Benefited from its high process feasibility and controllable costs,binary-metal layered structured LiNi_(0.8)Mn_(0.2)O_(2)(NM)can effectively alleviate the cobalt supply crisis under the surge of global electric vehic...Benefited from its high process feasibility and controllable costs,binary-metal layered structured LiNi_(0.8)Mn_(0.2)O_(2)(NM)can effectively alleviate the cobalt supply crisis under the surge of global electric vehicles(EVs)sales,which is considered as the most promising nextgeneration cathode material for lithium-ion batteries(LIBs).However,the lack of deep understanding on the failure mechanism of NM has seriously hindered its application,especially under the harsh condition of high-voltage without sacrifices of reversible capacity.Herein,singlecrystal LiNi_(0.8)Mn_(0.2)O_(2) is selected and compared with traditional LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM),mainly focusing on the failure mechanism of Cofree cathode and illuminating the significant effect of Co element on the Li/Ni antisite defect and dynamic characteristic.Specifically,the presence of high Li/Ni antisite defect in NM cathode easily results in the extremely dramatic H2/H3 phase transition,which exacerbates the distortion of the lattice,mechanical strain changes and exhibits poor electrochemical performance,especially under the high cutoff voltage.Furthermore,the reaction kinetic of NM is impaired due to the absence of Co element,especially at the single-crystal architecture.Whereas,the negative influence of Li/Ni antisite defect is controllable at low current densities,owing to the attenuated polarization.Notably,Co-free NM can exhibit better safety performance than that of NCM cathode.These findings are beneficial for understanding the fundamental reaction mechanism of single-crystal Ni-rich Co-free cathode materials,providing new insights and great encouragements to design and develop the next generation of LIBs with low-cost and high-safety performances.展开更多
Single-crystal Ni-rich cathodes are a promising candidate for high-energy lithium-ion batteries due to their higher structural and cycling stability than polycrystalline materials.However,the phase evolution and capac...Single-crystal Ni-rich cathodes are a promising candidate for high-energy lithium-ion batteries due to their higher structural and cycling stability than polycrystalline materials.However,the phase evolution and capacity degradation of these single-crystal cathodes during continuous lithation/delithation cycling remains unclear.Understanding the mapping relationship between the macroscopic electrochemical properties and the material physicochemical properties is crucial.Here,we investigate the correlation between the physical-chemical characteristics,phase transition,and capacity decay using capacity differential curve feature identification and in-situ X-ray spectroscopic imaging.We systematically clarify the dominant mechanism of phase evolution in aging cycling.Appropriately high cut-off voltages can mitigate the slow kinetic and electrochemical properties of single-crystal cathodes.We also find that second-order differential capacity discharge characteristic curves can be used to identify the crystal structure disorder of Ni-rich cathodes.These findings constitute a step forward in elucidating the correlation between the electrochemical extrinsic properties and the physicochemical intrinsic properties and provide new perspectives for failure analysis of layered electrode materials.展开更多
The poor electrochemical performance of all-solid-state batteries(ASSBs),which is assemblied by Ni-rich cathode and poly(ethylene oxide)(PEO)-based electrolytes,can be attributed to unstable cathodic interface and poo...The poor electrochemical performance of all-solid-state batteries(ASSBs),which is assemblied by Ni-rich cathode and poly(ethylene oxide)(PEO)-based electrolytes,can be attributed to unstable cathodic interface and poor crystal structure stability of Ni-rich cathode.Several coating strategies are previously employed to enhance the stability of the cathodic interface and crystal structure for Ni-rich cathode.However,these methods can hardly achieve simplicity and high efficiency simultaneously.In this work,polyacrylic acid(PAA)replaced traditional PVDF as a binder for cathode,which can achieve a uniform PAA-Li(LixPAA(0<x≤1))coating layer on the surface of single-crystal LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)due to H^(+)/Li^(+)exchange reaction during the initial charging-discharging process.The formation of PAA-Li coating layer on cathode can promote interfacial Li^(+)transport and enhance the stability of the cathodic interface.Furthermore,the partially-protonated surface of SC-NCM83 casued by H^(+)/Li^(+)exchange reaction can restrict Ni ions transport to enhance the crystal structure stability.The proposed SC-NCM83-PAA exhibits superior cycling performance with a retention of 92%compared with that(57.3%)of SC-NCM83-polyvinylidene difluoride(PVDF)after 200 cycles.This work provides a practical strategy to construct high-performance cathodes for ASSBs.展开更多
LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) is extensively researched as one of the most widely used commercially materials for Li-ion batteries at present.However,the poor high-voltage performance(≥4.3 V)with low reversible cap...LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) is extensively researched as one of the most widely used commercially materials for Li-ion batteries at present.However,the poor high-voltage performance(≥4.3 V)with low reversible capacity limits its replacement for LiCoO_(2) in high-end digital field.Herein,three-in-one modification,Na-doping and Al_(2)O_(3)@Li_(3)BO_(3) dual-coating simultaneously,is explored for single-crystalline LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(N-NCM@AB),which exhibits excellent high-voltage performance.N-NCM@AB displays a discharge-specific capacity of 201.8 mAh g^(−1) at 0.2 C with a high upper voltage of 4.6 V and maintains 158.9 mAh g^(−1) discharge capacity at 1 C over 200 cycles with the corresponding capacity retention of 87.8%.Remarkably,the N-NCM@AB||graphite pouch-type full cell retains 81.2% of its initial capacity with high working voltage of 4.4 V over 1600 cycles.More importantly,the fundamental understandings of three-in-one modification on surface morphology,crystal structure,and phase transformation of N-NCM@AB are clearly revealed.The Na+doped into the Li–O slab can enhance the bond energy,stabilize the crystal structure,and facilitate Li+transport.Additionally,the interior surface layer of Li^(+)-ions conductor Li_(3)BO_(3) relieves the charge transfer resistance with surface coating,whereas the outer surface Al_(2)O_(3) coating layer is beneficial for reducing the active materials loss and alleviating the electrode/electrolyte parasite reaction.This three-in-one strategy provides a reference for the further research on the performance attenuation mechanism of NCM,paving a new avenue to boost the high-voltage performance of NCM cathode in Li-ion batteries.展开更多
