Tin(Sn)holds great promise as an anode material for next-generation lithium(Li)ion batteries but suffers from massive volume change and poor cycling performance.To clarify the dynamic chemical and microstructural evol...Tin(Sn)holds great promise as an anode material for next-generation lithium(Li)ion batteries but suffers from massive volume change and poor cycling performance.To clarify the dynamic chemical and microstructural evolution of Sn anode during lithiation and delithiation,synchrotron X-ray energydispersive diffraction and X-ray tomography are simultaneously employed during Li/Sn cell operation.The intermediate Li-Sn alloy phases during de/lithiation are identified,and their dynamic phase transformation is unraveled which is further correlated with the volume variation of the Sn at particle-and electrode-level.Moreover,we find that the Sn particle expansion/shrinkage induced particle displacement is anisotropic:the displacement perpendicular to the electrode surface(z-axis)is more pronounced compared to the directions(x-and y-axis)along the electrode surface.This anisotropic particle displacement leads to an anisotropic volume variation at the electrode level and eventually generates a net electrode expansion towards the separator after cycling,which could be one of the root causes of mechanical detachment and delamination of electrodes during long-term operation.The unraveled chemical evolution of Li-Sn and deep insights into the microstructural evolution of Sn anode provided here could guide future design and engineering of Sn and other alloy anodes for high energy density Li-and Na-ion batteries.展开更多
Prevention of mechanical and finally electrochemical failures of lithium batteries is a critical aspect to be considered during their design and performance, especially for those with high specific capacities. Interna...Prevention of mechanical and finally electrochemical failures of lithium batteries is a critical aspect to be considered during their design and performance, especially for those with high specific capacities. Internal failure is observed as one of the most serious factors, including loss of electrode materials, structure deformation and dendrite growth. It usually incubates from atomic/molecular level and progressively aggravates along with lithiation. Understanding the internal failure is of great importance for developing solutions of failure prevention and advanced anode materials. In this research, different internal failure processes of anode materials for lithium batteries are discussed. The progress on observation technologies of the anode failure is further summarized in order to understand their mechanisms of internal failure. On top of them, this review aims to summarize innovative methods to investigate the anode failure mechanisms and to gain new insights to develop advanced and stable anodes for lithium batteries.展开更多
This paper addresses the damaging role of the parasitic hydrogen evolution reaction (HER) in the negative half-cell of a vanadium redox flow battery (VRFB) on state-of-the-art carbon felt electrodes at different tempe...This paper addresses the damaging role of the parasitic hydrogen evolution reaction (HER) in the negative half-cell of a vanadium redox flow battery (VRFB) on state-of-the-art carbon felt electrodes at different temperatures. It was found that increasing the temperature resulted in a better catalytic performance for both the positive and negative half-cell reactions. In addition, increasing the temperature significantly enhanced the undesired HER at the negative side. Operating the VRFB cell at higher temperature led to a decrease in the coulombic efficiency attributed to the higher hydrogen production. More pronounced hydrogen production caused an oxidation on the surface of the carb on fibers and a degradation of the electrode as indicated from scanning electron microscopy and X-ray photoelectron spectroscopy measurements. This observed degradation results in fading of the overall performance of the vanadium redox flow battery over time.展开更多
Carbon materials have been widely used as electrodes, but the mechanistic roles are still not clear due to the complexity of the carbon surface chemistry. Herein we clarify that intrinsic material properties of carbon...Carbon materials have been widely used as electrodes, but the mechanistic roles are still not clear due to the complexity of the carbon surface chemistry. Herein we clarify that intrinsic material properties of carbon have to be activated by extrinsic factors. Pure carbon has no catalytic activity when used as electrode for electrocatalytic water oxidation. The evolution of oxygen functional groups on the carbon surface with increasing potential and the subsequent formation of real active sites with iron impurities from the electrolyte have been confirmed. These in-situ formed active sites protect the carbon from deep oxidation. This unprecedented finding not only provides insight into the dynamic evolution of carbon electrode surface chemistry and raises awareness of the need for detailed surface analysis under operando conditions, but also suggests a direction for the development of scalable and high-performance carbonbased electrode systems for various electrochemical applications.展开更多
