Ion beam-induced luminescence(IBIL) experiments were performed to investigate the in situ luminescence of GaN/Al_(2)O_(3) at varying ion energies,which allowed for the measurement of defects at different depths within...Ion beam-induced luminescence(IBIL) experiments were performed to investigate the in situ luminescence of GaN/Al_(2)O_(3) at varying ion energies,which allowed for the measurement of defects at different depths within the material.The energies of H^(+)were set to 500 keV,640 keV and 2 MeV,the Bragg peaks of which correspond to the GaN film,GaN/Al_(2)O_(3) heterojunction and Al_(2)O_(3) substrate,respectively.A photoluminescence measurement at 250 K was also performed for comparison,during which only near band edge(NBE) and yellow band luminescence in the GaN film were observed.The evolution of the luminescence of the NBE and yellow band in the GaN film was discussed,and both exhibited a decrease with the fluence of H^(+).Additionally,the luminescence of F centers,induced by oxygen vacancies,and Cr^(3+),resulting from the ^(2)E →^(4)A_(2) radiative transition in Al_(2)O_(3),were measured using 2 MeV H^(+).The luminescence intensity of F centers increases gradually with the fluence of H^(+).The luminescence evolution of Cr^(3+)is consistent with a yellow band center,attributed to its weak intensity,and it is situated within the emission band of the yellow band in the GaN film.Our results show that IBIL measurement can effectively detect the luminescence behavior of multilayer films by adjusting the ion energy.Luminescence measurement can be excited by various techniques,but IBIL can satisfy in situ luminescence measurement,and multilayer structural materials of tens of micrometers can be measured through IBIL by adjusting the energy of the inducing ions.The evolution of defects at different layers with ion fluence can be obtained.展开更多
MoS_(2)targets were irradiated by infra-red(IR)pulsed laser in a high vacuum to determine hot plasma parameters,atomic,molecular and ion emission,and angular and charge state distributions.In this way,pulsed laser dep...MoS_(2)targets were irradiated by infra-red(IR)pulsed laser in a high vacuum to determine hot plasma parameters,atomic,molecular and ion emission,and angular and charge state distributions.In this way,pulsed laser deposition(PLD)of thin films on graphene oxide substrates was also realized.An Nd:YAG laser,operating at the 1064 nm wavelength with a 5 ns pulse duration and up to a 1 J pulse energy,in a single pulse or at a 10 Hz repetition rate,was employed.Ablation yield was measured as a function of the laser fluence.Plasma was characterized using different analysis techniques,such as time-of-flight measurements,quadrupole mass spectrometry and fast CCD visible imaging.The so-produced films were characterized by composition,thickness,roughness,wetting ability,and morphology.When compared to the MoS_(2)targets,they show a slight decrease of S with respect to Mo,due to higher ablation yield,low fusion temperature and high sublimation in vacuum.The pulsed IR laser deposited Mo Sx(with 1<x<2)films are uniform,with a thickness of about 130 nm,a roughness of about 50 nm and a higher wettability than the MoS_(2)targets.Some potential applications of the pulsed IR laser-deposited Mo Sx films are also presented and discussed.展开更多
Half-integer microwave induced steps(Shapiro steps)have been observed in many different Josephson junction systems,which have attracted a lot of attention because they signify the deviation of current phase relation(C...Half-integer microwave induced steps(Shapiro steps)have been observed in many different Josephson junction systems,which have attracted a lot of attention because they signify the deviation of current phase relation(CPR)and uncover many unconventional physical properties.In this article,we first report the discovery of half-integer Shapiro steps in MgB_(2)focused He ion beam(He-FIB)Josephson junctions.The half-integer steps'dependence on microwave frequency,temperature,microwave power,and magnetic field is also analyzed.We find that the existence of half-integer steps can be controlled by the magnetic field periodically,which is similar to that of high temperature superconductor(HTS)grain boundary junctions,and the similarity of the microstructures between gain boundary junctions and He-FIB junctions is discussed.As a consequence,we mainly attribute the physical origin of half-integer steps in MgB_(2)He-FIB junctions to the model that a He-FIB junction is analogous to a parallel junctions'array.Our results show that He-FIB technology is a promising platform for researching CPR in junctions made of different superconductors.展开更多
Josephson junction plays a key role not only in studying the basic physics of unconventional iron-based superconductors but also in realizing practical application of thin-film based devices,therefore the preparation ...Josephson junction plays a key role not only in studying the basic physics of unconventional iron-based superconductors but also in realizing practical application of thin-film based devices,therefore the preparation of high-quality iron pnictide Josephson junctions is of great importance.In this work,we have successfully fabricated Josephson junctions from Co-doped BaFe_(2)As_(2)thin films using a direct junction fabrication technique which utilizes high energy focused helium ion beam(FHIB).The electrical transport properties were investigated for junctions fabricated with various He^(+)irradiation doses.The junctions show sharp superconducting transition around 24 K with a narrow transition width of 2.5 K,and a dose correlated foot-structure resistance which corresponds to the effective tuning of junction properties by He^(+)irradiation.Significant J_c suppression by more than two orders of magnitude can be achieved by increasing the He^(+)irradiation dose,which is advantageous for the realization of low noise ion pnictide thin film devices.Clear Shapiro steps are observed under 10 GHz microwave irradiation.The above results demonstrate the successful fabrication of high quality and controllable Co-doped BaFe_(2)As_(2)Josephson junction with high reproducibility using the FHIB technique,laying the foundation for future investigating the mechanism of iron-based superconductors,and also the further implementation in various superconducting electronic devices.展开更多