The process of thermal stress damage during 1080 nm laser ablation of single-crystal germanium was recorded in real time using a high-speed charge-coupled device.A three-dimensional finite element numerical model base...The process of thermal stress damage during 1080 nm laser ablation of single-crystal germanium was recorded in real time using a high-speed charge-coupled device.A three-dimensional finite element numerical model based on Fourier's heat conduction equation,Hooke's law and the Alexander–Hasson equation was developed to analyze the thermal stress damage mechanism involved.The damage morphology of the ablated samples was observed using an optical microscope.The results show that the cooling process has an important influence on fracture in the laser-irradiated region of single-crystal germanium.Fracture is the result of a combination of thermal stress and reduction in local yield strength.展开更多
Lead halide perovskites have attracted considerable attention as potential candidates for high-performance nano/microlasers,owing to their outstanding optical properties.However,the further development of perovskite m...Lead halide perovskites have attracted considerable attention as potential candidates for high-performance nano/microlasers,owing to their outstanding optical properties.However,the further development of perovskite microlaser arrays(especially based on polycrystalline thin films)produced by the conventional processing techniques is hindered by the chemical instability and surface roughness of the perovskite structures.Herein,we demonstrate a laser patterning of large-scale,highly crystalline perovskite single-crystal films to fabricate reproducible perovskite single-crystal-based microlaser arrays.Perovskite thin films were directly ablated by femtosecond-laser in multiple low-power cycles at a minimum machining line width of approximately 300 nm to realize high-precision,chemically clean,and repeatable fabrication of microdisk arrays.The surface impurities generated during the process can be washed away to avoid external optical loss due to the robustness of the single-crystal film.Moreover,the high-quality,large-sized perovskite single-crystal films can significantly improve the quality of microcavities,thereby realizing a perovskite microdisk laser with narrow linewidth(0.09 nm)and low threshold(5.1µJ/cm2).Benefiting from the novel laser patterning method and the large-sized perovskite single-crystal films,a high power and high color purity laser display with single-mode microlasers as pixels was successfully fabricated.Thus,this study may offer a potential platform for mass-scale and reproducible fabrication of microlaser arrays,and further facilitate the development of highly integrated applications based on perovskite materials.展开更多
A single-crystal diamond detector is fabricated to diagnose 14.1 MeV deuterium-tritium(D-T)fusion neutrons.The size of its diamond film is 4.5 mm×4.5 mm×500μm.This film is sandwiched by a flat,strip-pattern...A single-crystal diamond detector is fabricated to diagnose 14.1 MeV deuterium-tritium(D-T)fusion neutrons.The size of its diamond film is 4.5 mm×4.5 mm×500μm.This film is sandwiched by a flat,strip-patterned gold electrode.The dark current of this detector is experimentally measured to be lower than 0.1 nA under an electric field of 30 kV cm^(-1).This diamond detector is used to measure D-T fusion neutrons with a flux of about 7.5×10^(5) s^(-1)cm^(-2).The pronounced peak with a central energy of 8.28 MeV characterizing the^(12)C(n,α)~9Be reaction in the neutron energy spectrum is experimentally diagnosed,and the energy resolution is better than 1.69%,which is the best result reported so far using a diamond detector.A clear peak with a central energy of 6.52 MeV characterizing the^(12)C(n,n')3αreaction is also identified with an energy resolution of better than 7.67%.展开更多
Chemical vapor deposition(CVD)-grown diamond films have been developed as irradiation-resistant materials to replace or upgrade current detectors for use in extreme radiation environments. However, their sensitivity i...Chemical vapor deposition(CVD)-grown diamond films have been developed as irradiation-resistant materials to replace or upgrade current detectors for use in extreme radiation environments. However, their sensitivity in practical applications has been inhibited by space charge stability issues caused by defects and impurities in pure diamond crystal materials. In this study, two high-quality CVD-grown single-crystal diamond(SCD) detectors with low content of nitrogen impurities were fabricated and characterized. The intrinsic properties of the SCD samples were characterized using Raman spectroscopy, stereomicroscopy, and X-ray diffraction with the rocking curve mode, cathode luminescence(CL), and infrared and ultraviolet-visible-near infrared spectroscopies. After packaging the detectors, the dark current and energy resolution under α particle irradiation were investigated. Dark currents of less than 5 pA at 100 V were obtained after annealing the electrodes, which is comparable with the optimal value previously reported. The detector that uses a diamond film with higher nitrogen content showed poor energy resolution, whereas the detector with more dislocations showed poor charge collection efficiency(CCE). This demonstrates that the nitrogen content in diamond has a significant effect on the energy resolution of detectors, while the dislocations in diamond largely contribute to the poor CCE of detectors.展开更多
The self-assembled silicon substrate. The resultant contact angle meter and atomic method was introduced to successfully obtain film was characterized by means of X-ray rare earth(RE) nanofilm on a single-crystal ph...The self-assembled silicon substrate. The resultant contact angle meter and atomic method was introduced to successfully obtain film was characterized by means of X-ray rare earth(RE) nanofilm on a single-crystal photoelectron spectroscopy (XPS), ellipsometer, force microscopy (AFM). The scratch experiment was performed for interfacial adhesion measurement of the RE film. The friction and wear behavior of RE nanofilm was examined on a DF-PM reciprocating friction and wear tester. The results indicate the RE nanofilm is of low coefficient of friction (COF) and high wear resistance. These desirable characteristics of RE nanofilm together with its nanometer thickness, strong bonding to the substrate and low surface energy make it a promising choice as a solid lubricant film in micro electromechanical system (MEMS) devices.展开更多
