block copolymer electrolytes with three-dimensional networks are designed by cross-linked copolymerization of the polyethylene glycol soft segments and hexamethylene diisocyanate trimer hard segments.Their ionic migration performances and interface compatibilities with Li metal anode have been optimized delicately by tailoring the ratio of these functional units.The optimized block copolymer electrolyte has shown an amorphous crystalline structure,a high ionic conductivity of ~5.7×10^(-4)S cm^(-1),high lithium ion transference number(~0.49),wide electrochemical window up to ~4.65 V(vs.Li+/Li) and favorable mechanical strength at 55℃.Furthermore,the enhanced interface compatibility can well support the normal operations of lithium metal batteries using both LiFePO4 and LiNi0.8Co0.15Al0.05O2 cathodes.This study not only paves a new way to develop solid polymer electrolyte with optimizing functional units,but also provides a polymer electrolyte design strategy for the application demand of lithium metal battery.
基金financially supported by the National Natural Science Foundation of China(No.U1604251)the Doctoral Start-up Foundation of Liaoning Province(No.2019-BS-178)the National Outstanding Youth Science Fund Project of National Natural Science Foundation of China(CN)(No.U52001216)。
文摘In this study, neutral salt spray accelerated corrosion test of copper–aluminium composite under 0–125 A DC current was carried out under 5% concentration. The effect of corrosion behaviour on copper–aluminium composite by DC current was carried out by a scanning electron microscope(SEM) with energy-dispersive spectroscopy(EDS), X-ray diffraction(XRD) patterns, X-ray photoelectron spectroscopy(XPS), weight-loss method and electrochemical analysis. The results show that the current can accelerate the corrosion rate. Meanwhile, the current temperature effect can reduce the corrosion rate. The current caused directional migration of ions resulting in different corrosion products on positive and negative poles of specimen, and the corrosion degree on the positive pole was more serious. The galvanic corrosion mechanism at the copper–aluminium interface is different from the pitting corrosion mechanism far away from the interface, and the latter is more affected by DC current.
基金financially supported by the National Natural Science Foundation of China (62174021 and 62104028)the Creative Research Groups of the National Natural Science Foundation of Sichuan Province (2023NSFSC1973)+7 种基金the Sichuan Science and Technology Program (MZGC20230008)the Natural Science Foundation of Sichuan Province (2022NSFSC0899)the China Postdoctoral Science Foundation (2021M700689)the Grant SCITLAB (20012) of Intelligent Terminal Key Laboratory of Sichuan ProvinceFundamental Research Funds for the Central Universities (ZYGX2019J054)the Guangdong Basic and Applied Basic Research Foundation (2019A1515110438)sponsored by the University of Kentuckythe Sichuan Province Key Laboratory of Display Science and Technology。
文摘Two-dimensional(2D) alternating cation(ACI) perovskite surface defects,especially dominant iodine vacancies(V_Ⅰ) and undercoordinated Pb^(2+),limit the performance of perovskite solar cells(PVSCs).To address the issue,1-butyl-3-methylimidazolium trifluoro-methane-sulfonate(BMIMOTF) and its iodide counterpart(BMIMI) are utilized to modify the perovskite surface respectively.We find that BMIMI can change the perovskite surface,whereas BMIMOTF shows a nondestructive and more effective defect passivation,giving significantly reduced defect density and suppressed charge-carrier nonradiative recombination.This mainly attributes to the marked passivation efficacy of OTF-anion on V_Ⅰ and undercoordinated Pb^(2+),rather than BMIMI^(+) cation.Benefiting from the rational surface-modification of BMMIMOTF,the films exhibit an optimized energy level alignment,enhanced hydrophobicity and suppressed ion migration.Consequently,the BMIMOTF-modified devices achieve an impressive efficiency of 21.38% with a record open-circuit voltage of 1.195 V,which is among the best efficiencies reported for 2D PVSCs,and display greatly enhanced humidity and thermal stability.
基金supported by the National Natural Science Foundation of China(Nos.51771094 and 21835004)the National Key Research and Development(R&D)Program of China(No.2016YFB0901500)+1 种基金the Ministry of Education of China(No.B12015)Tianjin Natural Science Foundation(No.18JCZDJC31500).
文摘Polymerization is a valid strategy to solve the dissolution issue of organic electrode materials in aprotic electrolytes.However,conventional polymers usually with amorphous structures and morphology’s influence on electrochemistry have rarely been studied.Herein,a hollow tubular poly phenyl pyrene-4,5,9,10-tetraone(T-PPh-PTO)organic cathode material was designed and synthesized based on the concentration-gradient of the precursor(PTO-Br2)and asymmetrical internal diffusion during the reaction.The unique hollow structure endowed T-PPh-PTO with a short Li+diffusion path accompanied by a high diffusion Li+coefficient(D≈10−8 cm^(2)·s^(−1)).Thus,T-PPh-PTO presented a capacitance-dominated redox pseudocapacitance action with an outstanding rate performance(173 mAh·g^(−1)at 2 A·g^(−1))and high cycle stability(capacity retention ratio is 91.7%after 2,000 cycles).Our study leads to further developments in designing unique organic structures for energy storage.