The large volumetric variations experienced by metal selenides within conversion reaction result in inferior rate capability and cycling stability,ultimately hindering the achievement of superior electrochemical perfo...The large volumetric variations experienced by metal selenides within conversion reaction result in inferior rate capability and cycling stability,ultimately hindering the achievement of superior electrochemical performance.Herein,metallic Cu_(2)Se encapsulated with N-doped carbon(Cu_(2)Se@NC)was prepared using Cu_(2)O nanocubes as templates through a combination of dopamine polymerization and hightemperature selenization.The unique nanocubic structure and uniform N-doped carbon coating could shorten the ion transport distance,accelerate electron/charge diffusion,and suppress volume variation,ultimately ensuring Cu_(2)Se@NC with excellent electrochemical performance in sodium ion batteries(SIBs)and potassium ion batteries(PIBs).The composite exhibited excellent rate performance(187.7 mA h g^(-1)at 50 A g^(-1)in SIBs and 179.4 mA h g^(-1)at 5 A g^(-1)in PIBs)and cyclic stability(246,8 mA h g^(-1)at 10 A g^(-1)in SIBs over 2500 cycles).The reaction mechanism of intercalation combined with conversion in both SIBs and PIBs was disclosed by in situ X-ray diffraction(XRD)and ex situ transmission electron microscope(TEM).In particular,the final products in PIBs of K_(2)Se and K_(2)Se_(3)species were determined after discharging,which is different from that in SIBs with the final species of Na_(2)Se.The density functional theory calculation showed that carbon induces strong coupling and charge interactions with Cu_(2)Se,leading to the introduction of built-in electric field on heterojunction to improve electron mobility.Significantly,the theoretical calculations discovered that the underlying cause for the relatively superior rate capability in SIBs to that in PIBs is the agile Na~+diffusion with low energy barrier and moderate adsorption energy.These findings offer theoretical support for in-depth understanding of the performance differences of Cu-based materials in different ion storage systems.展开更多
Planar Na ion micro-supercapacitors(NIMSCs) that offer both high energy density and power density are deemed to a promising class of miniaturized power sources for wearable and portable microelectron-ics. Nevertheless...Planar Na ion micro-supercapacitors(NIMSCs) that offer both high energy density and power density are deemed to a promising class of miniaturized power sources for wearable and portable microelectron-ics. Nevertheless, the development of NIMSCs are hugely impeded by the low capacity and sluggish Na ion kinetics in the negative electrode.Herein, we demonstrate a novel carbon-coated Nb_(2)O_5 microflower with a hierarchical structure composed of vertically intercrossed and porous nanosheets, boosting Na ion storage performance. The unique structural merits, including uniform carbon coating, ultrathin nanosheets and abun-dant pores, endow the Nb_(2)O_5 microflower with highly reversible Na ion storage capacity of 245 mAh g^(-1) at 0.25 C and excellent rate capability.Benefiting from high capacity and fast charging of Nb_(2)O_5 microflower, the planar NIMSCs consisted of Nb_(2)O_5 negative electrode and activated car-bon positive electrode deliver high areal energy density of 60.7 μWh cm^(-2),considerable voltage window of 3.5 V and extraordinary cyclability. Therefore, this work exploits a structural design strategy towards electrode materials for application in NIMSCs, holding great promise for flexible microelectronics.展开更多
The efficient extraction of sodium(Na^(+))and lithium(Li^(+))from seawater and salt lakes is increasingly demanding due to their great application value in chemical industries.However,coexisting cations such as divale...The efficient extraction of sodium(Na^(+))and lithium(Li^(+))from seawater and salt lakes is increasingly demanding due to their great application value in chemical industries.However,coexisting cations such as divalent calcium(Ca^(2+))and magnesium(Mg^(2+))ions are at the subnanometer scale in diameter,similar to target monovalent ions,making ion separation a great challenge.Here,we propose a simple and fast secondary growth method for the preparation of MIL-53(Al)-NH_(2)membranes on the surface of anodic aluminum oxide.Such membranes contain angstrom-scale(~7Å)channels for the entrance of small monovalent ions and water molecules,endowing the selectivities for monovalent cations over divalent cations and water over salt molecules.The resulting high-connectivity MIL-53(Al)-NH_(2)membranes exhibit excellent ion separation performance(a selectivity of 121.42 for Na^(+)/Ca^(2+)and 93.81 for Li^(+)/Mg^(2+))and desalination performance(a water/salt selectivity of up to 5196).This work highlights metal–organic framework membranes as potential candidates for realizing ion separation and desalination in liquid treatment.展开更多