Epitaxial high-crystallization film semiconductor heterostructures has been proved to be an effective method to prepare single-crystal films for different functional devices in modern microelectronics,electro-optics,a...Epitaxial high-crystallization film semiconductor heterostructures has been proved to be an effective method to prepare single-crystal films for different functional devices in modern microelectronics,electro-optics,and optoelectronics.With superior semiconducting properties,halide perovskite materials are rising as building blocks for heterostructures.Here,the conformal vapor phase epitaxy of CsPbBr3 on PbS single-crystal films is realized to form the CsPbBr3/PbS heterostructures via a two-step vapor deposition process.The structural characterization reveals that PbS substrates and the epilayer CsPbBr3 have clear relationships:CsPbBr3(110)//PbS(100),CsPbBr3[001]//PbS[001]and CsPbBr3[001]//PbS[010].The absorption and photoluminescence(PL)characteristics of CsPbBr3/PbS heterostructures show the broadband light absorption and efficient photogenerated carrier transfer.Photodetectors based on the heterostructures show superior photoresponsivity of 15 A/W,high detectivity of 2.65×10^(11) Jones,fast response speed of 96 ms and obvious rectification behavior.Our study offers a convenient method for establishing the high-quality CsPbBr3/PbS single-crystal film heterostructures and providing an effective way for their application in optoelectronic devices.展开更多
A novel star-like single-crystal ZnO structure was synthesized by a simple solvothermal method. The as-prepared products were characterized by XRD, SEM and TEM. The star-like ZnO, which shows sixfold symmetry, was con...A novel star-like single-crystal ZnO structure was synthesized by a simple solvothermal method. The as-prepared products were characterized by XRD, SEM and TEM. The star-like ZnO, which shows sixfold symmetry, was constructed by six uniform arms distributing symmetrically around the [0001] zone axis. It is also found that the arms are not perpendicular to the [0001] zone axis and each arm is grown at a certain angle with the [0001] direction. CBED pattern and corresponding simulation demonstrate that the convex part of the star-like ZnO is O-terminated (000-1) plane and the concave part is Zn-terminated (0001) plane. H2S plays a crucial role in the synthesis process. The anisotropic growth habit along [0001] and [000-1] results in the formation of star-like structure.展开更多
The relationship between the spatial position of the diamond seed and growth mode is investigated with an enclosedtype holder for single-crystal diamond growth using the microwave plasma chemical vapor deposition epit...The relationship between the spatial position of the diamond seed and growth mode is investigated with an enclosedtype holder for single-crystal diamond growth using the microwave plasma chemical vapor deposition epitaxial method.The results demonstrate that there are three main regions by varying the spatial position of the seed.Due to the plasma concentration occurring at the seed edge,a larger depth is beneficial to transfer the plasma to the holder surface and suppress the polycrystalline diamond rim around the seed edge.However,the plasma density at the edge decreases drastically when the depth is too large,resulting in the growth of a vicinal grain plane and the reduction of surface area.By adopting an appropriate spatial location,the size of single-crystal diamond can be increased from 7 mm×7 mm×0.35 mm to8.6 mm×8.6 mm×2.8 mm without the polycrystalline diamond rim.展开更多
Single-crystal rods with different diameters and deviation angles with respect to the solidification direction were produced by Bridgman rapid solidification method at withdrawal rates of 3 and 6 mm·min^(-1) and ...Single-crystal rods with different diameters and deviation angles with respect to the solidification direction were produced by Bridgman rapid solidification method at withdrawal rates of 3 and 6 mm·min^(-1) and used as grain continuators.The crystallographic orientation of the rods,which cross-sections were perpendicular to the solidification direction at different solidification heights,was measured by electron backscattered diffraction,while the corresponding microstructures were observed by optical microscopy.The mushy zone morphology and the distribution of the temperature gradient were simulated by the finite element analysis software ProCAST.The experimental results indicate that the crystallographic orientation of the single-crystal rods corresponds to the statistical average value of all the dendrite orientations in cross-section.The crystallographic orientation of the primary and secondary dendrites of each single-crystal rod at different cross-sections fluctuates irregularly within a small range(less than 4°).The crystallographic orientation of the dendrite in each single-crystal rod is not exactly consistent with each other and is affected by their branching mode of dendrites in the solidification space.In addition,the simulation results show that the mushy zone shapes and the temperature gradient of single-crystal rods change with the increase of solidification height during the solidification process.Finally,the evolution mechanism of the crystallographic orientations and the corresponding influence factors were analyzed and discussed.展开更多
The mosaic structure in a Ni-based single-crystal superalloy is simulated by molecular dynamics using a potential employed in a modified analytic embedded atom method. From the calculated results we find that a closed...The mosaic structure in a Ni-based single-crystal superalloy is simulated by molecular dynamics using a potential employed in a modified analytic embedded atom method. From the calculated results we find that a closed threedimensional misfit dislocation network, with index of (011){100} and the side length of the mesh 89.6A, is formed around a cuboidal γ′ precipitate. Comparing the simulation results of the different mosaic models, we find that the side length of the mesh only depends on the lattice parameters of the γ and γ′ phases as well as the γ/γ′ interface direction, but is independent of the size and number of the cuboidal γ′ precipitate. The density of dislocations is inversely proportional to the size of the cuboidal γ′ precipitate, i.e. the amount of the dislocation is proportional to the total area of the γ/γ′ interface, which may be used to explain the relation between the amount of the fine γ′ particles and the creep rupture life of the superalloy. In addition, the closed three-dimensional networks assembled with the misfit dislocations can play a significant role in improving the mechanical properties of superalloys.展开更多
