Orthorhombic Nb_(2)O_(5)(T-Nb_(2)O_(5))is attractive for fast-charging Li-ion batteries,but it is still hard to realize rapid charge transfer kinetics for Li-ion storage.Herein,F-doped T-Nb_(2)O_(5) microflowers(F-Nb_(...Orthorhombic Nb_(2)O_(5)(T-Nb_(2)O_(5))is attractive for fast-charging Li-ion batteries,but it is still hard to realize rapid charge transfer kinetics for Li-ion storage.Herein,F-doped T-Nb_(2)O_(5) microflowers(F-Nb_(2)O_(5))are rationally synthesized through topotactic conversion.Specifically,F-Nb_(2)O_(5) are assembled by single-crystal nanoflakes with nearly 97%exposed(100)facet,which maximizes the exposure of the feasible Li^(+)transport pathways along loosely packed 4g atomic layers to the electrolytes,thus effectively enhancing the Li^(+)-intercalation performance.Besides,the band gap of F-Nb_(2)O_(5) is reduced to 2.87 eV due to the doping of F atoms,leading to enhanced electrical conductivity.The synergetic effects between tailored exposed crystal facets,F-doping,and ultrathin building blocks,speed up the Li^(+)/electron transfer kinetics and improve the pseudocapacitive properties of F-Nb_(2)O_(5).Therefore,F-Nb_(2)O_(5) exhibit superior rate capability(210.8 and 164.9 mAh g^(-1) at 1 and 10 C,respectively)and good long-term 10 C cycling performance(132.7 mAh g^(-1) after 1500 cycles).展开更多
Sophisticated efficient electrocatalysts are essential to rectifying the shuttle effect and realizing the high performance of flexible lithium-sulfur batteries(LSBs).Phase transformation of MoSe_(2) from the 2H phase ...Sophisticated efficient electrocatalysts are essential to rectifying the shuttle effect and realizing the high performance of flexible lithium-sulfur batteries(LSBs).Phase transformation of MoSe_(2) from the 2H phase to the 1T phase has been proven to be a significant method to improve the catalytic activity.However,precisely controllable phase engineering of MoSe_(2) has rarely been reported.Herein,by in situ Li ions intercalation in MoSe_(2),a precisely controllable phase evolution from 2H-MoSe_(2) to 1T-MoSe_(2) was realized.More importantly,the definite functional relationship between cut-off voltage and phase structure was first identified for phase engineering through in situ observation and modulation methods.The sulfur host(CNFs/1T-MoSe_(2))presents high charge density,strong polysulfides adsorption,and catalytic kinetics.Moreover,Li-S cells based on it display capacity retention of 875.3mAh g^(-1) after 500 cycles at 1 C and an areal capacity of 8.71mAh cm^(-2) even at a high sulfur loading of 8.47mg cm^(-2).Furthermore,the flexible pouch cell exhibiting decent performance will endow a promising potential in the wearable energy storage field.This study proposes an effective strategy to precisely control the phase structure of MoSe_(2),which may provide the reference to fabricate the highly efficient electrocatalysts for LSBs and other energy systems.展开更多
Fault rupture propagation is more complex in the overlying soil with intercalation than in homogeneous soil,and it is challenging to simulate this phenomenon accurately using the finite element method.To address this ...Fault rupture propagation is more complex in the overlying soil with intercalation than in homogeneous soil,and it is challenging to simulate this phenomenon accurately using the finite element method.To address this issue,an improved nonlocal model that incorporates softening modulus modification is proposed.The methodology has the advantage that the solutions are independent of both mesh sizes and characteristic lengths,while maintaining objective softening rates of materials.Using the proposed methodology,a series of numerical simulations are conducted to investigate the effects of different mechanical parameters,such as elastic modulus,friction angle and dilation angle of the soil within the intercalation,as well as the impact of geometries,such as the depth and thickness of the intercalation,on the fault rupture progress.This study not only provides significant insights into the mechanisms of fault rupture propagation,specifically in relation to intercalations,but also shows a great value in promoting the current research on fault rupture.展开更多
Intercalation of insulating materials between epitaxial graphene and the metal substrates is highly demanded to restore the intrinsic properties of graphene,and thus essential for the graphene-based devices.Here we de...Intercalation of insulating materials between epitaxial graphene and the metal substrates is highly demanded to restore the intrinsic properties of graphene,and thus essential for the graphene-based devices.Here we demonstrate a successful solution for the intercalation of hafnium oxide into the interface between full-layer graphene and Ir(111)substrate.We first intercalate hafnium atoms beneath the epitaxial graphene.The intercalation of the hafnium atoms leads to the variation of the graphene moire superstructure periodicity,which is characterized by low-energy electron diffraction(LEED)and lowtemperature scanning tunneling microscopy(LT-STM).Subsequently,we introduce oxygen into the interface,resulting in oxidization of the intercalated hafnium.STM and Raman's characterizations reveal that the intercalated hafnium oxide layer could effectively decouple the graphene from the metallic substrate,while the graphene maintains its high quality.Our work suggests a high-k dielectric layer has been successfully intercalated between high-quality epitaxial graphene and metal substrate,providing a platform for applications of large-scale,high-quality graphene for electronic devices.展开更多