As one of the most promising Kitaev quantum-spin-liquid(QSL)candidates,α-RuCl_(3)has received a great deal of attention.However,its ground state exhibits a long-range zigzag magnetic order,which defies the QSL phase....As one of the most promising Kitaev quantum-spin-liquid(QSL)candidates,α-RuCl_(3)has received a great deal of attention.However,its ground state exhibits a long-range zigzag magnetic order,which defies the QSL phase.Nevertheless,the magnetic order is fragile and can be completely suppressed by applying an external magnetic field.Here,we explore the evolution of magnetic excitations ofα-RuCl;under an in-plane magnetic field,by carrying out inelastic neutron scattering measurements on high-quality single crystals.Under zero field,there exist spin-wave excitations near the M point and a continuum near theΓpoint,which are believed to be associated with the zigzag magnetic order and fractional excitations of the Kitaev QSL state,respectively.By increasing the magnetic field,the spin-wave excitations gradually give way to the continuous excitations.On the verge of the critical fieldμ_(0)H_(c)=7.5 T,the former ones vanish and only the latter ones are left,indicating the emergence of a pure QSL state.By further increasing the field strength,the excitations near theΓpoint become more intense.By following the gap evolution of the excitations near theΓpoint,we are able to establish a phase diagram composed of three interesting phases,including a gapped zigzag order phase at low fields,possibly gapless QSL phase nearμ;H;,and gapped partially polarized phase at high fields.These results demonstrate that an in-plane magnetic field can driveα-RuCl;into a long-sought QSL state near the critical field.展开更多
It is known that α-RuCl_(3) has been studied extensively because of its proximity to the Kitaev quantum-spin-liquid(QSL)phase and the possibility of approaching it by tuning the competing interactions.Here we present...It is known that α-RuCl_(3) has been studied extensively because of its proximity to the Kitaev quantum-spin-liquid(QSL)phase and the possibility of approaching it by tuning the competing interactions.Here we present the first polarized inelastic neutron scattering study on α-RuCl_(3) single crystals to explore the scattering continuum around the Γ point at the Brillouin zone center,which was hypothesized to be resulting from the Kitaev QSL state but without concrete evidence.With polarization analyses,we find that,while the spin-wave excitations around the Γ point vanish above the transition temperature T_(N),the pure magnetic continuous excitations around the Γ point are robust against temperature.Furthermore,by calculating the dynamical spin-spin correlation function using the cluster perturbation theory,we derive magnetic dispersion spectra based on the K-Γ model,which involves with a ferromagnetic Kitaev interaction of −7.2 meV and an off-diagonal interaction of 5.6 meV.We find this model can reproduce not only the spin-wave excitation spectra around the Γ point,but also the non-spin-wave continuous magnetic excitations around the Γ point.These results provide evidence for the existence of fractional excitations around the Γ point originating from the Kitaev QSL state,and further support the validity of the K-Γ model as the effective minimal spin model to describe α-RuCl_(3).展开更多
Muon spin relaxation/rotation(μSR) is a vital technique for probing the superconducting gap structure, pairing symmetry and time reversal symmetry breaking, enabling an understanding of the mechanisms behind the unco...Muon spin relaxation/rotation(μSR) is a vital technique for probing the superconducting gap structure, pairing symmetry and time reversal symmetry breaking, enabling an understanding of the mechanisms behind the unconventional superconductivity of cuprates and Fe-based high-temperature superconductors, which remain a puzzle. Very recently double layered Fe-based superconductors having quasi-2 D crystal structures and Cr-based superconductors with a quasi-1D structure have drawn considerable attention. Here we present a brief review of the characteristics of a few selected Fe-and Cr-based superconducting materials and highlight some of the major outstanding problems, with an emphasis on the superconducting pairing symmetries of these materials. We focus on μSR studies of the newly discovered superconductors ACa_2Fe_4As_4F_2(A = K, Rb, and Cs), ThFeAsN, and A_2Cr_3As_3(A = K, Cs), which were used to determine the superconducting gap structures, the presence of spin fluctuations, and to search for time reversal symmetry breaking in the superconducting states. We also briefly discuss the results of μSR investigations of the superconductivity in hole and electron doped BaFe_2As_2.展开更多
