Graphene Nanoribbons Enhancing the Electronic Conductivity and Ionic Diffusion of Graphene Electrodes for High-Performance Microsupercapacitors

The electrochemical performance of microsupercapacitors with graphene electrodes is reduced by the issue of graphene sheets aggregation,which limits electrolyte ions penetration into electrode.Increasing the space between graphene sheets in electrodes facilitates the electrolyte ions penetration,but sacrifices its electronic conductivity which also influences the charge storage ability.The challenging task is to improve the electrodes’electronic conductivity and ionic diffusion simultaneously,boosting the device’s electrochemical performance.Herein,we experimentally realize the enhancement of both electronic conductivity and ionic diffusion from 2D graphene nanoribbons assisted graphene electrode with porous layer-uponlayer structure,which is tailored by graphene nanoribbons and self-sacrificial templates ethyl cellulose.The designed electrode-based device delivers a high areal capacitance of 71 mF cm^(-2)and areal energy density of 9.83μWh cm^(-2),promising rate performance,outstanding cycling stability with 97%capacitance retention after 20000 cycles,and good mechanical properties.The strategy paves the way for fabricating high-performance graphene-based MSCs.

The complex band structure for armchair graphene nanoribbons

Using a tight binding transfer matrix method, we calculate the complex band structure of armchair graphene nanoribbons. The real part of the complex band structure calculated by the transfer matrix method fits well with the bulk band structure calculated by a Hermitian matrix. The complex band structure gives extra information on carrier＇s decay behaviour. The imaginary loop connects the conduction and valence band, and can profoundly affect the characteristics of nanoscale electronic device made with graphene nanoribbons. In this work, the complex band structure calculation includes not only the first nearest neighbour interaction, but also the effects of edge bond relaxation and the third nearest neighbour interaction. The band gap is classified into three classes. Due to the edge bond relaxation and the third nearest neighbour interaction term, it opens a band gap for N = 3M- 1. The band gap is almost unchanged for N =3M ＋ 1, but decreased for N = 3M. The maximum imaginary wave vector length provides additional information about the electrical characteristics of graphene nanoribbons, and is also classified into three classes.

Band structure and edge states of star-like zigzag graphene nanoribbons

Connecting three zigzag graphene nanoribbons（ZGNRs） together through the sp^3 hybrid bonds forms a star-like ZGNR（S-ZGNR）. Its band structure shows that there are four edge states at k = 0.5, in which the three electrons distribute at three outside edge sites, and the last electron is shared equally（50%） by two sites near the central site. The lowest conductance step in the valley is 2, two times higher than that of monolayer ZGNR（M-ZGNR）. Furthermore, in one quasithree-dimensional hexagonal lattice built, both of the Dirac points and the zero-energy states appear in the band structure along the z-axis for the fixed zero k-point in the x-y plane. In addition, it is an insulator in the x-y plane due to band gap 4 eV, however, for any k-point in the x-y plane the zero-energy states always exist at kz = 0.5.

One-dimensional method of investigating the localized states in armchair graphene-like nanoribbons with defects

In this paper we propose a type of new analytical method to investigate the localized states in the armchair graphene-like nanoribbons. The method is based on the tight-binding model and with a standing wave assumption. The system of armchair graphene-like nanoribbons includes the armchair supercells with arbitrary elongation-type line defects and the semi-infinite nanoribbons. With this method, we analyze many interesting localized states near the line defects in the graphene and boron-nitride nanoribbons. We also derive the analytical expressions and the criteria for the localized states in the semi-infinite nanoribbons.

Energy band engineering via“Bite”defect located on N=8 armchair graphene nanoribbons

Graphene nanoribbons(GNRs)not only share many superlative properties of graphene but also display an exceptional degree of tunability of their electronic properties.The bandgaps of GNRs depend greatly on their widths,edges,etc.Herein,we report the synthesis path and the physical properties of atomic accuracy staggered narrow N=8 armchair graphene nanoribbons(sn-8AGNR)with alternating"Bite"defects on the opposite side.The intermediate structures in the surface physicochemical reactions from the precursors to the sn-8AGNR are characterized by scanning tunneling microscopy.The electronic properties of the sn-8AGNR are characterized by scanning tunneling spectroscopies and 6//6V mappings.Compared with the perfect N=8 armchair graphene nanoribbons(8AGNR),the sn-8AGNR has a larger bandgap,indicating that the liB\Xen edges can effectively regulate the electronic structures of GNRs.