In-depth understanding of the electrolyte-dependent intercalation chemistry in batteries through direct operando/in situ characterizations is crucial for the development of the high-performance batteries.Herein,taking...In-depth understanding of the electrolyte-dependent intercalation chemistry in batteries through direct operando/in situ characterizations is crucial for the development of the high-performance batteries.Herein,taking the Al/graphite battery as a model system,the effect of electrolyte coordination structure on the intercalation processes has been investigated over the batteries with either 1-hexyl-3-methylimidazolium chloride(HMICl)-AlCl_(3) or 1-ethyl-3-methylimidazolium chloride(EMICl)-AlCl_(3) ionic liquid electrolyte using operando X-ray photoelectron spectroscopy(XPS)and X-ray diffraction.With a weaker anion-cation interaction in HMI-based electrolyte,the XPS-derived atomic ratio between cointercalated N and intercalated Al is 0.9,which is lower than 1.6 for EMI-based electrolyte.Attributed to the additional de-solvation process,the batteries with the HMI-based electrolyte show a lower ionic diffusion rate,capacity,and cycling performance,which agree with the operando characterization results.Our findings highlight the critical role of the electrolyte coordination structure on the(co-)intercalation chemistry.展开更多
Intercalation of atomic species is a practicable method for epitaxial graphene to adjust the electronic band structure and to tune the coupling between graphene and Si C substrate. In this work, atomically flat epitax...Intercalation of atomic species is a practicable method for epitaxial graphene to adjust the electronic band structure and to tune the coupling between graphene and Si C substrate. In this work, atomically flat epitaxial graphene is prepared on 4H-SiC(0001) using the flash heating method in an ultrahigh vacuum system. Scanning tunneling microscopy, Raman spectroscopy and electrical transport measurements are utilized to investigate surface morphological structures and transport properties of pristine and Er-intercalated epitaxial graphene. It is found that Er atoms are intercalated underneath the graphene layer after annealing at 900℃, and the intercalation sites of Er atoms are located mainly at the bufferlayer/monolayer-graphene interface in monolayer domains. We also report the different behaviors of Er intercalation in monolayer and bilayer regions, and the experimental results show that the diffusion barrier for Er intercalated atoms in the buffer-layer/monolayer interface is at least 0.2 eV higher than that in the first/second graphene-layer interface. The appearance of Er atoms is found to have distinct impacts on the electronic transports of epitaxial graphene on SiC(0001).展开更多
Although MXenes is highly attractive as anode materials of lithium ion batteries,it sets a bottleneck for higher capacity of the V2CTxMXene due to the limited interlayer space and the derived surface terminations.Here...Although MXenes is highly attractive as anode materials of lithium ion batteries,it sets a bottleneck for higher capacity of the V2CTxMXene due to the limited interlayer space and the derived surface terminations.Herein,the cation intercalation and ion-exchange were well employed to achieve a K+and Ca2+intercalated V2CTxMXene.A larger interlayer distance and low F surface terminations were thereof obtained,which accelerates the ion transport and promotes the delicate surface of V2CTx MXene.As a result,a package of enhanced capacity,rate performance and cyclability can be achieved.Furthermore,the ion exchange approach can be extended to other 2 D layered materials,and both the interlayer control and the surface modification will be achieved.展开更多
The intercalation compounds of CuCl2 were synthesized with expanded graphite, whose magni-tude of the electrical conductivity is about 103S.cm1. Their electrical conductivity is 3-6 times as high as that of the expand...The intercalation compounds of CuCl2 were synthesized with expanded graphite, whose magni-tude of the electrical conductivity is about 103S.cm1. Their electrical conductivity is 3-6 times as high as that of the expanded graphite, and about 10 times as high as that of GIC made of the non-expanded graphite. The microanalysis results of chemical compounds by X-ray energy spectrum scanning of TEM testified that the atomic ratio of chloride and cupric is nonstoichoi-metric. The multivalence and exchange of electrovalence of the cupric ion was confirmed by the XPS-ESCA. Vacancy of chlorine anion increases the concentration of charge carrier. The special stage structure, made of graphite and chloride, produces a weak chemical bond belt and provides a carrier space in the direction of GIC layer. These factors develop the electrical properties.展开更多
Aqueous zinc-ion batteries(ZIBs) have attracted great attention as the candidates for large-scale energy storage system,recently,because of their low cost,environment-friendly,high safety,and high theoretical energy d...Aqueous zinc-ion batteries(ZIBs) have attracted great attention as the candidates for large-scale energy storage system,recently,because of their low cost,environment-friendly,high safety,and high theoretical energy densities.Among the numerous cathode materials,layered structure vanadium based polyanionic compounds,such as VOPO_(4),exhibit high specific capacity for Zn ion storage.However,the low Zn ion diffusion coefficient and limited interlayer spacing make the cathodes low reversible capacity and inferior cycling stability.Herein,K ions were pre-intercalated into the VOPO_(4) layers via ions exchange adopting VOPO_(4)·2 H_(2) O as the precursor.When evaluated as the cathode for ZIBs,an excellent cycle stability of 400 cycles under a current density of 500 mA g^(-1) was achieved by the obtained KVOPO_(4) electrode,verifying the positive effect of intercalation engineering.Furtherly,a solid-solution reaction Zn ion storage mechanism was confirmed.This study provides a new insight to explore high performance cathode materials for ZIBs.展开更多
Graphite is a universal host material for ion intercalation. Li+-graphite intercalation compounds (GICs) have been successfully utilized as the anode material in commercial lithium-ion batteries.Similarly, anion-graph...Graphite is a universal host material for ion intercalation. Li+-graphite intercalation compounds (GICs) have been successfully utilized as the anode material in commercial lithium-ion batteries.Similarly, anion-graphite intercalation compounds (AGICs) have been coming into their own in dual-ion batteries [1]. It is imperative to deepen an understanding of anion storage mechanisms in graphite electrode.展开更多