Fresnel zone plates are the key optical elements for nanoscale focusing of X-ray beams with high spatial resolution. Conventional zone plates manufactured by planar nanotechnology processes are limited by the achievab...Fresnel zone plates are the key optical elements for nanoscale focusing of X-ray beams with high spatial resolution. Conventional zone plates manufactured by planar nanotechnology processes are limited by the achievable aspect ratios of their zone structures. Additionally, ultra-high resolution X-ray optics with high efficiency requires three-dimensional （3-D） shaped tilted zones. The combination of high spatial resolution and high diffraction efficiency is a fundamental problem in X-ray optics. Based on electrodynamical simulations, we find that the optimized zone plate profile for volume diffraction is given by zone structures with radially increasing tilt angles and decreasing zone heights. On-chip stacking permits the realization of such advanced 3-D profiles without significant loss of the maximum theoretical efficiency. We developed triple layer on-chip stacked zone plates with an overlay accuracy of sub-2 nm which fulfills the nanofabrication requirements. Efficiency measurements of on-chip stacked zone plates show significantly increased values compared to conventional zone plates.展开更多
基金sponsored by the Helmholtz Association,the China Scholarship Council(CSC)partially funded by the German Research Foundation,DFG(Project No.MA 5039/4-1)。
文摘Tin(Sn)holds great promise as an anode material for next-generation lithium(Li)ion batteries but suffers from massive volume change and poor cycling performance.To clarify the dynamic chemical and microstructural evolution of Sn anode during lithiation and delithiation,synchrotron X-ray energydispersive diffraction and X-ray tomography are simultaneously employed during Li/Sn cell operation.The intermediate Li-Sn alloy phases during de/lithiation are identified,and their dynamic phase transformation is unraveled which is further correlated with the volume variation of the Sn at particle-and electrode-level.Moreover,we find that the Sn particle expansion/shrinkage induced particle displacement is anisotropic:the displacement perpendicular to the electrode surface(z-axis)is more pronounced compared to the directions(x-and y-axis)along the electrode surface.This anisotropic particle displacement leads to an anisotropic volume variation at the electrode level and eventually generates a net electrode expansion towards the separator after cycling,which could be one of the root causes of mechanical detachment and delamination of electrodes during long-term operation.The unraveled chemical evolution of Li-Sn and deep insights into the microstructural evolution of Sn anode provided here could guide future design and engineering of Sn and other alloy anodes for high energy density Li-and Na-ion batteries.
基金the financial support on this research from National Key Research and Development Program of China (2017YFB0403300/2017YFB043305)National Natural Science Foundation of China under Grant No. 51425405+1 种基金Key Program of Chinese Academy of Sciences KFZD-SW-3151000 Talents Program of China (Z.S.)
文摘Prevention of mechanical and finally electrochemical failures of lithium batteries is a critical aspect to be considered during their design and performance, especially for those with high specific capacities. Internal failure is observed as one of the most serious factors, including loss of electrode materials, structure deformation and dendrite growth. It usually incubates from atomic/molecular level and progressively aggravates along with lithiation. Understanding the internal failure is of great importance for developing solutions of failure prevention and advanced anode materials. In this research, different internal failure processes of anode materials for lithium batteries are discussed. The progress on observation technologies of the anode failure is further summarized in order to understand their mechanisms of internal failure. On top of them, this review aims to summarize innovative methods to investigate the anode failure mechanisms and to gain new insights to develop advanced and stable anodes for lithium batteries.