Ba^(2+)pre-crosslinked carrageenan fiber(Ba/CAF)was prepared by adding a small amount of Ba^(2+) to the carrageenan(CA)solution as the spinning solution.Ba/CAF-n/A,Ba/CAF-n/B and Ba/CAF-n/C were prepared with ethanol ...Ba^(2+)pre-crosslinked carrageenan fiber(Ba/CAF)was prepared by adding a small amount of Ba^(2+) to the carrageenan(CA)solution as the spinning solution.Ba/CAF-n/A,Ba/CAF-n/B and Ba/CAF-n/C were prepared with ethanol solution(combine A),high concentration BaCl_(2)solution(combine B)and low concentration BaCl_(2)solution(combine C),as coagulation bath and stretch bath,respectively.The combination of coagulation bath and stretch bath suitable for Ba^(2+) pre-crosslinking wet spinning was screened.The results showed that Ba^(2+) can induce the birefringence of the CA molecular chain,and the Ba^(2+) pre-crosslinking effect is the best when the CA mass fraction is 8.0 wt%.From the perspective of production safety,fiber performance and spinning cost,the coagulation bath of 3.5 wt%BaCl_(2)solution and stretch bath of 1.7 wt%BaCl_(2)solution,that is,combination C with low concentration BaCl_(2)solution,is the best choice.Ba/CAF-8.0/C was obtained under the best conditions.The linear intensity,water absorption and flame retardancy study showed that the breaking strength of Ba/CAF-8.0/C is as high as 1.61 cN/dtex,the water absorption was 649.2%and 574.3%,in deionized water and normal saline,respectively,and the LOI value reached 32.展开更多
Magnesium ion batteries(MIBs)are a potential field for the energy storage of the future but are restricted by insufficient rate capability and rapid capacity degradation.Magnesium-sodium hybrid ion batteries(MSHBs)are...Magnesium ion batteries(MIBs)are a potential field for the energy storage of the future but are restricted by insufficient rate capability and rapid capacity degradation.Magnesium-sodium hybrid ion batteries(MSHBs)are an effective way to address these problems.Here,we report a new type of MSHBs that use layered sodium vanadate((Na,Mn)V_(8)O_(20)·5H_(2)O,Mn-NVO)cathodes coupled with an organic 3,4,9,10-perylenetetracarboxylic diimide(PTCDI)anode in Mg^(2+)/Na^(+)hybrid electrolytes.During electrochemical cycling,Mg^(2+)and Na^(+)co-participate in the cathode reactions,and the introduction of Na^(+)promotes the structural stability of the Mn-NVO cathode,as cleared by several ex-situ characterizations.Consequently,the Mn-NVO cathode presents great specific capacity(249.9 mA h g^(−1)at 300 mA g^(−1))and cycling(1500 cycles at 1500 mA g^(−1))in the Mg^(2+)/Na^(+)hybrid electrolytes.Besides,full battery displays long lifespan with 10,000 cycles at 1000 mA g^(−1).The rate performance and cycling stability of MSHBs have been improved by an economical and scalable method,and the mechanism for these improvements is discussed.展开更多
采用溶胶-凝胶法制备出Y_(2-2 x)MgTiO_(6)∶2 x Eu^(3+)(YMT∶2 x Eu^(3+),0≤x≤0.11)新型红色荧光粉。通过X射线衍射仪(XRD)检测样品的纯度,结果显示YMT∶Eu^(3+)样品属于单斜晶系,空间群为P21/n,无其他杂相。扫描电子显微镜(SEM)照...采用溶胶-凝胶法制备出Y_(2-2 x)MgTiO_(6)∶2 x Eu^(3+)(YMT∶2 x Eu^(3+),0≤x≤0.11)新型红色荧光粉。通过X射线衍射仪(XRD)检测样品的纯度,结果显示YMT∶Eu^(3+)样品属于单斜晶系,空间群为P21/n,无其他杂相。扫描电子显微镜(SEM)照片显示荧光粉为2μm的不规则颗粒。当激发波长为264 nm时,发射光谱出现四个尖锐的发射峰,分别位于591(^(5)D_(0)→^(7)F_(1))、619(^(5)D_(0)→^(7)F_(2))、657(^(5)D_(0)→^(7)F_(3))和693 nm(^(5)D_(0)→^(7)F_(4))。Eu^(3+)离子之间能量传递为电偶极子-电偶极子(d-d)相互作用。YMT∶0.14Eu^(3+)荧光粉的CIE色度坐标为(0.645,0.332),与红光标准色坐标(0.67,0.33)非常接近。变温PL光谱及热激活能计算结果显示荧光粉具有一定的热稳定性,因此YMT∶Eu^(3+)是一种具有潜在应用价值的LED红色荧光粉。展开更多
Developing efficient energy storage for sodium-ion batteries(SIBs)by creating high-performance heterojunctions and understanding their interfacial interaction at the atomic/molecular level holds promise but is also ch...Developing efficient energy storage for sodium-ion batteries(SIBs)by creating high-performance heterojunctions and understanding their interfacial interaction at the atomic/molecular level holds promise but is also challenging.Besides,sluggish reaction kinetics at low temperatures restrict the operation of SIBs in cold climates.Herein,cross-linking nanoarchitectonics of WS_(2)/Ti_(3)C_(2)T_(x) heterojunction,featuring built-in electric field(BIEF),have been developed,employing as a model to reveal the positive effect of heterojunction design and BIEF for modifying the reaction kinetics and electrochemical activity.Particularly,the theoretical analysis manifests the discrepancy in work functions leads to the electronic flow from the electron-rich Ti_(3)C_(2)T_(x) to layered WS_(2),spontaneously forming the BIEF and“ion reservoir”at the heterogeneous interface.Besides,the generation of cross-linking pathways further promotes the transportation of electrons/ions,which guarantees rapid diffusion kinetics and excellent structure coupling.Consequently,superior sodium storage performance is obtained for the WS_(2)/Ti_(3)C_(2)T_(x) heterojunction,with only 0.2%decay per cycle at 5.0 A g^(-1)(25℃)up to 1000 cycles and a high capacity of 293.5 mA h g^(-1)(0.1A g^(-1)after 100 cycles)even at-20℃.Importantly,the spontaneously formed BIEF,accompanied by“ion reservoir”,in heterojunction provides deep understandings of the correlation between structure fabricated and performance obtained.展开更多
Sodium-ion batteries(SIBs)have rapidly risen to the forefront of energy storage systems as a promising supplementary for Lithium-ion batteries(LIBs).Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)as a common cathode of SIBs,featur...Sodium-ion batteries(SIBs)have rapidly risen to the forefront of energy storage systems as a promising supplementary for Lithium-ion batteries(LIBs).Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)as a common cathode of SIBs,features the merits of high operating voltage,small volume change and favorable specific energy density.However,it suffers from poor cycling stability and rate performance induced by its low intrinsic conductivity.Herein,we propose an ingenious strategy targeting superior SIBs through cross-linked NVPF with multi-dimensional nanocarbon frameworks composed of amorphous carbon and carbon nanotubes(NVPF@C@CNTs).This rational design ensures favorable particle size for shortened sodium ion transmission pathway as well as improved electronic transfer network,thus leading to enhanced charge transfer kinetics and superior cycling stability.Benefited from this unique structure,significantly improved electrochemical properties are obtained,including high specific capacity(126.9 mAh g^(-1)at 1 C,1 C=128 mA g^(-1))and remarkably improved long-term cycling stability with 93.9%capacity retention after 1000 cycles at 20 C.The energy density of 286.8 Wh kg^(-1)can be reached for full cells with hard carbon as anode(NVPF@C@CNTs//HC).Additionally,the electrochemical performance of the full cell at high temperature is also investigated(95.3 mAh g^(-1)after 100 cycles at 1 C at 50℃).Such nanoscale dual-carbon networks engineering and thorough discussion of ion diffusion kinetics might make contributions to accelerating the process of phosphate cathodes in SIBs for large-scale energy storages.展开更多