Inspired by a well-known architecture notion that load-bearing walls enable maintaining a highly-stable multiple-floored building,superior advantages are afforded via fabricating the NH_(4)+ions pre-intercalated Mo_(2...Inspired by a well-known architecture notion that load-bearing walls enable maintaining a highly-stable multiple-floored building,superior advantages are afforded via fabricating the NH_(4)+ions pre-intercalated Mo_(2)CT_(x) MXene(Mo_(2)CT_(x)-N)in a mixed solution of NH_(4)F and HCl via a simple one-step hydrothermal method.As a result of the synergistic effects of pillared structure,immobilizing-F groups and unlocking Mo-based redox,the Mo_(2)CT_(x)-N remarkably delivered a reversible capacity of 384.6 mAh ^(g-1) at 200 mA g^(-1) after 100 cycles.Our work lays a foundation for fully packaging its optimal performance via carding and architecting the chemistry of the MXene layers and between them.展开更多
NdCl 3 FeCl 3 graphite intercalation compounds were synthesized by molten salt exchange method. The state of the intercalates and the relative contents of Nd, Fe, Cl, C in the product were determined by X ray photoele...NdCl 3 FeCl 3 graphite intercalation compounds were synthesized by molten salt exchange method. The state of the intercalates and the relative contents of Nd, Fe, Cl, C in the product were determined by X ray photoelectron spectroscopy(XPS). From the XPS data, it is concluded that the binding energy of Fe2p electrons is about 711 20～710 3 eV, the binding energy of Nd3d electrons is about 983 08～983 20 eV, and Fe in the product has two valence states (Fe 3+ and Fe 2+ ).展开更多
NdCl3-FeCl3-graphite intercalation compounds were synthesized by means of molten salt-exchange method.Their layer structure and the relative content of the elements were investigated by X-ray diffraction, scanning ele...NdCl3-FeCl3-graphite intercalation compounds were synthesized by means of molten salt-exchange method.Their layer structure and the relative content of the elements were investigated by X-ray diffraction, scanning electronmicroscopy and energy dispersive X-ray spectroscopy. The results show that the products are mixtures of 2, 3,4-stages,among them, the c-axis repeat distance, Ic, of stage-3 NdCl3-GIC is 1. 6536±0. 0024 nm. In addition, the mechanismof RECl3 intercalation reaction was discussed.展开更多
We report a large-scale, high-quality heterostructure composed of vertically-stacked graphene and two-dimensional(2D) germanium.The heterostructure is constructed by the intercalation-assisted technique.We first synth...We report a large-scale, high-quality heterostructure composed of vertically-stacked graphene and two-dimensional(2D) germanium.The heterostructure is constructed by the intercalation-assisted technique.We first synthesize large-scale,single-crystalline graphene on Ir(111) surface and then intercalate germanium at the interface of graphene and Ir(111).The intercalated germanium forms a well-defined 2D layer with a 2 × 2 superstructure with respect to Ir(111).Theoretical calculations demonstrate that the 2D germanium has a double-layer structure.Raman characterizations show that the 2D germanium effectively weakens the interaction between graphene and Ir substrate, making graphene more like the intrinsic one.Further experiments of low-energy electron diffraction, scanning tunneling microscopy, and x-ray photoelectron spectroscopy(XPS) confirm the formation of large-scale and high-quality graphene/2D-germanium vertical heterostructure.The integration of graphene with a traditional 2D semiconductor provides a platform to explore new physical phenomena in the future.展开更多
The processing capability is vital for the wide applications of materials to forge structures as-demand.Graphene-based macroscopic materials have shown excellent mechanical and functional properties.However,different ...The processing capability is vital for the wide applications of materials to forge structures as-demand.Graphene-based macroscopic materials have shown excellent mechanical and functional properties.However,different from usual polymers and metals,graphene solids exhibit limited deformability and processibility for precise forming.Here,we present a precise thermoplastic forming of graphene materials by polymer intercalation from graphene oxide(GO)precursor.The intercalated polymer enables the thermoplasticity of GO solids by thermally activated motion of polymer chains.We detect a critical minimum containing of intercalated polymer that can expand the interlayer spacing exceeding 1.4 nm to activate thermoplasticity,which becomes the criteria for thermal plastic forming of GO solids.By thermoplastic forming,the flat GO-composite films are forged to Gaussian curved shapes and imprinted to have surface relief patterns with size precision down to 360 nm.The plastic-formed structures maintain the structural integration with outstanding electrical(3.07×10^(5) S m^(−1))and thermal conductivity(745.65 W m^(−1) K^(−1))after removal of polymers.The thermoplastic strategy greatly extends the forming capability of GO materials and other layered materials and promises versatile structural designs for more broad applications.展开更多