基金a fellowship from the Alexander von Humboldt Foundation (AvH)
文摘This paper addresses the damaging role of the parasitic hydrogen evolution reaction (HER) in the negative half-cell of a vanadium redox flow battery (VRFB) on state-of-the-art carbon felt electrodes at different temperatures. It was found that increasing the temperature resulted in a better catalytic performance for both the positive and negative half-cell reactions. In addition, increasing the temperature significantly enhanced the undesired HER at the negative side. Operating the VRFB cell at higher temperature led to a decrease in the coulombic efficiency attributed to the higher hydrogen production. More pronounced hydrogen production caused an oxidation on the surface of the carb on fibers and a degradation of the electrode as indicated from scanning electron microscopy and X-ray photoelectron spectroscopy measurements. This observed degradation results in fading of the overall performance of the vanadium redox flow battery over time.
文摘Carbon materials have been widely used as electrodes, but the mechanistic roles are still not clear due to the complexity of the carbon surface chemistry. Herein we clarify that intrinsic material properties of carbon have to be activated by extrinsic factors. Pure carbon has no catalytic activity when used as electrode for electrocatalytic water oxidation. The evolution of oxygen functional groups on the carbon surface with increasing potential and the subsequent formation of real active sites with iron impurities from the electrolyte have been confirmed. These in-situ formed active sites protect the carbon from deep oxidation. This unprecedented finding not only provides insight into the dynamic evolution of carbon electrode surface chemistry and raises awareness of the need for detailed surface analysis under operando conditions, but also suggests a direction for the development of scalable and high-performance carbonbased electrode systems for various electrochemical applications.
基金supported by the National Key Research and Development Program of China(Grant No.2021YFA1400400)the National Natural Science Foundation of China(Grant Nos.11822405,12074174,12074175,92165205,11904170,12004249,12004251,and 12004191)+1 种基金the Natural Science Foundation of Jiangsu Province(Grant Nos.BK20180006,BK20190436,and BK20200738)the Shanghai Sailing Program(Grant Nos.20YF1430600 and 21YF1429200)。
文摘As one of the most promising Kitaev quantum-spin-liquid(QSL)candidates,α-RuCl_(3)has received a great deal of attention.However,its ground state exhibits a long-range zigzag magnetic order,which defies the QSL phase.Nevertheless,the magnetic order is fragile and can be completely suppressed by applying an external magnetic field.Here,we explore the evolution of magnetic excitations ofα-RuCl;under an in-plane magnetic field,by carrying out inelastic neutron scattering measurements on high-quality single crystals.Under zero field,there exist spin-wave excitations near the M point and a continuum near theΓpoint,which are believed to be associated with the zigzag magnetic order and fractional excitations of the Kitaev QSL state,respectively.By increasing the magnetic field,the spin-wave excitations gradually give way to the continuous excitations.On the verge of the critical fieldμ_(0)H_(c)=7.5 T,the former ones vanish and only the latter ones are left,indicating the emergence of a pure QSL state.By further increasing the field strength,the excitations near theΓpoint become more intense.By following the gap evolution of the excitations near theΓpoint,we are able to establish a phase diagram composed of three interesting phases,including a gapped zigzag order phase at low fields,possibly gapless QSL phase nearμ;H;,and gapped partially polarized phase at high fields.These results demonstrate that an in-plane magnetic field can driveα-RuCl;into a long-sought QSL state near the critical field.