In-situ XRD,^(31)P NMR and ^(23)Na NMR were used to analyze the interaction behavior of Na_(3)V_(2)(PO_(4))_(3) at low voltage,and then a new intercalation model was proposed.During the transition from Na_(3)V_(2)(PO_...In-situ XRD,^(31)P NMR and ^(23)Na NMR were used to analyze the interaction behavior of Na_(3)V_(2)(PO_(4))_(3) at low voltage,and then a new intercalation model was proposed.During the transition from Na_(3)V_(2)(PO_(4))_(3) to Na_(4)V_(2)(PO_(4))_(3),Na ions insert into M1,M2 and M3 sites simultaneously.Afterwards,during the transition of Na_(4)V_(2)(PO_(4))_(3)to Na_(5)V_(2)(PO_(4))_(3),Na ions mainly insert into M3 site.展开更多
Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and on...Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and only a limited candidates have been reported so far.In this work,we found for the first time that a continuous solid solution,Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2)(0≤α≤1,could be obtained by mutual substitution of cations at center‐symmetric Na3 and Na4 sites while keeping the crystal building blocks of anionic P_(2)O_(7) unchanged.In particular,a novel off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)is thus proposed,and its structure,energy storage mechanism,and electrochemical performance are extensively investigated to unveil the structure–function relationship.The as‐prepared off‐stoichiometric electrode delivers appealing performance with a reversible discharge capacity of 83 mAh g^(−1),a working voltage of 2.9 V(vs.Na^(+)/Na),the retention of 89.2%of the initial capacity after 500 cycles,and enhanced rate capability of 51 mAh g^(−1)at a current density of 1600 mA g^(−1).This research shows that sodium ferric pyrophosphate could form extended solid solution composition and promising phase is concealed in the range of Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2),offering more chances for exploration of new cathode materials for the construction of high‐performance SIBs.展开更多
Vanadium oxide cathode materials with stable crystal structure and fast Zn^(2+)storage capabilities are extremely important to achieving outstanding electrochemical performance in aqueous zinc‐ion batteries.In this w...Vanadium oxide cathode materials with stable crystal structure and fast Zn^(2+)storage capabilities are extremely important to achieving outstanding electrochemical performance in aqueous zinc‐ion batteries.In this work,a one‐step hydrothermal method was used to manipulate the bimetallic ion intercalation into the interlayer of vanadium oxide.The pre‐intercalated Cu ions act as pillars to pin the vanadium oxide(V‐O)layers,establishing stabilized two‐dimensional channels for fast Zn^(2+)diffusion.The occupation of Mn ions between V‐O interlayer further expands the layer spacing and increases the concentration of oxygen defects(Od),which boosts the Zn^(2+)diffusion kinetics.As a result,as‐prepared Cu_(0.17)Mn_(0.03)V_(2)O_(5−□)·2.16H_(2)O cathode shows outstanding Zn‐storage capabilities under room‐and lowtemperature environments(e.g.,440.3 mAh g^(−1)at room temperature and 294.3 mAh g^(−1)at−60°C).Importantly,it shows a long cycling life and high capacity retention of 93.4%over 2500 cycles at 2 A g^(−1)at−60°C.Furthermore,the reversible intercalation chemistry mechanisms during discharging/charging processes were revealed via operando X‐ray powder diffraction and ex situ Raman characterizations.The strategy of a couple of 3d transition metal doping provides a solution for the development of superior room‐/lowtemperature vanadium‐based cathode materials.展开更多
文摘Ion beam-induced luminescence(IBIL) experiments were performed to investigate the in situ luminescence of GaN/Al_(2)O_(3) at varying ion energies,which allowed for the measurement of defects at different depths within the material.The energies of H^(+)were set to 500 keV,640 keV and 2 MeV,the Bragg peaks of which correspond to the GaN film,GaN/Al_(2)O_(3) heterojunction and Al_(2)O_(3) substrate,respectively.A photoluminescence measurement at 250 K was also performed for comparison,during which only near band edge(NBE) and yellow band luminescence in the GaN film were observed.The evolution of the luminescence of the NBE and yellow band in the GaN film was discussed,and both exhibited a decrease with the fluence of H^(+).Additionally,the luminescence of F centers,induced by oxygen vacancies,and Cr^(3+),resulting from the ^(2)E →^(4)A_(2) radiative transition in Al_(2)O_(3),were measured using 2 MeV H^(+).The luminescence intensity of F centers increases gradually with the fluence of H^(+).The luminescence evolution of Cr^(3+)is consistent with a yellow band center,attributed to its weak intensity,and it is situated within the emission band of the yellow band in the GaN film.Our results show that IBIL measurement can effectively detect the luminescence behavior of multilayer films by adjusting the ion energy.Luminescence measurement can be excited by various techniques,but IBIL can satisfy in situ luminescence measurement,and multilayer structural materials of tens of micrometers can be measured through IBIL by adjusting the energy of the inducing ions.The evolution of defects at different layers with ion fluence can be obtained.