Rechargeable aqueous magnesium-ion batteries(MIBs)show great promise for low-cost,high-safety,and high-performance energy storage applications.Although manganese dioxide(MnO_(2))is considered as a potential electrode ...Rechargeable aqueous magnesium-ion batteries(MIBs)show great promise for low-cost,high-safety,and high-performance energy storage applications.Although manganese dioxide(MnO_(2))is considered as a potential electrode material for aqueous MIBs,the low electrical conductivity and unsatisfactory cycling performance greatly hinder the practical application of MnO_(2)electrode.To overcome these problems,herein,a novel Mg-intercalation engineering approach for MnO_(2)electrode to be used in aqueous MIBs is presented,wherein the structural regulation and electrochemical performance of the Mg-intercalation MnO_(2)(denoted as MMO)electrode were thoroughly investigated by density functional theory(DFT)calculations and in-situ Raman investigation.The results demonstrate that the Mg intercalation is essential to adjusting the charge/ion state and electronic band gap of MMO electrode,as well as the highly reversible phase transition of the MMO electrode during the charging-discharging process.Because of these remarkable characteristics,the MMO electrode can be capable of delivering a significant specific capacity of~419.8 mAh·g^(−1),while exhibiting a good cycling capability over 1000 cycles in 1 M aqueous MgCl_(2) electrolyte.On the basis of such MMO electrode,we have successfully developed a soft-packaging aqueous MIB with excellent electrochemical properties,revealing its huge application potential as the efficient energy storage devices.展开更多
The formation of solid electrolyte interphase(SEI) and ion intercalation are two key processes in rechargeable batteries, which need to be explored under dynamic operating conditions. In this work, both planar and san...The formation of solid electrolyte interphase(SEI) and ion intercalation are two key processes in rechargeable batteries, which need to be explored under dynamic operating conditions. In this work, both planar and sandwich model lithium batteries consisting of Li metal | ionic liquid electrolyte | graphite electrode have been constructed and investigated by a series of in situ surface analysis platforms including atomic force microscopy, Raman and X-ray photoelectron spectroscopy. It is found that the choice of electrolyte, including the concentration and contents, has a profound effect on the SEI formation and evolution, and the subsequent ion intercalation. A smooth and compact SEI is preferably produced in highconcentration electrolytes, with FSI^(-) salt superior to TFSI^(-) salt, facilitating the lithiation/delithiation to achieve high capacity and excellent cycle stability, while suppressing the co-intercalation of electrolyte solvent ions. The innovative research scenario of well-defined model batteries in combination with multiple genuinely in situ surface analysis methods presented herein leads to insightful results, which provide valuable strategies for the rational design and optimization of practical batteries, and energy storage devices in general.展开更多
Br_(2)/Br^(−)is a promising redox couple in fl ow batteries because of its high potential,solubility,and low cost.However,the reaction between Br^(−)and Br_(2)only involves a single-electron transfer process,which lim...Br_(2)/Br^(−)is a promising redox couple in fl ow batteries because of its high potential,solubility,and low cost.However,the reaction between Br^(−)and Br_(2)only involves a single-electron transfer process,which limits its energy density.Herein,a novel two-electron transfer reaction based on Br^(−)/Br^(+) was studied and realized through Br^(+) intercalation into graphite to form a bromine-graphite intercalation compound(Br-GIC).Compared with the pristine Br^(−)/Br_(2)redox pair,the redox potential of Br intercalation/deintercalation in graphite is 0.5 V higher,which has the potential to substantially increase the energy density.Diff erent from Br_(2)/Br^(−)in the electrolyte,the diff usion rate of Br intercalation in graphite decreases with increasing charge state because of the decreasing intercalation sites in graphite,and the integrity of the graphite structure is important for the intercalation reaction.As a result,the battery can continuously run for more than 300 cycles with a Coulombic effi-ciency exceeding 97%and an energy effi ciency of approximately 80%at 30 mA/cm^(2),and the energy density increases by 65%compared with Br^(−)/Br_(2).Combined with double-electron transfer and a highly reversible electrochemical process,the Br intercalation redox couple demonstrates very promising prospects for stationary energy storage.展开更多
Graphite carbon has been successfully used for the anode materials of secondary ion batteries due to its capability of accommodating ions between graphite layers.The intercalation dynamics intrinsically determine the ...Graphite carbon has been successfully used for the anode materials of secondary ion batteries due to its capability of accommodating ions between graphite layers.The intercalation dynamics intrinsically determine the performance of the batteries.In this review,we summarize recent research progresses of structural characterizations on graphite intercalation in electrochemical devices,especially on the in‐situ study on the intercalations of Li/Na/K ions,AlCl4−and other anions,or solvents.These techniques,including X‐ray,electron microscopy,Raman,neutron scattering,nuclear magnetic resonance,and optical microscopy provide direct information of the reaction dynamics and help to understand the factors affecting the electrochemical performances of metallic ion batteries.展开更多
The following article has been retracted due to the investigation of complaints received against it. The Editorial Board found that substantial portions of the text came from other published papers. Unethical behavior...The following article has been retracted due to the investigation of complaints received against it. The Editorial Board found that substantial portions of the text came from other published papers. Unethical behavior such as self-plagiarism and misuse of published figures and data without copyright consent will be treated very seriously. The scientific community takes a very strong view on this matter, and the OJSTA treats all unethical behavior such as plagiarism seriously. This paper published in Vol.2 No. 1,1-7, 2013, has been removed from this site.展开更多
基金supported by the National Natural Science Foundation of China(No.51802163)the Natural Science Foundation of Henan Province of China(No.222300420252)the Natural Science Foundation of Henan Department of Education(No.20A480004).