TiO2 is a wide band gap semiconductor with important applications in photovoltaic cells. Vertically aligned Tit2 nanorod arrays (NRs) are grown on the fluorine-doped tin oxide (FTO) substrates by a multicycle hydr...TiO2 is a wide band gap semiconductor with important applications in photovoltaic cells. Vertically aligned Tit2 nanorod arrays (NRs) are grown on the fluorine-doped tin oxide (FTO) substrates by a multicycle hydrothermal synthesis process. The samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and selected-area electron diffraction (SAED). It is found that dye-sensitized solar cells (DSSCs) assembled by the as-prepared Tit2 single-crystal NRs exhibit different trends under the condition of different nucleation and growth concentrations. Optimum cell performance is obtained with high nucleation concentration and low growth cycle concentration. The efficiency enhancement is mainly attributed to the improved specific surface area of the nanorod.展开更多
An Ni-AI-Co system embedded-atom-method potential is constructed for the γ(Ni)/γ'(Ni3A1) superalloy based on experiments and first-principles calculations. The stacking fault energies (SFEs) of the Ni(Co, A1...An Ni-AI-Co system embedded-atom-method potential is constructed for the γ(Ni)/γ'(Ni3A1) superalloy based on experiments and first-principles calculations. The stacking fault energies (SFEs) of the Ni(Co, A1) random solid solutions are calculated as a function of the concentrations of Co and A1. The calculated SFEs decrease with increasing concentrations of Co and A1, which is consistent with the experimental results. The embedding energy term in the present potential has an important influence on the SFEs of the random solid solutions. The cross-slip processes of a screw dislocation in homogenous Ni(Co) solid solutions are simulated using the present potential and the nudged elastic band method. The cross-slip activation energies increase with increasing Co concentration, which implies that the creep resistance of γ(Ni) may be improved by the addition of Co.展开更多
Graphene with a Dirac cone-like electronic structure has been extensively studied because of its novel transport properties and potential application for future electronic devices.For epitaxially grown graphene,the pr...Graphene with a Dirac cone-like electronic structure has been extensively studied because of its novel transport properties and potential application for future electronic devices.For epitaxially grown graphene,the process conditions and the microstructures are strongly dependent on various substrate materials with different lattice constants and interface energies.Utilizing angle-resolved photoemission spectroscopy,here we report an investigation of the electronic structure of single-crystalline graphene grown on Cu/Ni(111)alloy film by chemical vapor deposition.With a relatively low growth temperature,graphene on Cu/Ni(111)exhibits a Dirac cone-like dispersion comparable to that of graphene grown on Cu(111).The linear dispersions forming Dirac cone are as wide as 2 e V,with the Fermi velocity of approximately 1.1×10^6 m/s.Dirac cone opens a gap of approximately 152 meV at the binding energy of approximately 304 meV.Our findings would promote the study of engineering of graphene on different substrate materials.展开更多
Remarkable room temperature ferromagnetism in pure single-crystal rutile TiO2 (001) samples irradiated by D-D neutron has been investigated. By combining X-ray diffraction and positron annihilation lifetime, the con...Remarkable room temperature ferromagnetism in pure single-crystal rutile TiO2 (001) samples irradiated by D-D neutron has been investigated. By combining X-ray diffraction and positron annihilation lifetime, the contracted lattice has been clearly identified in irradiated TiO2, where Ti4+ ions can be easily reduced to the state of Ti3+. As there were no magnetic impurities that could contaminate the samples during the whole procedure, some Ti3+ ions reside on interstitial or substituted sites accompanied by oxygen vacancies should be responsible for the ferromagnetism.展开更多
Finite element (FE) analysis was employed to investigate the casting microcrack and micropore growth in nickel-base single-crystal superalloys DD3. Based on the finite deformation rate-dependent crystallographic con...Finite element (FE) analysis was employed to investigate the casting microcrack and micropore growth in nickel-base single-crystal superalloys DD3. Based on the finite deformation rate-dependent crystallographic constitutive equation, the simulations of casting microcrack and micropore growth in three-dimensional unit cell model were carried out in a range of parameters including stress triaxiality, Lode parameter and type of activated slip systems. The FE results show that the stress triaxiality has profound effects on growth behavior, and the Lode parameter is also important for the casting microcrack and micropore growth. The type of operative slip systems has remarkable effect on casting microcrack and micropore growth, so the life of single- crystal component is associated with the type of activated slip systems, which is related to Schmid factor and the number of activated slip systems. The growth comparison between microcrack and micropore reveals that when the material is subjected to large deformation, the growth rate of microcrack is faster than that of micropore, i.e. microcrack is more dangerous than micropore; the microcrack is easier to result in brittle fracture than micropore. The stress triaxiality and Lode parameter have strong influence on the growth of microcrack and micropore.展开更多
The magnetic structure of the spin-chain antiferromagnet SrCo2 V208 is determined by single-crystal neutron diffraction experiment. The system undergoes a long-range magnetic order below the critical temperature TN=4....The magnetic structure of the spin-chain antiferromagnet SrCo2 V208 is determined by single-crystal neutron diffraction experiment. The system undergoes a long-range magnetic order below the critical temperature TN=4.96 K. The moment of 2.16#B per Co at 1.6K in the screw chain running along the c axis Mternates in the c axis. The moments of neighboring screw chains are arranged antiferromagnetically along one in-plane axis and ferromagnetieally Monk the other in-plane axis. This magnetic configuration breaks the four-fold symmetry of the tetragonM crystal structure and leads to two equally populated magnetic twins with the antiferromagnetic vector in the a or b axis. The very similar magnetic state to the isostructural BaCo2 V~ 08 warrants SrCo2 V2 08 as another interesting half-integer spin-chain antiferromagnet for investigation on quantum antiferromagnetism.展开更多
基金the National Natural Science Foundation of China(52070194,52073309,51902347,51908555)Natural Science Foundation of Hunan Province(2022JJ20069,2020JJ5741).