基金supported by OP RDE,MEYS,Czech Republic under the project CANAM OP(No.CZ.02.1.01/0.0/0.0/16_013/0001812)by the Czech Science Foundation GACR(No.23-06702S)。
文摘MoS_(2)targets were irradiated by infra-red(IR)pulsed laser in a high vacuum to determine hot plasma parameters,atomic,molecular and ion emission,and angular and charge state distributions.In this way,pulsed laser deposition(PLD)of thin films on graphene oxide substrates was also realized.An Nd:YAG laser,operating at the 1064 nm wavelength with a 5 ns pulse duration and up to a 1 J pulse energy,in a single pulse or at a 10 Hz repetition rate,was employed.Ablation yield was measured as a function of the laser fluence.Plasma was characterized using different analysis techniques,such as time-of-flight measurements,quadrupole mass spectrometry and fast CCD visible imaging.The so-produced films were characterized by composition,thickness,roughness,wetting ability,and morphology.When compared to the MoS_(2)targets,they show a slight decrease of S with respect to Mo,due to higher ablation yield,low fusion temperature and high sublimation in vacuum.The pulsed IR laser deposited Mo Sx(with 1<x<2)films are uniform,with a thickness of about 130 nm,a roughness of about 50 nm and a higher wettability than the MoS_(2)targets.Some potential applications of the pulsed IR laser-deposited Mo Sx films are also presented and discussed.
基金supported by the National Natural Science Foundation of China (Grant No.12104016)the National Key Research and Development Program of China (Grant No.2020YFF01014706)。
文摘Half-integer microwave induced steps(Shapiro steps)have been observed in many different Josephson junction systems,which have attracted a lot of attention because they signify the deviation of current phase relation(CPR)and uncover many unconventional physical properties.In this article,we first report the discovery of half-integer Shapiro steps in MgB_(2)focused He ion beam(He-FIB)Josephson junctions.The half-integer steps'dependence on microwave frequency,temperature,microwave power,and magnetic field is also analyzed.We find that the existence of half-integer steps can be controlled by the magnetic field periodically,which is similar to that of high temperature superconductor(HTS)grain boundary junctions,and the similarity of the microstructures between gain boundary junctions and He-FIB junctions is discussed.As a consequence,we mainly attribute the physical origin of half-integer steps in MgB_(2)He-FIB junctions to the model that a He-FIB junction is analogous to a parallel junctions'array.Our results show that He-FIB technology is a promising platform for researching CPR in junctions made of different superconductors.
基金Project supported by the National Key Research and Development Program of China (Grant Nos.2020YFF01014706 and 2017YFC0601901)the National Natural Science Foundation of China (Grant Nos.61571019 and 52177026)。
文摘Josephson junction plays a key role not only in studying the basic physics of unconventional iron-based superconductors but also in realizing practical application of thin-film based devices,therefore the preparation of high-quality iron pnictide Josephson junctions is of great importance.In this work,we have successfully fabricated Josephson junctions from Co-doped BaFe_(2)As_(2)thin films using a direct junction fabrication technique which utilizes high energy focused helium ion beam(FHIB).The electrical transport properties were investigated for junctions fabricated with various He^(+)irradiation doses.The junctions show sharp superconducting transition around 24 K with a narrow transition width of 2.5 K,and a dose correlated foot-structure resistance which corresponds to the effective tuning of junction properties by He^(+)irradiation.Significant J_c suppression by more than two orders of magnitude can be achieved by increasing the He^(+)irradiation dose,which is advantageous for the realization of low noise ion pnictide thin film devices.Clear Shapiro steps are observed under 10 GHz microwave irradiation.The above results demonstrate the successful fabrication of high quality and controllable Co-doped BaFe_(2)As_(2)Josephson junction with high reproducibility using the FHIB technique,laying the foundation for future investigating the mechanism of iron-based superconductors,and also the further implementation in various superconducting electronic devices.