文摘Orthorhombic Nb_(2)O_(5)(T-Nb_(2)O_(5))is attractive for fast-charging Li-ion batteries,but it is still hard to realize rapid charge transfer kinetics for Li-ion storage.Herein,F-doped T-Nb_(2)O_(5) microflowers(F-Nb_(2)O_(5))are rationally synthesized through topotactic conversion.Specifically,F-Nb_(2)O_(5) are assembled by single-crystal nanoflakes with nearly 97%exposed(100)facet,which maximizes the exposure of the feasible Li^(+)transport pathways along loosely packed 4g atomic layers to the electrolytes,thus effectively enhancing the Li^(+)-intercalation performance.Besides,the band gap of F-Nb_(2)O_(5) is reduced to 2.87 eV due to the doping of F atoms,leading to enhanced electrical conductivity.The synergetic effects between tailored exposed crystal facets,F-doping,and ultrathin building blocks,speed up the Li^(+)/electron transfer kinetics and improve the pseudocapacitive properties of F-Nb_(2)O_(5).Therefore,F-Nb_(2)O_(5) exhibit superior rate capability(210.8 and 164.9 mAh g^(-1) at 1 and 10 C,respectively)and good long-term 10 C cycling performance(132.7 mAh g^(-1) after 1500 cycles).
基金National Natural Science Foundation of China,Grant/Award Numbers:U2004172,51972287 and 51502269the Foundation for University Key Teachers of Henan Province,Grant/Award Number:2020GGJS009Natural Science Foundation of Henan Province,Grant/Award Number:202300410368。
文摘Sophisticated efficient electrocatalysts are essential to rectifying the shuttle effect and realizing the high performance of flexible lithium-sulfur batteries(LSBs).Phase transformation of MoSe_(2) from the 2H phase to the 1T phase has been proven to be a significant method to improve the catalytic activity.However,precisely controllable phase engineering of MoSe_(2) has rarely been reported.Herein,by in situ Li ions intercalation in MoSe_(2),a precisely controllable phase evolution from 2H-MoSe_(2) to 1T-MoSe_(2) was realized.More importantly,the definite functional relationship between cut-off voltage and phase structure was first identified for phase engineering through in situ observation and modulation methods.The sulfur host(CNFs/1T-MoSe_(2))presents high charge density,strong polysulfides adsorption,and catalytic kinetics.Moreover,Li-S cells based on it display capacity retention of 875.3mAh g^(-1) after 500 cycles at 1 C and an areal capacity of 8.71mAh cm^(-2) even at a high sulfur loading of 8.47mg cm^(-2).Furthermore,the flexible pouch cell exhibiting decent performance will endow a promising potential in the wearable energy storage field.This study proposes an effective strategy to precisely control the phase structure of MoSe_(2),which may provide the reference to fabricate the highly efficient electrocatalysts for LSBs and other energy systems.
基金supported by the National Natural Science Foundation of China(Grant Nos.51988101 and 42007262).
文摘Fault rupture propagation is more complex in the overlying soil with intercalation than in homogeneous soil,and it is challenging to simulate this phenomenon accurately using the finite element method.To address this issue,an improved nonlocal model that incorporates softening modulus modification is proposed.The methodology has the advantage that the solutions are independent of both mesh sizes and characteristic lengths,while maintaining objective softening rates of materials.Using the proposed methodology,a series of numerical simulations are conducted to investigate the effects of different mechanical parameters,such as elastic modulus,friction angle and dilation angle of the soil within the intercalation,as well as the impact of geometries,such as the depth and thickness of the intercalation,on the fault rupture progress.This study not only provides significant insights into the mechanisms of fault rupture propagation,specifically in relation to intercalations,but also shows a great value in promoting the current research on fault rupture.
基金the Ministry of Science and Technology of China(Grant Nos.2018YFA0305800 and2019YFA0308500)the National Natural Science Foundation of China(Grant No.61925111)+2 种基金the Chinese Academy of Sciences(Grant Nos.XDB28000000 and YSBR-003)the Fundamental Research Funds for the Central Universitiesthe CAS Key Laboratory of Vacuum Physics。
文摘Intercalation of insulating materials between epitaxial graphene and the metal substrates is highly demanded to restore the intrinsic properties of graphene,and thus essential for the graphene-based devices.Here we demonstrate a successful solution for the intercalation of hafnium oxide into the interface between full-layer graphene and Ir(111)substrate.We first intercalate hafnium atoms beneath the epitaxial graphene.The intercalation of the hafnium atoms leads to the variation of the graphene moire superstructure periodicity,which is characterized by low-energy electron diffraction(LEED)and lowtemperature scanning tunneling microscopy(LT-STM).Subsequently,we introduce oxygen into the interface,resulting in oxidization of the intercalated hafnium.STM and Raman's characterizations reveal that the intercalated hafnium oxide layer could effectively decouple the graphene from the metallic substrate,while the graphene maintains its high quality.Our work suggests a high-k dielectric layer has been successfully intercalated between high-quality epitaxial graphene and metal substrate,providing a platform for applications of large-scale,high-quality graphene for electronic devices.