Band engineering of B_2H_2 nanoribbons

Freestanding honeycomb borophene is unstable due to the electron-deficiency of boron atoms. B_2H_2 monolayer, a typical borophene hydride, has been predicted to be structurally stable and attracts great attention. Here, we investigate the electronic structures of B_2H_2 nanoribbons. Based on first-principles calculations, we have found that all narrow armchair nanoribbons with and without mirror symmetry(ANR-s and ANR-as, respectively) are semiconducting. The energy gap has a relation with the width of the ribbon. When the ribbon is getting wider, the gap disappears. The zigzag ribbons without mirror symmetry(ZNR-as) have the same trend. But the zigzag ribbons with mirror symmetry(ZNR-s) are always metallic. We have also found that the metallic ANR-as and ZNR-s can be switched to semiconducting by applying a tensile strain along the nanoribbon. A gap of 1.10 eV is opened under 16% strain for the 11.0-■ ANR-as. Structural stability under such a large strain has also been confirmed. The flexible band tunability of B_2H_2 nanoribbon increases its possibility of potential applications in nanodevices.

Band Gap of Strained Graphene Nanoribbons

The band structures of strained graphene nanoribbons(GNRs)are examined using a tight-binding Hamiltonian that is directly related to the type and magnitude of strain.Compared to a two-dimensional graphene whose band gap remains close to zero even if a large strain is applied,the band gap of a graphene nanoribbon(GNR)is sensitive to both uniaxial and shear strains.The effect of strain on the electronic structure of a GNR depends strongly on its edge shape and structural indices.For an armchair GNR,a weak uniaxial strain changes the band gap in a linear fashion,whereas a large strain results in periodic oscillation of the band gap.On the other hand,shear strain always tends to reduce the band gap.For a zigzag GNR,the effect of strain is to change the spin polarization at the edges of GNR,and thereby modulate the band gap.A simple analytical model,which agrees with the numerical results,is proposed to interpret the response of the band gap to strain in armchair GNRs.

Strain Effects in Graphene and Graphene Nanoribbons:The Underlying Mechanism

A tight-binding analytic framework is combined with first-principles calculations to reveal the mechanism underlying the strain effects on electronic structures of graphene and graphene nanoribbons(GNRs).It provides a unified and precise formulation of the strain effects under various circumstances-including the shift of the Fermi(Dirac)points,the change in band gap of armchair GNRs with uniaxial strain in a zigzag pattern and its insensitivity to shear strain,and the variation of the k-range of edge states in zigzag GNRs under uniaxial and shear strains which determine the gap behavior via the spin polarization interaction.

Progress on band structure engineering of twisted bilayer and two-dimensional moiré heterostructures

Artificially constructed van der Waals heterostructures(vdWHs)provide an ideal platform for realizing emerging quantum phenomena in condensed matter physics.Two methods for building vdWHs have been developed:stacking two-dimensional(2D)materials into a bilayer structure with different lattice constants,or with different orientations.The interlayer coupling stemming from commensurate or incommensurate superlattice pattern plays an important role in vdWHs for modulating the band structures and generating new electronic states.In this article,we review a series of novel quantum states discovered in two model vdWH systems—graphene/hexagonal boron nitride(hBN)hetero-bilayer and twisted bilayer graphene(tBLG),and discuss how the electronic structures are modified by such stacking and twisting.We also provide perspectives for future studies on hetero-bilayer materials,from which an expansion of 2D material phase library is expected.

Rb吸附石墨烯纳米带电子性质和光学性质的研究

本文基于密度泛函理论的第一性原理方法了计算了Rb、O和H吸附石墨烯纳米带的差分电荷密度、能带结构、分波态密度和介电函数,调制了石墨烯纳米带的电子性质和光学性质,给出了不同杂质影响材料光学特性的规律.结果表明本征石墨烯纳米带为n型直接带隙半导体且带隙值为0.639 eV;Rb原子吸附石墨烯纳米带之后变为n型简并直接带隙半导体,带隙值为0.494 eV;Rb和O吸附石墨烯纳米带变为p型简并直接带隙半导体,带隙值增加为0.996 eV;增加H吸附石墨烯纳米带后,半导体类型变为n型直接带隙半导体,且带隙变为0.299 eV,带隙值相对减小,更有利于半导体发光器件制备.吸附Rb、O和H原子后,石墨烯纳米带中电荷密度发生转移,导致C、Rb、O和H之间成键作用显著.吸附Rb之后,在费米能级附近由C-2p、Rb-5s贡献;增加O原子吸附之后,O-2p在费米能级附近贡献非常活跃,C-2p、Rb-5s和O-2p电子态之间强烈的杂化效应,促使费米能级附近的杂质能级分裂成能带;再增加H原子吸附之后,Rb-4p贡献发生蓝移,O-2p在费米能级附近贡献非常强,费米能级分裂出两条能带.Rb、O和H的吸附后,明显调制了石墨烯纳米带的光学性质.