基金The Natural Science Foundation of Henan Province(222300420083)the Opening Foundation of State Key Laboratory of Chemistry and Utilization of Carbon-based Energy Resource of Xinjiang University(KFKT2021004)。
文摘The large volumetric variations experienced by metal selenides within conversion reaction result in inferior rate capability and cycling stability,ultimately hindering the achievement of superior electrochemical performance.Herein,metallic Cu_(2)Se encapsulated with N-doped carbon(Cu_(2)Se@NC)was prepared using Cu_(2)O nanocubes as templates through a combination of dopamine polymerization and hightemperature selenization.The unique nanocubic structure and uniform N-doped carbon coating could shorten the ion transport distance,accelerate electron/charge diffusion,and suppress volume variation,ultimately ensuring Cu_(2)Se@NC with excellent electrochemical performance in sodium ion batteries(SIBs)and potassium ion batteries(PIBs).The composite exhibited excellent rate performance(187.7 mA h g^(-1)at 50 A g^(-1)in SIBs and 179.4 mA h g^(-1)at 5 A g^(-1)in PIBs)and cyclic stability(246,8 mA h g^(-1)at 10 A g^(-1)in SIBs over 2500 cycles).The reaction mechanism of intercalation combined with conversion in both SIBs and PIBs was disclosed by in situ X-ray diffraction(XRD)and ex situ transmission electron microscope(TEM).In particular,the final products in PIBs of K_(2)Se and K_(2)Se_(3)species were determined after discharging,which is different from that in SIBs with the final species of Na_(2)Se.The density functional theory calculation showed that carbon induces strong coupling and charge interactions with Cu_(2)Se,leading to the introduction of built-in electric field on heterojunction to improve electron mobility.Significantly,the theoretical calculations discovered that the underlying cause for the relatively superior rate capability in SIBs to that in PIBs is the agile Na~+diffusion with low energy barrier and moderate adsorption energy.These findings offer theoretical support for in-depth understanding of the performance differences of Cu-based materials in different ion storage systems.
基金financially supported by the National Natural Science Foundation of China (Grants. 22075279, 22279137, 22125903, 22109040)National Key R&D Program of China (Grant 2022YFA1504100)+2 种基金Dalian Innovation Support Plan for High Level Talents (2019RT09)Dalian National Labo- ratory For Clean Energy (DNL), CAS, DNL Cooperation Fund, CAS (DNL202016, DNL202019), DICP (DICP I2020032)the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy (YLU-DNL Fund 2021002, YLU- DNL Fund 2021009)。
文摘Planar Na ion micro-supercapacitors(NIMSCs) that offer both high energy density and power density are deemed to a promising class of miniaturized power sources for wearable and portable microelectron-ics. Nevertheless, the development of NIMSCs are hugely impeded by the low capacity and sluggish Na ion kinetics in the negative electrode.Herein, we demonstrate a novel carbon-coated Nb_(2)O_5 microflower with a hierarchical structure composed of vertically intercrossed and porous nanosheets, boosting Na ion storage performance. The unique structural merits, including uniform carbon coating, ultrathin nanosheets and abun-dant pores, endow the Nb_(2)O_5 microflower with highly reversible Na ion storage capacity of 245 mAh g^(-1) at 0.25 C and excellent rate capability.Benefiting from high capacity and fast charging of Nb_(2)O_5 microflower, the planar NIMSCs consisted of Nb_(2)O_5 negative electrode and activated car-bon positive electrode deliver high areal energy density of 60.7 μWh cm^(-2),considerable voltage window of 3.5 V and extraordinary cyclability. Therefore, this work exploits a structural design strategy towards electrode materials for application in NIMSCs, holding great promise for flexible microelectronics.
基金supported by the Fundamental Research Funds for the Central Universities(WK2060000030)USTC Research Funds of the Double First Class Initiative(YD2060002022)Major Science and Technology Innovation Projects in Shandong Province(2022CXGC020415).
文摘The efficient extraction of sodium(Na^(+))and lithium(Li^(+))from seawater and salt lakes is increasingly demanding due to their great application value in chemical industries.However,coexisting cations such as divalent calcium(Ca^(2+))and magnesium(Mg^(2+))ions are at the subnanometer scale in diameter,similar to target monovalent ions,making ion separation a great challenge.Here,we propose a simple and fast secondary growth method for the preparation of MIL-53(Al)-NH_(2)membranes on the surface of anodic aluminum oxide.Such membranes contain angstrom-scale(~7Å)channels for the entrance of small monovalent ions and water molecules,endowing the selectivities for monovalent cations over divalent cations and water over salt molecules.The resulting high-connectivity MIL-53(Al)-NH_(2)membranes exhibit excellent ion separation performance(a selectivity of 121.42 for Na^(+)/Ca^(2+)and 93.81 for Li^(+)/Mg^(2+))and desalination performance(a water/salt selectivity of up to 5196).This work highlights metal–organic framework membranes as potential candidates for realizing ion separation and desalination in liquid treatment.
基金supported by the Program of the National Natural Science Foundation of China(52173037)Natural Science Foundation of Shandong Province(ZR2020ME061)+1 种基金State Key Laboratory of Bio-Fibers and Eco-Textiles of Qingdao University(ZFT201810,ZKT17,TSKT202107)the Program for Changjiang Scholars and Innovative Research Team in University of Ministry of Education of China(IRT14R30).
文摘Ba^(2+)pre-crosslinked carrageenan fiber(Ba/CAF)was prepared by adding a small amount of Ba^(2+) to the carrageenan(CA)solution as the spinning solution.Ba/CAF-n/A,Ba/CAF-n/B and Ba/CAF-n/C were prepared with ethanol solution(combine A),high concentration BaCl_(2)solution(combine B)and low concentration BaCl_(2)solution(combine C),as coagulation bath and stretch bath,respectively.The combination of coagulation bath and stretch bath suitable for Ba^(2+) pre-crosslinking wet spinning was screened.The results showed that Ba^(2+) can induce the birefringence of the CA molecular chain,and the Ba^(2+) pre-crosslinking effect is the best when the CA mass fraction is 8.0 wt%.From the perspective of production safety,fiber performance and spinning cost,the coagulation bath of 3.5 wt%BaCl_(2)solution and stretch bath of 1.7 wt%BaCl_(2)solution,that is,combination C with low concentration BaCl_(2)solution,is the best choice.Ba/CAF-8.0/C was obtained under the best conditions.The linear intensity,water absorption and flame retardancy study showed that the breaking strength of Ba/CAF-8.0/C is as high as 1.61 cN/dtex,the water absorption was 649.2%and 574.3%,in deionized water and normal saline,respectively,and the LOI value reached 32.