基金financially supported by the National Key R&D Program of China (2021YFA1502800)the National Natural Science Foundation of China (21825203,22288201,and 91945302)+1 种基金the Photon Science Center for Carbon Neutrality,Liao Ning Revitalization Talents Program (XLYC1902117)the Youth Innovation Fund of Dalian institute of Chemical Physics (DICP I202125)。
文摘In-depth understanding of the electrolyte-dependent intercalation chemistry in batteries through direct operando/in situ characterizations is crucial for the development of the high-performance batteries.Herein,taking the Al/graphite battery as a model system,the effect of electrolyte coordination structure on the intercalation processes has been investigated over the batteries with either 1-hexyl-3-methylimidazolium chloride(HMICl)-AlCl_(3) or 1-ethyl-3-methylimidazolium chloride(EMICl)-AlCl_(3) ionic liquid electrolyte using operando X-ray photoelectron spectroscopy(XPS)and X-ray diffraction.With a weaker anion-cation interaction in HMI-based electrolyte,the XPS-derived atomic ratio between cointercalated N and intercalated Al is 0.9,which is lower than 1.6 for EMI-based electrolyte.Attributed to the additional de-solvation process,the batteries with the HMI-based electrolyte show a lower ionic diffusion rate,capacity,and cycling performance,which agree with the operando characterization results.Our findings highlight the critical role of the electrolyte coordination structure on the(co-)intercalation chemistry.
基金Project supported by the Natural Science Foundation of Shanghai Science and Technology Committee (Grant No. 18ZR1403300)。
文摘Intercalation of atomic species is a practicable method for epitaxial graphene to adjust the electronic band structure and to tune the coupling between graphene and Si C substrate. In this work, atomically flat epitaxial graphene is prepared on 4H-SiC(0001) using the flash heating method in an ultrahigh vacuum system. Scanning tunneling microscopy, Raman spectroscopy and electrical transport measurements are utilized to investigate surface morphological structures and transport properties of pristine and Er-intercalated epitaxial graphene. It is found that Er atoms are intercalated underneath the graphene layer after annealing at 900℃, and the intercalation sites of Er atoms are located mainly at the bufferlayer/monolayer-graphene interface in monolayer domains. We also report the different behaviors of Er intercalation in monolayer and bilayer regions, and the experimental results show that the diffusion barrier for Er intercalated atoms in the buffer-layer/monolayer interface is at least 0.2 eV higher than that in the first/second graphene-layer interface. The appearance of Er atoms is found to have distinct impacts on the electronic transports of epitaxial graphene on SiC(0001).
基金financial support provided by the National Natural Science Foundation of China(No.51932005)Liao Ning Revitalization Talents Program(XLYC1807175)+4 种基金the Joint Research Fund Liaoning Shenyang National Laboratory for Materials Science(SYNL)(20180510047)the Research Fund of SYNL(L2019F38)the Youth Innovation Promotion Association CAS(2015152)the Program for the Development of Science and Technology of Jilin Province(No.20190201309JC)the Project of Development and Reform Commission of Jilin Province(No.2019C042-1)。
文摘Although MXenes is highly attractive as anode materials of lithium ion batteries,it sets a bottleneck for higher capacity of the V2CTxMXene due to the limited interlayer space and the derived surface terminations.Herein,the cation intercalation and ion-exchange were well employed to achieve a K+and Ca2+intercalated V2CTxMXene.A larger interlayer distance and low F surface terminations were thereof obtained,which accelerates the ion transport and promotes the delicate surface of V2CTx MXene.As a result,a package of enhanced capacity,rate performance and cyclability can be achieved.Furthermore,the ion exchange approach can be extended to other 2 D layered materials,and both the interlayer control and the surface modification will be achieved.
基金This paper was the part of doctor thesis of China Uni-versity of Geoscience, (Beijing). The project was sup-' ported by Natio
文摘The intercalation compounds of CuCl2 were synthesized with expanded graphite, whose magni-tude of the electrical conductivity is about 103S.cm1. Their electrical conductivity is 3-6 times as high as that of the expanded graphite, and about 10 times as high as that of GIC made of the non-expanded graphite. The microanalysis results of chemical compounds by X-ray energy spectrum scanning of TEM testified that the atomic ratio of chloride and cupric is nonstoichoi-metric. The multivalence and exchange of electrovalence of the cupric ion was confirmed by the XPS-ESCA. Vacancy of chlorine anion increases the concentration of charge carrier. The special stage structure, made of graphite and chloride, produces a weak chemical bond belt and provides a carrier space in the direction of GIC layer. These factors develop the electrical properties.
基金financially supported by the National Natural Science Foundation of China (52025013,52071184,and 21835004)the Ministry of Science and Technology of China(2017YFA0206702, and 2016YFB0901502)+2 种基金the 111 Project(B12015)the Natural Science Foundation of Tianjin(18ZXJMTG00040, and 19JCZDJC31800)the Fundamental Research Funds for the Central Universities。
文摘Aqueous zinc-ion batteries(ZIBs) have attracted great attention as the candidates for large-scale energy storage system,recently,because of their low cost,environment-friendly,high safety,and high theoretical energy densities.Among the numerous cathode materials,layered structure vanadium based polyanionic compounds,such as VOPO_(4),exhibit high specific capacity for Zn ion storage.However,the low Zn ion diffusion coefficient and limited interlayer spacing make the cathodes low reversible capacity and inferior cycling stability.Herein,K ions were pre-intercalated into the VOPO_(4) layers via ions exchange adopting VOPO_(4)·2 H_(2) O as the precursor.When evaluated as the cathode for ZIBs,an excellent cycle stability of 400 cycles under a current density of 500 mA g^(-1) was achieved by the obtained KVOPO_(4) electrode,verifying the positive effect of intercalation engineering.Furtherly,a solid-solution reaction Zn ion storage mechanism was confirmed.This study provides a new insight to explore high performance cathode materials for ZIBs.