文摘Benefited from its high process feasibility and controllable costs,binary-metal layered structured LiNi_(0.8)Mn_(0.2)O_(2)(NM)can effectively alleviate the cobalt supply crisis under the surge of global electric vehicles(EVs)sales,which is considered as the most promising nextgeneration cathode material for lithium-ion batteries(LIBs).However,the lack of deep understanding on the failure mechanism of NM has seriously hindered its application,especially under the harsh condition of high-voltage without sacrifices of reversible capacity.Herein,singlecrystal LiNi_(0.8)Mn_(0.2)O_(2) is selected and compared with traditional LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM),mainly focusing on the failure mechanism of Cofree cathode and illuminating the significant effect of Co element on the Li/Ni antisite defect and dynamic characteristic.Specifically,the presence of high Li/Ni antisite defect in NM cathode easily results in the extremely dramatic H2/H3 phase transition,which exacerbates the distortion of the lattice,mechanical strain changes and exhibits poor electrochemical performance,especially under the high cutoff voltage.Furthermore,the reaction kinetic of NM is impaired due to the absence of Co element,especially at the single-crystal architecture.Whereas,the negative influence of Li/Ni antisite defect is controllable at low current densities,owing to the attenuated polarization.Notably,Co-free NM can exhibit better safety performance than that of NCM cathode.These findings are beneficial for understanding the fundamental reaction mechanism of single-crystal Ni-rich Co-free cathode materials,providing new insights and great encouragements to design and develop the next generation of LIBs with low-cost and high-safety performances.
文摘Single-crystal Ni-rich cathodes are a promising candidate for high-energy lithium-ion batteries due to their higher structural and cycling stability than polycrystalline materials.However,the phase evolution and capacity degradation of these single-crystal cathodes during continuous lithation/delithation cycling remains unclear.Understanding the mapping relationship between the macroscopic electrochemical properties and the material physicochemical properties is crucial.Here,we investigate the correlation between the physical-chemical characteristics,phase transition,and capacity decay using capacity differential curve feature identification and in-situ X-ray spectroscopic imaging.We systematically clarify the dominant mechanism of phase evolution in aging cycling.Appropriately high cut-off voltages can mitigate the slow kinetic and electrochemical properties of single-crystal cathodes.We also find that second-order differential capacity discharge characteristic curves can be used to identify the crystal structure disorder of Ni-rich cathodes.These findings constitute a step forward in elucidating the correlation between the electrochemical extrinsic properties and the physicochemical intrinsic properties and provide new perspectives for failure analysis of layered electrode materials.
基金the financial support from the National Natural Science Foundation of China(Nos.52034011 and 52204328)the Science and Technology Innovation Program of Hunan Province(2023RC305)the Changsha Municipal Natural Science Foundation(kq2202085)。
文摘The poor electrochemical performance of all-solid-state batteries(ASSBs),which is assemblied by Ni-rich cathode and poly(ethylene oxide)(PEO)-based electrolytes,can be attributed to unstable cathodic interface and poor crystal structure stability of Ni-rich cathode.Several coating strategies are previously employed to enhance the stability of the cathodic interface and crystal structure for Ni-rich cathode.However,these methods can hardly achieve simplicity and high efficiency simultaneously.In this work,polyacrylic acid(PAA)replaced traditional PVDF as a binder for cathode,which can achieve a uniform PAA-Li(LixPAA(0<x≤1))coating layer on the surface of single-crystal LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)due to H^(+)/Li^(+)exchange reaction during the initial charging-discharging process.The formation of PAA-Li coating layer on cathode can promote interfacial Li^(+)transport and enhance the stability of the cathodic interface.Furthermore,the partially-protonated surface of SC-NCM83 casued by H^(+)/Li^(+)exchange reaction can restrict Ni ions transport to enhance the crystal structure stability.The proposed SC-NCM83-PAA exhibits superior cycling performance with a retention of 92%compared with that(57.3%)of SC-NCM83-polyvinylidene difluoride(PVDF)after 200 cycles.This work provides a practical strategy to construct high-performance cathodes for ASSBs.
基金We gratefully acknowledge the financial support from the National Natural Science Foundation of China(52070194,51902347,51908555,and 51822812)Natural Science Foundation of Hunan Province(2020JJ5741)the Graduate Innovation Project of Central South University(2020zzts093).