基金the financial support from the National Natural Science Foundation of China, China (22005207, 52261160384)the Guangdong Basic and Applied Basic Research Foundation, Guangdong Province, China (2019A1515011819)+2 种基金the Outstanding Youth Basic Research Project of Shenzhen, Shenzhen, China (RCYX20221008092934093)the Joint Funds of the National Natural Science Foundation of China, China (U22A20140)the Science and Technology Development Fund, Macao SAR (0090/2021/A2 and 0049/2021/AGJ)
文摘Magnesium ion batteries(MIBs)are a potential field for the energy storage of the future but are restricted by insufficient rate capability and rapid capacity degradation.Magnesium-sodium hybrid ion batteries(MSHBs)are an effective way to address these problems.Here,we report a new type of MSHBs that use layered sodium vanadate((Na,Mn)V_(8)O_(20)·5H_(2)O,Mn-NVO)cathodes coupled with an organic 3,4,9,10-perylenetetracarboxylic diimide(PTCDI)anode in Mg^(2+)/Na^(+)hybrid electrolytes.During electrochemical cycling,Mg^(2+)and Na^(+)co-participate in the cathode reactions,and the introduction of Na^(+)promotes the structural stability of the Mn-NVO cathode,as cleared by several ex-situ characterizations.Consequently,the Mn-NVO cathode presents great specific capacity(249.9 mA h g^(−1)at 300 mA g^(−1))and cycling(1500 cycles at 1500 mA g^(−1))in the Mg^(2+)/Na^(+)hybrid electrolytes.Besides,full battery displays long lifespan with 10,000 cycles at 1000 mA g^(−1).The rate performance and cycling stability of MSHBs have been improved by an economical and scalable method,and the mechanism for these improvements is discussed.
文摘采用溶胶-凝胶法制备出Y_(2-2 x)MgTiO_(6)∶2 x Eu^(3+)(YMT∶2 x Eu^(3+),0≤x≤0.11)新型红色荧光粉。通过X射线衍射仪(XRD)检测样品的纯度,结果显示YMT∶Eu^(3+)样品属于单斜晶系,空间群为P21/n,无其他杂相。扫描电子显微镜(SEM)照片显示荧光粉为2μm的不规则颗粒。当激发波长为264 nm时,发射光谱出现四个尖锐的发射峰,分别位于591(^(5)D_(0)→^(7)F_(1))、619(^(5)D_(0)→^(7)F_(2))、657(^(5)D_(0)→^(7)F_(3))和693 nm(^(5)D_(0)→^(7)F_(4))。Eu^(3+)离子之间能量传递为电偶极子-电偶极子(d-d)相互作用。YMT∶0.14Eu^(3+)荧光粉的CIE色度坐标为(0.645,0.332),与红光标准色坐标(0.67,0.33)非常接近。变温PL光谱及热激活能计算结果显示荧光粉具有一定的热稳定性,因此YMT∶Eu^(3+)是一种具有潜在应用价值的LED红色荧光粉。
基金supported by the faculty startup funds from the Yangzhou Universitythe Natural Science Foundation of Jiangsu Province(BK20210821)+1 种基金the National Natural Science Foundation of China(22102141)the Lvyangjinfeng Talent Program of Yangzhou。
文摘Developing efficient energy storage for sodium-ion batteries(SIBs)by creating high-performance heterojunctions and understanding their interfacial interaction at the atomic/molecular level holds promise but is also challenging.Besides,sluggish reaction kinetics at low temperatures restrict the operation of SIBs in cold climates.Herein,cross-linking nanoarchitectonics of WS_(2)/Ti_(3)C_(2)T_(x) heterojunction,featuring built-in electric field(BIEF),have been developed,employing as a model to reveal the positive effect of heterojunction design and BIEF for modifying the reaction kinetics and electrochemical activity.Particularly,the theoretical analysis manifests the discrepancy in work functions leads to the electronic flow from the electron-rich Ti_(3)C_(2)T_(x) to layered WS_(2),spontaneously forming the BIEF and“ion reservoir”at the heterogeneous interface.Besides,the generation of cross-linking pathways further promotes the transportation of electrons/ions,which guarantees rapid diffusion kinetics and excellent structure coupling.Consequently,superior sodium storage performance is obtained for the WS_(2)/Ti_(3)C_(2)T_(x) heterojunction,with only 0.2%decay per cycle at 5.0 A g^(-1)(25℃)up to 1000 cycles and a high capacity of 293.5 mA h g^(-1)(0.1A g^(-1)after 100 cycles)even at-20℃.Importantly,the spontaneously formed BIEF,accompanied by“ion reservoir”,in heterojunction provides deep understandings of the correlation between structure fabricated and performance obtained.