Reinforcing oxygen electrocatalytic activity via selective dualphase heterointerface engineering for rechargeable Zn-air batteries

Dual-phase heterointerface electrocatalysts(DPHE)constructed by oxygen reduction reaction(ORR)-and oxygen evolution reaction(OER)-active elements exhibit excellent bifunctional activity and long-term durability due to the abundant interface exposure and synergistic catalytic effect.Herein,low-dimensional N-doped graphene nanoribbons(N-GNRs)coupling with ultrathin CoO nanocomposites(N-GNRs/CoO)were controllably fabricated through a facile two-step approach using synthesized Co(OH)_2 nanosheet as CoO precursor.Density functional theory(DFT)calculations and experimental characterizations prove that the formation of interface between N-GNRs and CoO can induce local charge redistribution,contributing to the improvement of catalytic activity and stability.The optimal N-GNRs/CoO DPHE possesses hierarchically porous architectures and presents outstanding bifunctional activities with a small potential gap of 0.729 V between the potential at 10 mA·cm^(-2)for OER and the halfwave potential for ORR,which outperforms Pt/C+IrO_(2)and the majority of noble-metal-free bifunctional catalysts.Liquid-and solid-state rechargeable Zn-air batteries assembled with N-GNRs/CoO as the cathode also display high peak power density and fantastic cycle stability,superior to that of benchmark Pt/C+IrO_(2)catalyst.It is anticipated to offer significant benefits toward high activity,stability and mechanical flexibility bifunctional oxygen electrocatalysts for rechargeable Zn-air batteries.

含有碳链通道的石墨烯纳米带电子特性的第一性原理研究

采用第一性原理的密度泛函理论结合非平衡格林函数的计算方法,研究了含有多碳链通道的石墨烯纳米带的原子结构、电子能带结构与电子输运特性.结果表明,移除大量原子后含有双碳原子链的纳米带的能隙显著增大,这说明电子从占据态到未占据态的跃迁将更加困难;并且最高占据子能带与最低未占据子能带几乎与费米能级平行,说明边缘态几乎完全消失.电子输运特性的计算结果与电子能带结果是自洽的,碳链的引入导致纳米带电导隙的增大和费米能级位置电导的湮没.这说明通过电子束轰击的方式裁剪纳米带的原子结构来制备集成度更高、尺度更小的一维半导体纳米器件是可行的.

石墨烯纳米带的制备与电学特性调控

石墨烯由于其独特的晶体结构展现出了特殊的电学特性,其导带与价带相交于第一布里渊区的六个顶点处,形成带隙为零的半金属材料,具有优异的电子传输特性的同时也限制了其在电子学器件中的使用.因而科研人员尝试各种方法来打开其带隙并调控其能带特性,主要有利用缺陷、应力、掺杂、表面吸附、结构调控等手段.其中石墨烯纳米带由于量子边界效应和限制效应,存在带隙.本综述主要介绍了制备各类石墨烯纳米带的方法,并通过精确调控其细微结构,从而对其进行精确的能带调控,改变其电学特性,为其在电子学器件中的应用提供一些可行的方向.

基于第一性原理对硅取代、掺杂锯齿形石墨烯纳米带的电子结构及输运性质的研究

本文基于第一性原理对硅取代、掺杂石墨烯纳米带不同位置的电子能带结构、态密度及电子器件的电子输运性质进行了分析与研究。结果表明,锯齿形石墨烯纳米带(ZGNRs)在硅原子取代及掺杂后由原来的半导体态转变为金属态。在各种模型中,对于体系态密度有贡献的一般为原子指数为1、在p轨道的硅原子(Si1p);原子指数为2、在p轨道的硅原子(Si2p)和碳原子(C2p);少量的原子指数为1、在s轨道的氢原子(H1s)和碳原子(C1s)。经分析,在各取代位置中两端硅原子取代的锯齿形石墨烯纳米带的体系能量最小,表明其为最有可能发生的取代位置。在掺杂位置中,体系能量计算结果显示填隙硅原子的能量更低,最有可能发生此种掺杂。电子输运性质的研究中,在所有的取代位置中单边硅原子取代组成的电子器件电子输运性质最好。在所有电子器件模型中电子输运性质最好的是填隙硅原子掺杂模型。