基金supported by National Key Research and Development Program of China(Grant No.2021YFA1400400)the National Natural Science Foundation of China(Grant Nos.11822405,12074174,12074175,11774152,11904170,12004249,12004251,and 12004191)+3 种基金the Natural Science Foundation of Jiangsu Province(Grant Nos.BK20180006,BK20190436 and BK20200738)the Shanghai Sailing Program(Grant Nos.20YF1430600 and21YF1429200)the Fundamental Research Funds for the Central Universities(Grant No.020414380183)the Office of International Cooperation and Exchanges of Nanjing University。
文摘It is known that α-RuCl_(3) has been studied extensively because of its proximity to the Kitaev quantum-spin-liquid(QSL)phase and the possibility of approaching it by tuning the competing interactions.Here we present the first polarized inelastic neutron scattering study on α-RuCl_(3) single crystals to explore the scattering continuum around the Γ point at the Brillouin zone center,which was hypothesized to be resulting from the Kitaev QSL state but without concrete evidence.With polarization analyses,we find that,while the spin-wave excitations around the Γ point vanish above the transition temperature T_(N),the pure magnetic continuous excitations around the Γ point are robust against temperature.Furthermore,by calculating the dynamical spin-spin correlation function using the cluster perturbation theory,we derive magnetic dispersion spectra based on the K-Γ model,which involves with a ferromagnetic Kitaev interaction of −7.2 meV and an off-diagonal interaction of 5.6 meV.We find this model can reproduce not only the spin-wave excitation spectra around the Γ point,but also the non-spin-wave continuous magnetic excitations around the Γ point.These results provide evidence for the existence of fractional excitations around the Γ point originating from the Kitaev QSL state,and further support the validity of the K-Γ model as the effective minimal spin model to describe α-RuCl_(3).
基金supported by the National Natural Science Foundation of China(Grant No.11874320)the National Key Research and Development Program of China(Grant No.2017YFA0303100)+2 种基金the Royal Society of London for the UK-China Newton funding and CMPC-STFC(Grant No.CMPC-09108)the DST India,for Inspire Faculty Research(Grant No.DST/INSPIRE/04/2015/000169)and UK-India Newton funding
文摘Muon spin relaxation/rotation(μSR) is a vital technique for probing the superconducting gap structure, pairing symmetry and time reversal symmetry breaking, enabling an understanding of the mechanisms behind the unconventional superconductivity of cuprates and Fe-based high-temperature superconductors, which remain a puzzle. Very recently double layered Fe-based superconductors having quasi-2 D crystal structures and Cr-based superconductors with a quasi-1D structure have drawn considerable attention. Here we present a brief review of the characteristics of a few selected Fe-and Cr-based superconducting materials and highlight some of the major outstanding problems, with an emphasis on the superconducting pairing symmetries of these materials. We focus on μSR studies of the newly discovered superconductors ACa_2Fe_4As_4F_2(A = K, Rb, and Cs), ThFeAsN, and A_2Cr_3As_3(A = K, Cs), which were used to determine the superconducting gap structures, the presence of spin fluctuations, and to search for time reversal symmetry breaking in the superconducting states. We also briefly discuss the results of μSR investigations of the superconductivity in hole and electron doped BaFe_2As_2.
文摘Fresnel zone plates are the key optical elements for nanoscale focusing of X-ray beams with high spatial resolution. Conventional zone plates manufactured by planar nanotechnology processes are limited by the achievable aspect ratios of their zone structures. Additionally, ultra-high resolution X-ray optics with high efficiency requires three-dimensional （3-D） shaped tilted zones. The combination of high spatial resolution and high diffraction efficiency is a fundamental problem in X-ray optics. Based on electrodynamical simulations, we find that the optimized zone plate profile for volume diffraction is given by zone structures with radially increasing tilt angles and decreasing zone heights. On-chip stacking permits the realization of such advanced 3-D profiles without significant loss of the maximum theoretical efficiency. We developed triple layer on-chip stacked zone plates with an overlay accuracy of sub-2 nm which fulfills the nanofabrication requirements. Efficiency measurements of on-chip stacked zone plates show significantly increased values compared to conventional zone plates.