基金financially supported by Science and Technology Foundation of Guizhou Province(QKHZC[2020]2Y037)the Science and Technology Innovation Program of Hunan Province(2020RC4005,2019RS1004)+2 种基金Research start-up funding from Central South University(202044019)Innovation Mover Program of Central South University(2020CX007)National Natural Science Foundation of China(U21A20284)
文摘Sodium-ion batteries(SIBs)have rapidly risen to the forefront of energy storage systems as a promising supplementary for Lithium-ion batteries(LIBs).Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)as a common cathode of SIBs,features the merits of high operating voltage,small volume change and favorable specific energy density.However,it suffers from poor cycling stability and rate performance induced by its low intrinsic conductivity.Herein,we propose an ingenious strategy targeting superior SIBs through cross-linked NVPF with multi-dimensional nanocarbon frameworks composed of amorphous carbon and carbon nanotubes(NVPF@C@CNTs).This rational design ensures favorable particle size for shortened sodium ion transmission pathway as well as improved electronic transfer network,thus leading to enhanced charge transfer kinetics and superior cycling stability.Benefited from this unique structure,significantly improved electrochemical properties are obtained,including high specific capacity(126.9 mAh g^(-1)at 1 C,1 C=128 mA g^(-1))and remarkably improved long-term cycling stability with 93.9%capacity retention after 1000 cycles at 20 C.The energy density of 286.8 Wh kg^(-1)can be reached for full cells with hard carbon as anode(NVPF@C@CNTs//HC).Additionally,the electrochemical performance of the full cell at high temperature is also investigated(95.3 mAh g^(-1)after 100 cycles at 1 C at 50℃).Such nanoscale dual-carbon networks engineering and thorough discussion of ion diffusion kinetics might make contributions to accelerating the process of phosphate cathodes in SIBs for large-scale energy storages.
基金supported by grants from the National Natural Science Foundation of China(No.22272055)multifunctional platform for innovation of ECNU(EPR).
文摘In-situ XRD,^(31)P NMR and ^(23)Na NMR were used to analyze the interaction behavior of Na_(3)V_(2)(PO_(4))_(3) at low voltage,and then a new intercalation model was proposed.During the transition from Na_(3)V_(2)(PO_(4))_(3) to Na_(4)V_(2)(PO_(4))_(3),Na ions insert into M1,M2 and M3 sites simultaneously.Afterwards,during the transition of Na_(4)V_(2)(PO_(4))_(3)to Na_(5)V_(2)(PO_(4))_(3),Na ions mainly insert into M3 site.
基金National Natural Science Foundation of China,Grant/Award Numbers:21972108,U20A20249,U22A20438Changzhou Science and Technology Bureau,Grant/Award Number:CM20223017Innovation and Technology Commission(ITC)of Hong Kong,The Innovation&Technology Fund(ITF)with Project No.ITS/126/21。
文摘Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and only a limited candidates have been reported so far.In this work,we found for the first time that a continuous solid solution,Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2)(0≤α≤1,could be obtained by mutual substitution of cations at center‐symmetric Na3 and Na4 sites while keeping the crystal building blocks of anionic P_(2)O_(7) unchanged.In particular,a novel off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)is thus proposed,and its structure,energy storage mechanism,and electrochemical performance are extensively investigated to unveil the structure–function relationship.The as‐prepared off‐stoichiometric electrode delivers appealing performance with a reversible discharge capacity of 83 mAh g^(−1),a working voltage of 2.9 V(vs.Na^(+)/Na),the retention of 89.2%of the initial capacity after 500 cycles,and enhanced rate capability of 51 mAh g^(−1)at a current density of 1600 mA g^(−1).This research shows that sodium ferric pyrophosphate could form extended solid solution composition and promising phase is concealed in the range of Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2),offering more chances for exploration of new cathode materials for the construction of high‐performance SIBs.
基金National Natural Science Foundation of China,Grant/Award Numbers:52372188,51902090,51922008,520721142023 Introduction of studying abroad talent program,the China Postdoctoral Science Foundation,Grant/Award Number:2019 M652546+3 种基金Xinxiang Major Science and Technology Projects,Grant/Award Number:21ZD001Henan Province Postdoctoral Start‐Up Foundation,Grant/Award Number:1901017Henan Center for Outstanding Overseas Scientists,Grant/Award Number:GZS2018003Overseas Expertise Introduction Project for Discipline Innovation,Grant/Award Number:D17007。
文摘Vanadium oxide cathode materials with stable crystal structure and fast Zn^(2+)storage capabilities are extremely important to achieving outstanding electrochemical performance in aqueous zinc‐ion batteries.In this work,a one‐step hydrothermal method was used to manipulate the bimetallic ion intercalation into the interlayer of vanadium oxide.The pre‐intercalated Cu ions act as pillars to pin the vanadium oxide(V‐O)layers,establishing stabilized two‐dimensional channels for fast Zn^(2+)diffusion.The occupation of Mn ions between V‐O interlayer further expands the layer spacing and increases the concentration of oxygen defects(Od),which boosts the Zn^(2+)diffusion kinetics.As a result,as‐prepared Cu_(0.17)Mn_(0.03)V_(2)O_(5−□)·2.16H_(2)O cathode shows outstanding Zn‐storage capabilities under room‐and lowtemperature environments(e.g.,440.3 mAh g^(−1)at room temperature and 294.3 mAh g^(−1)at−60°C).Importantly,it shows a long cycling life and high capacity retention of 93.4%over 2500 cycles at 2 A g^(−1)at−60°C.Furthermore,the reversible intercalation chemistry mechanisms during discharging/charging processes were revealed via operando X‐ray powder diffraction and ex situ Raman characterizations.The strategy of a couple of 3d transition metal doping provides a solution for the development of superior room‐/lowtemperature vanadium‐based cathode materials.