基金financially supported by the National Natural Science Foundation of China(21975251)。
文摘Graphite is a universal host material for ion intercalation. Li+-graphite intercalation compounds (GICs) have been successfully utilized as the anode material in commercial lithium-ion batteries.Similarly, anion-graphite intercalation compounds (AGICs) have been coming into their own in dual-ion batteries [1]. It is imperative to deepen an understanding of anion storage mechanisms in graphite electrode.
基金Supported by the National Natural Science Foundation of China(51932003,51872115)2020 International Cooperation Project of the Department of Science and Technology of Jilin Province(20200801001GH)+1 种基金the Science and Technology Research Project of Education Department of Jilin Province(JJKH20210453KJ,JJKH20210449KJ)the Joint Research Fund of Key Laboratory of Functional Materials Physics and Chemistry(Jilin Normal University)Ministry of Education(202101)。
文摘Inspired by a well-known architecture notion that load-bearing walls enable maintaining a highly-stable multiple-floored building,superior advantages are afforded via fabricating the NH_(4)+ions pre-intercalated Mo_(2)CT_(x) MXene(Mo_(2)CT_(x)-N)in a mixed solution of NH_(4)F and HCl via a simple one-step hydrothermal method.As a result of the synergistic effects of pillared structure,immobilizing-F groups and unlocking Mo-based redox,the Mo_(2)CT_(x)-N remarkably delivered a reversible capacity of 384.6 mAh ^(g-1) at 200 mA g^(-1) after 100 cycles.Our work lays a foundation for fully packaging its optimal performance via carding and architecting the chemistry of the MXene layers and between them.
文摘NdCl 3 FeCl 3 graphite intercalation compounds were synthesized by molten salt exchange method. The state of the intercalates and the relative contents of Nd, Fe, Cl, C in the product were determined by X ray photoelectron spectroscopy(XPS). From the XPS data, it is concluded that the binding energy of Fe2p electrons is about 711 20～710 3 eV, the binding energy of Nd3d electrons is about 983 08～983 20 eV, and Fe in the product has two valence states (Fe 3+ and Fe 2+ ).
文摘NdCl3-FeCl3-graphite intercalation compounds were synthesized by means of molten salt-exchange method.Their layer structure and the relative content of the elements were investigated by X-ray diffraction, scanning electronmicroscopy and energy dispersive X-ray spectroscopy. The results show that the products are mixtures of 2, 3,4-stages,among them, the c-axis repeat distance, Ic, of stage-3 NdCl3-GIC is 1. 6536±0. 0024 nm. In addition, the mechanismof RECl3 intercalation reaction was discussed.
基金Project supported by the National Key Research&Development Program of China(Grant Nos.2016YFA0202300 and 2018YFA0305800)the National Natural Science Foundation of China(Grant Nos.61390501,61888102,and 51872284)+2 种基金the Strategic Priority Research Program of Chinese Academy of Sciences(Grant Nos.XDB30000000 and XDB28000000)Beijing Nova Program,China(Grant No.Z181100006218023)the University of Chinese Academy of Sciences
文摘We report a large-scale, high-quality heterostructure composed of vertically-stacked graphene and two-dimensional(2D) germanium.The heterostructure is constructed by the intercalation-assisted technique.We first synthesize large-scale,single-crystalline graphene on Ir(111) surface and then intercalate germanium at the interface of graphene and Ir(111).The intercalated germanium forms a well-defined 2D layer with a 2 × 2 superstructure with respect to Ir(111).Theoretical calculations demonstrate that the 2D germanium has a double-layer structure.Raman characterizations show that the 2D germanium effectively weakens the interaction between graphene and Ir substrate, making graphene more like the intrinsic one.Further experiments of low-energy electron diffraction, scanning tunneling microscopy, and x-ray photoelectron spectroscopy(XPS) confirm the formation of large-scale and high-quality graphene/2D-germanium vertical heterostructure.The integration of graphene with a traditional 2D semiconductor provides a platform to explore new physical phenomena in the future.
基金the support of the National Natural Science Foundation of China(Nos.51803177,51973191,51533008,and 51636002)National Key R&D Program of China(No.2016YFA0200200)+5 种基金the China Postdoctoral Science Foundation(No.2021M690134)Hundred Talents Program of Zhejiang University(188020*194231701/113)Key Research and Development Plan of Zhejiang Province(2018C01049)the National Postdoctoral Program for Innovative Talents(No.BX201700209)the Fundamental Research Funds for the Central Universities(2021FZZX001-17),the Natural Science Foundation of Jiangsu Province(BK20210353)the Fundamental Research Funds for the Central Universities(No.30920041106).
文摘The processing capability is vital for the wide applications of materials to forge structures as-demand.Graphene-based macroscopic materials have shown excellent mechanical and functional properties.However,different from usual polymers and metals,graphene solids exhibit limited deformability and processibility for precise forming.Here,we present a precise thermoplastic forming of graphene materials by polymer intercalation from graphene oxide(GO)precursor.The intercalated polymer enables the thermoplasticity of GO solids by thermally activated motion of polymer chains.We detect a critical minimum containing of intercalated polymer that can expand the interlayer spacing exceeding 1.4 nm to activate thermoplasticity,which becomes the criteria for thermal plastic forming of GO solids.By thermoplastic forming,the flat GO-composite films are forged to Gaussian curved shapes and imprinted to have surface relief patterns with size precision down to 360 nm.The plastic-formed structures maintain the structural integration with outstanding electrical(3.07×10^(5) S m^(−1))and thermal conductivity(745.65 W m^(−1) K^(−1))after removal of polymers.The thermoplastic strategy greatly extends the forming capability of GO materials and other layered materials and promises versatile structural designs for more broad applications.