文摘LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) is extensively researched as one of the most widely used commercially materials for Li-ion batteries at present.However,the poor high-voltage performance(≥4.3 V)with low reversible capacity limits its replacement for LiCoO_(2) in high-end digital field.Herein,three-in-one modification,Na-doping and Al_(2)O_(3)@Li_(3)BO_(3) dual-coating simultaneously,is explored for single-crystalline LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(N-NCM@AB),which exhibits excellent high-voltage performance.N-NCM@AB displays a discharge-specific capacity of 201.8 mAh g^(−1) at 0.2 C with a high upper voltage of 4.6 V and maintains 158.9 mAh g^(−1) discharge capacity at 1 C over 200 cycles with the corresponding capacity retention of 87.8%.Remarkably,the N-NCM@AB||graphite pouch-type full cell retains 81.2% of its initial capacity with high working voltage of 4.4 V over 1600 cycles.More importantly,the fundamental understandings of three-in-one modification on surface morphology,crystal structure,and phase transformation of N-NCM@AB are clearly revealed.The Na+doped into the Li–O slab can enhance the bond energy,stabilize the crystal structure,and facilitate Li+transport.Additionally,the interior surface layer of Li^(+)-ions conductor Li_(3)BO_(3) relieves the charge transfer resistance with surface coating,whereas the outer surface Al_(2)O_(3) coating layer is beneficial for reducing the active materials loss and alleviating the electrode/electrolyte parasite reaction.This three-in-one strategy provides a reference for the further research on the performance attenuation mechanism of NCM,paving a new avenue to boost the high-voltage performance of NCM cathode in Li-ion batteries.
文摘The process of thermal stress damage during 1080 nm laser ablation of single-crystal germanium was recorded in real time using a high-speed charge-coupled device.A three-dimensional finite element numerical model based on Fourier's heat conduction equation,Hooke's law and the Alexander–Hasson equation was developed to analyze the thermal stress damage mechanism involved.The damage morphology of the ablated samples was observed using an optical microscope.The results show that the cooling process has an important influence on fracture in the laser-irradiated region of single-crystal germanium.Fracture is the result of a combination of thermal stress and reduction in local yield strength.
基金the support from the National Natural Science Foundation of China (No. 61925506)the Natural Science Foundation of Shanghai (No. 20JC1414605)+1 种基金Hangzhou Science and Technology Bureau of Zhejiang Province (No. TD2020002)the Academic/Technology Research Leader Program of Shanghai (23XD1404500)
文摘Lead halide perovskites have attracted considerable attention as potential candidates for high-performance nano/microlasers,owing to their outstanding optical properties.However,the further development of perovskite microlaser arrays(especially based on polycrystalline thin films)produced by the conventional processing techniques is hindered by the chemical instability and surface roughness of the perovskite structures.Herein,we demonstrate a laser patterning of large-scale,highly crystalline perovskite single-crystal films to fabricate reproducible perovskite single-crystal-based microlaser arrays.Perovskite thin films were directly ablated by femtosecond-laser in multiple low-power cycles at a minimum machining line width of approximately 300 nm to realize high-precision,chemically clean,and repeatable fabrication of microdisk arrays.The surface impurities generated during the process can be washed away to avoid external optical loss due to the robustness of the single-crystal film.Moreover,the high-quality,large-sized perovskite single-crystal films can significantly improve the quality of microcavities,thereby realizing a perovskite microdisk laser with narrow linewidth(0.09 nm)and low threshold(5.1µJ/cm2).Benefiting from the novel laser patterning method and the large-sized perovskite single-crystal films,a high power and high color purity laser display with single-mode microlasers as pixels was successfully fabricated.Thus,this study may offer a potential platform for mass-scale and reproducible fabrication of microlaser arrays,and further facilitate the development of highly integrated applications based on perovskite materials.
基金supported by National Natural Science Foundation of China(No.12075241)。
文摘A single-crystal diamond detector is fabricated to diagnose 14.1 MeV deuterium-tritium(D-T)fusion neutrons.The size of its diamond film is 4.5 mm×4.5 mm×500μm.This film is sandwiched by a flat,strip-patterned gold electrode.The dark current of this detector is experimentally measured to be lower than 0.1 nA under an electric field of 30 kV cm^(-1).This diamond detector is used to measure D-T fusion neutrons with a flux of about 7.5×10^(5) s^(-1)cm^(-2).The pronounced peak with a central energy of 8.28 MeV characterizing the^(12)C(n,α)~9Be reaction in the neutron energy spectrum is experimentally diagnosed,and the energy resolution is better than 1.69%,which is the best result reported so far using a diamond detector.A clear peak with a central energy of 6.52 MeV characterizing the^(12)C(n,n')3αreaction is also identified with an energy resolution of better than 7.67%.
基金This work was financially supported by the Natural Science Foundation of Beijing,China(No.4192038)National Key Research and Development Program of China(Nos.2016YFE0133200 and 2018YFB0406501)European Union’s Horizon 2020 Research and Innovation Staff Exchange Scheme(No.734578).
文摘Chemical vapor deposition(CVD)-grown diamond films have been developed as irradiation-resistant materials to replace or upgrade current detectors for use in extreme radiation environments. However, their sensitivity in practical applications has been inhibited by space charge stability issues caused by defects and impurities in pure diamond crystal materials. In this study, two high-quality CVD-grown single-crystal diamond(SCD) detectors with low content of nitrogen impurities were fabricated and characterized. The intrinsic properties of the SCD samples were characterized using Raman spectroscopy, stereomicroscopy, and X-ray diffraction with the rocking curve mode, cathode luminescence(CL), and infrared and ultraviolet-visible-near infrared spectroscopies. After packaging the detectors, the dark current and energy resolution under α particle irradiation were investigated. Dark currents of less than 5 pA at 100 V were obtained after annealing the electrodes, which is comparable with the optimal value previously reported. The detector that uses a diamond film with higher nitrogen content showed poor energy resolution, whereas the detector with more dislocations showed poor charge collection efficiency(CCE). This demonstrates that the nitrogen content in diamond has a significant effect on the energy resolution of detectors, while the dislocations in diamond largely contribute to the poor CCE of detectors.