氧化石墨烯纳米带能带结构和态密度的第一性原理研究

基于密度泛函理论,采用第一性原理方法,计算了氧化石墨烯纳米带的电荷密度、能带结构和分波态密度。结果表明,石墨烯纳米带被氧化后,转变为间接带隙半导体,带隙值为0.375 e V。电荷差分密度表明,从C原子和H原子到O原子之间有电荷的转移。分波态密度显示,在导带和价带中C-2s、2p,O-2p,H-1s电子态之间存在强烈的杂化效应。在费米能级附近,O-2p态电子局域效应的贡献明显,对于改善氧化石墨烯纳米带的半导体发光效应起到了主要作用。

石墨烯的能带调控及其应用的研究进展

在过去的十多年时间里,石墨烯以其优异的物理性能、化学可调性以及潜在的应用前景引起了广泛关注。然而本征石墨烯是一种零带隙的半金属,这极大地限制了其在很多领域的应用。因此,石墨烯的能带调控并将其由金属性转变为半导体性的相关研究,具有极其重要的意义。综述了现阶段在石墨烯电子结构和能带调控方面的研究进展,并深入探讨了半导体性石墨烯的应用领域和前景,为石墨烯的应用和产业化提供借鉴。

边缘修饰对石墨烯纳米带电子和磁性性质的影响

在广义梯度近似(GGA)下,利用基于密度泛函理论(DFT)框架投影缀加波赝势方法(PAW)的第一性原理,计算了边缘用H原子饱和的锯齿形边缘的石墨烯纳米带(6-ZGNR)和由Al,N和C原子所组成的六边形网状锯齿型薄片(AlN)1(C2)5的结构、电子和磁性性质。计算结果表明:6-ZGNR是直接半导体,基态是反铁磁态,自旋向上和自旋向下的电荷密度都来源于π电子;锯齿形边缘的(AlN)1(C2)5是金属,基态是反铁磁态。由于锯齿形边缘两端的原子的不同使得LUCB在X点是局域在C原子与N原子周围的边界态,拥有π的反键态性质;HOVB在X点是局域在C原子周围的边缘态,拥有π成键态的性质。

锯齿型石墨烯纳米带边界态

基于Kane-Mele紧束缚模型,在包含自旋轨道耦合作用和塞曼作用项后,我们又引入更为合理的自洽在位库仑相互作用,分析研究各相互作用项对边界带的能带结构和电子分布特征的影响.研究结果表明,自旋轨道耦合作用导致自旋简并劈裂出现非常小的能隙,自洽在位库仑相互作用可使能隙增加,边界带范围增加,而塞曼效应却能保护边界带原有的拓扑属性,使边界带穿过能隙,同时也保护边界态在局域边界的自旋极化特征;4个边界能带由左右两组边界子能带系构成,各边界子能带系在费米能处形成左右能隙和费米波矢,其自旋量子霍尔系统构型属于B型.

平面石墨烯纳米带隧穿场效应管理论设计

不同于传统的立体结构隧穿器件,本文给出了一种新型平面石墨烯纳米带隧穿场效应管的理论设计。基于石墨烯纳米带几何宽度调控禁带宽度的思想,构建"双十字形"石墨烯纳米带超晶格作为沟道,设计了石墨烯纳米带超晶格场效应管。从能带结构和传输谱上给出了该器件负微分电阻特性的理论解释,并由器件的输出特性得到了验证。在此基础上对器件的隧穿工作机理做出了探讨。该场效应管在一个器件上实现了多个负微分电阻区域,可应用于多值逻辑电路设计。

扶手椅型石墨烯纳米带场效应管的开关电流及复能带结构

基于对复能带结构的考虑,给出了扶手椅型石墨烯纳米带场效应管的量子输运计算结果,并比较了ID-VG曲线所给出的最小泄漏电流值与ID-VD曲线所给出的开电流值。对于纳米尺度下的石墨烯纳米带场效应管,为了获得最佳性能,指出在关状态下的泄漏电流与开电流之间存在某种折衷,也就是说,ID-VG曲线给出的较小/大的关状态泄漏电流可能伴随着ID-VD曲线的一个较小/大的开电流。随后利用复能带的特性对此作了解释。