基金financially supported by the National Nature Science Foundations of China(Nos. 52002157 and 51873083)the Nature Science Foundations of Jiangsu Province,China(No. BK20190976)the Undergraduate Research & Practice Innovation Program of Jiangsu Province,China(No. 202010289017Z)
文摘Rechargeable aqueous magnesium-ion batteries(MIBs)show great promise for low-cost,high-safety,and high-performance energy storage applications.Although manganese dioxide(MnO_(2))is considered as a potential electrode material for aqueous MIBs,the low electrical conductivity and unsatisfactory cycling performance greatly hinder the practical application of MnO_(2)electrode.To overcome these problems,herein,a novel Mg-intercalation engineering approach for MnO_(2)electrode to be used in aqueous MIBs is presented,wherein the structural regulation and electrochemical performance of the Mg-intercalation MnO_(2)(denoted as MMO)electrode were thoroughly investigated by density functional theory(DFT)calculations and in-situ Raman investigation.The results demonstrate that the Mg intercalation is essential to adjusting the charge/ion state and electronic band gap of MMO electrode,as well as the highly reversible phase transition of the MMO electrode during the charging-discharging process.Because of these remarkable characteristics,the MMO electrode can be capable of delivering a significant specific capacity of~419.8 mAh·g^(−1),while exhibiting a good cycling capability over 1000 cycles in 1 M aqueous MgCl_(2) electrolyte.On the basis of such MMO electrode,we have successfully developed a soft-packaging aqueous MIB with excellent electrochemical properties,revealing its huge application potential as the efficient energy storage devices.
基金financially supported by the National Key R&D Program of China(No.2016YFA0200200)the National Natural Science Foundation of China(Nos.21688102 and 21825203)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB17020000)。
文摘The formation of solid electrolyte interphase(SEI) and ion intercalation are two key processes in rechargeable batteries, which need to be explored under dynamic operating conditions. In this work, both planar and sandwich model lithium batteries consisting of Li metal | ionic liquid electrolyte | graphite electrode have been constructed and investigated by a series of in situ surface analysis platforms including atomic force microscopy, Raman and X-ray photoelectron spectroscopy. It is found that the choice of electrolyte, including the concentration and contents, has a profound effect on the SEI formation and evolution, and the subsequent ion intercalation. A smooth and compact SEI is preferably produced in highconcentration electrolytes, with FSI^(-) salt superior to TFSI^(-) salt, facilitating the lithiation/delithiation to achieve high capacity and excellent cycle stability, while suppressing the co-intercalation of electrolyte solvent ions. The innovative research scenario of well-defined model batteries in combination with multiple genuinely in situ surface analysis methods presented herein leads to insightful results, which provide valuable strategies for the rational design and optimization of practical batteries, and energy storage devices in general.
基金supported by National Natural Science Foundation of China(Nos.21935003,21925804)the Strategic Priority Research Program of the Chinese Academy of Sci-ences(No.XDA21070100)+1 种基金CAS Engineering Laboratory for Electro-chemical Energy Storage(KFJ-PTXM-027)DICP funding(DICP I202137).
文摘Br_(2)/Br^(−)is a promising redox couple in fl ow batteries because of its high potential,solubility,and low cost.However,the reaction between Br^(−)and Br_(2)only involves a single-electron transfer process,which limits its energy density.Herein,a novel two-electron transfer reaction based on Br^(−)/Br^(+) was studied and realized through Br^(+) intercalation into graphite to form a bromine-graphite intercalation compound(Br-GIC).Compared with the pristine Br^(−)/Br_(2)redox pair,the redox potential of Br intercalation/deintercalation in graphite is 0.5 V higher,which has the potential to substantially increase the energy density.Diff erent from Br_(2)/Br^(−)in the electrolyte,the diff usion rate of Br intercalation in graphite decreases with increasing charge state because of the decreasing intercalation sites in graphite,and the integrity of the graphite structure is important for the intercalation reaction.As a result,the battery can continuously run for more than 300 cycles with a Coulombic effi-ciency exceeding 97%and an energy effi ciency of approximately 80%at 30 mA/cm^(2),and the energy density increases by 65%compared with Br^(−)/Br_(2).Combined with double-electron transfer and a highly reversible electrochemical process,the Br intercalation redox couple demonstrates very promising prospects for stationary energy storage.
文摘Graphite carbon has been successfully used for the anode materials of secondary ion batteries due to its capability of accommodating ions between graphite layers.The intercalation dynamics intrinsically determine the performance of the batteries.In this review,we summarize recent research progresses of structural characterizations on graphite intercalation in electrochemical devices,especially on the in‐situ study on the intercalations of Li/Na/K ions,AlCl4−and other anions,or solvents.These techniques,including X‐ray,electron microscopy,Raman,neutron scattering,nuclear magnetic resonance,and optical microscopy provide direct information of the reaction dynamics and help to understand the factors affecting the electrochemical performances of metallic ion batteries.
文摘The following article has been retracted due to the investigation of complaints received against it. The Editorial Board found that substantial portions of the text came from other published papers. Unethical behavior such as self-plagiarism and misuse of published figures and data without copyright consent will be treated very seriously. The scientific community takes a very strong view on this matter, and the OJSTA treats all unethical behavior such as plagiarism seriously. This paper published in Vol.2 No. 1,1-7, 2013, has been removed from this site.