文摘The self-assembled silicon substrate. The resultant contact angle meter and atomic method was introduced to successfully obtain film was characterized by means of X-ray rare earth(RE) nanofilm on a single-crystal photoelectron spectroscopy (XPS), ellipsometer, force microscopy (AFM). The scratch experiment was performed for interfacial adhesion measurement of the RE film. The friction and wear behavior of RE nanofilm was examined on a DF-PM reciprocating friction and wear tester. The results indicate the RE nanofilm is of low coefficient of friction (COF) and high wear resistance. These desirable characteristics of RE nanofilm together with its nanometer thickness, strong bonding to the substrate and low surface energy make it a promising choice as a solid lubricant film in micro electromechanical system (MEMS) devices.
基金This work was supported by the Natural Science Foundation of China(Grant No.11704389)Scientific Equipment Development Project and Youth Innovation Promotion Association Project of Chinese Academy of Sciences.
文摘Epitaxial high-crystallization film semiconductor heterostructures has been proved to be an effective method to prepare single-crystal films for different functional devices in modern microelectronics,electro-optics,and optoelectronics.With superior semiconducting properties,halide perovskite materials are rising as building blocks for heterostructures.Here,the conformal vapor phase epitaxy of CsPbBr3 on PbS single-crystal films is realized to form the CsPbBr3/PbS heterostructures via a two-step vapor deposition process.The structural characterization reveals that PbS substrates and the epilayer CsPbBr3 have clear relationships:CsPbBr3(110)//PbS(100),CsPbBr3[001]//PbS[001]and CsPbBr3[001]//PbS[010].The absorption and photoluminescence(PL)characteristics of CsPbBr3/PbS heterostructures show the broadband light absorption and efficient photogenerated carrier transfer.Photodetectors based on the heterostructures show superior photoresponsivity of 15 A/W,high detectivity of 2.65×10^(11) Jones,fast response speed of 96 ms and obvious rectification behavior.Our study offers a convenient method for establishing the high-quality CsPbBr3/PbS single-crystal film heterostructures and providing an effective way for their application in optoelectronic devices.
文摘A novel star-like single-crystal ZnO structure was synthesized by a simple solvothermal method. The as-prepared products were characterized by XRD, SEM and TEM. The star-like ZnO, which shows sixfold symmetry, was constructed by six uniform arms distributing symmetrically around the [0001] zone axis. It is also found that the arms are not perpendicular to the [0001] zone axis and each arm is grown at a certain angle with the [0001] direction. CBED pattern and corresponding simulation demonstrate that the convex part of the star-like ZnO is O-terminated (000-1) plane and the concave part is Zn-terminated (0001) plane. H2S plays a crucial role in the synthesis process. The anisotropic growth habit along [0001] and [000-1] results in the formation of star-like structure.
基金Project supported by the Key-Area Research and Development Program of Guangdong Province,China(Grant No.2020B0101690001)。
文摘The relationship between the spatial position of the diamond seed and growth mode is investigated with an enclosedtype holder for single-crystal diamond growth using the microwave plasma chemical vapor deposition epitaxial method.The results demonstrate that there are three main regions by varying the spatial position of the seed.Due to the plasma concentration occurring at the seed edge,a larger depth is beneficial to transfer the plasma to the holder surface and suppress the polycrystalline diamond rim around the seed edge.However,the plasma density at the edge decreases drastically when the depth is too large,resulting in the growth of a vicinal grain plane and the reduction of surface area.By adopting an appropriate spatial location,the size of single-crystal diamond can be increased from 7 mm×7 mm×0.35 mm to8.6 mm×8.6 mm×2.8 mm without the polycrystalline diamond rim.
基金supported by the National Natural Science Foundation of China(No.51674235)the National Key Research and Development Program of China(Nos.2017-VI0001-0070 and 2017-VI-0019-0091)。
文摘Single-crystal rods with different diameters and deviation angles with respect to the solidification direction were produced by Bridgman rapid solidification method at withdrawal rates of 3 and 6 mm·min^(-1) and used as grain continuators.The crystallographic orientation of the rods,which cross-sections were perpendicular to the solidification direction at different solidification heights,was measured by electron backscattered diffraction,while the corresponding microstructures were observed by optical microscopy.The mushy zone morphology and the distribution of the temperature gradient were simulated by the finite element analysis software ProCAST.The experimental results indicate that the crystallographic orientation of the single-crystal rods corresponds to the statistical average value of all the dendrite orientations in cross-section.The crystallographic orientation of the primary and secondary dendrites of each single-crystal rod at different cross-sections fluctuates irregularly within a small range(less than 4°).The crystallographic orientation of the dendrite in each single-crystal rod is not exactly consistent with each other and is affected by their branching mode of dendrites in the solidification space.In addition,the simulation results show that the mushy zone shapes and the temperature gradient of single-crystal rods change with the increase of solidification height during the solidification process.Finally,the evolution mechanism of the crystallographic orientations and the corresponding influence factors were analyzed and discussed.
基金Project supported by the State Key Development Program for Basic Research of China (Grant No G2000067102) and the National Natural Science Foundation of China (Grant No 90101004).
文摘The mosaic structure in a Ni-based single-crystal superalloy is simulated by molecular dynamics using a potential employed in a modified analytic embedded atom method. From the calculated results we find that a closed threedimensional misfit dislocation network, with index of (011){100} and the side length of the mesh 89.6A, is formed around a cuboidal γ′ precipitate. Comparing the simulation results of the different mosaic models, we find that the side length of the mesh only depends on the lattice parameters of the γ and γ′ phases as well as the γ/γ′ interface direction, but is independent of the size and number of the cuboidal γ′ precipitate. The density of dislocations is inversely proportional to the size of the cuboidal γ′ precipitate, i.e. the amount of the dislocation is proportional to the total area of the γ/γ′ interface, which may be used to explain the relation between the amount of the fine γ′ particles and the creep rupture life of the superalloy. In addition, the closed three-dimensional networks assembled with the misfit dislocations can play a significant role in improving the mechanical properties of superalloys.
基金Project supported by the Fundamental Research Funds for the Central Universities,China(Grant No.2013XK07)
文摘TiO2 is a wide band gap semiconductor with important applications in photovoltaic cells. Vertically aligned Tit2 nanorod arrays (NRs) are grown on the fluorine-doped tin oxide (FTO) substrates by a multicycle hydrothermal synthesis process. The samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and selected-area electron diffraction (SAED). It is found that dye-sensitized solar cells (DSSCs) assembled by the as-prepared Tit2 single-crystal NRs exhibit different trends under the condition of different nucleation and growth concentrations. Optimum cell performance is obtained with high nucleation concentration and low growth cycle concentration. The efficiency enhancement is mainly attributed to the improved specific surface area of the nanorod.
基金Project supported by the National Basic Research Program of China(Grant No.2011CB606402)the National Natural Science Foundation of China(Grant No.51071091)
文摘An Ni-AI-Co system embedded-atom-method potential is constructed for the γ(Ni)/γ'(Ni3A1) superalloy based on experiments and first-principles calculations. The stacking fault energies (SFEs) of the Ni(Co, A1) random solid solutions are calculated as a function of the concentrations of Co and A1. The calculated SFEs decrease with increasing concentrations of Co and A1, which is consistent with the experimental results. The embedding energy term in the present potential has an important influence on the SFEs of the random solid solutions. The cross-slip processes of a screw dislocation in homogenous Ni(Co) solid solutions are simulated using the present potential and the nudged elastic band method. The cross-slip activation energies increase with increasing Co concentration, which implies that the creep resistance of γ(Ni) may be improved by the addition of Co.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51772317,11604356,and 11704394)
文摘Graphene with a Dirac cone-like electronic structure has been extensively studied because of its novel transport properties and potential application for future electronic devices.For epitaxially grown graphene,the process conditions and the microstructures are strongly dependent on various substrate materials with different lattice constants and interface energies.Utilizing angle-resolved photoemission spectroscopy,here we report an investigation of the electronic structure of single-crystalline graphene grown on Cu/Ni(111)alloy film by chemical vapor deposition.With a relatively low growth temperature,graphene on Cu/Ni(111)exhibits a Dirac cone-like dispersion comparable to that of graphene grown on Cu(111).The linear dispersions forming Dirac cone are as wide as 2 e V,with the Fermi velocity of approximately 1.1×10^6 m/s.Dirac cone opens a gap of approximately 152 meV at the binding energy of approximately 304 meV.Our findings would promote the study of engineering of graphene on different substrate materials.
基金Project supported by the Open Project of Key Laboratory for Magnetism and Magnetic Materials of the Ministry of Education,Lanzhou University(Grant No.LZUMMM2012003)the Open Project of Key Laboratory of Beam Technology and Material Modification of Ministry of Education,Beijing Normal University(Grant No.201204)the Open Project of State Key Laboratory of Crystal Material,Shandong University,China(Grant No.KF1311)
文摘Remarkable room temperature ferromagnetism in pure single-crystal rutile TiO2 (001) samples irradiated by D-D neutron has been investigated. By combining X-ray diffraction and positron annihilation lifetime, the contracted lattice has been clearly identified in irradiated TiO2, where Ti4+ ions can be easily reduced to the state of Ti3+. As there were no magnetic impurities that could contaminate the samples during the whole procedure, some Ti3+ ions reside on interstitial or substituted sites accompanied by oxygen vacancies should be responsible for the ferromagnetism.
基金This work was supported by the Postdoctoral Science Foundation of China under Grant No.2004035688.
文摘Finite element (FE) analysis was employed to investigate the casting microcrack and micropore growth in nickel-base single-crystal superalloys DD3. Based on the finite deformation rate-dependent crystallographic constitutive equation, the simulations of casting microcrack and micropore growth in three-dimensional unit cell model were carried out in a range of parameters including stress triaxiality, Lode parameter and type of activated slip systems. The FE results show that the stress triaxiality has profound effects on growth behavior, and the Lode parameter is also important for the casting microcrack and micropore growth. The type of operative slip systems has remarkable effect on casting microcrack and micropore growth, so the life of single- crystal component is associated with the type of activated slip systems, which is related to Schmid factor and the number of activated slip systems. The growth comparison between microcrack and micropore reveals that when the material is subjected to large deformation, the growth rate of microcrack is faster than that of micropore, i.e. microcrack is more dangerous than micropore; the microcrack is easier to result in brittle fracture than micropore. The stress triaxiality and Lode parameter have strong influence on the growth of microcrack and micropore.
基金Supported by the National Basic Research Program of China under Grant Nos 2012CB921700 and 2011CBA00112the National Natural Science Foundation of China under Grant Nos 11034012 and 11190024
文摘The magnetic structure of the spin-chain antiferromagnet SrCo2 V208 is determined by single-crystal neutron diffraction experiment. The system undergoes a long-range magnetic order below the critical temperature TN=4.96 K. The moment of 2.16#B per Co at 1.6K in the screw chain running along the c axis Mternates in the c axis. The moments of neighboring screw chains are arranged antiferromagnetically along one in-plane axis and ferromagnetieally Monk the other in-plane axis. This magnetic configuration breaks the four-fold symmetry of the tetragonM crystal structure and leads to two equally populated magnetic twins with the antiferromagnetic vector in the a or b axis. The very similar magnetic state to the isostructural BaCo2 V~ 08 warrants SrCo2 V2 08 as another interesting half-integer spin-chain antiferromagnet for investigation on quantum antiferromagnetism.