Zhang 2016

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Article
Could Borophene Be Used as A Promising Anode
Material for High-performance Li Ion Battery?
Yang Zhang, Zhi-Feng Wu, Peng-Fei Gao, Shengli Zhang, and Yu-Hua Wen
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b05747 • Publication Date (Web): 03 Aug 2016
Downloaded from http://pubs.acs.org on August 6, 2016
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Page 1 of 19 ACS Applied Materials & Interfaces
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4 Could Borophene Be Used as A Promising Anode Material for
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6 High-performance Li Ion Battery?
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8 Yang Zhang,1* Zhi-Feng Wu,1 Peng-Fei Gao,1 Sheng-Li Zhang,1* and Yu-Hua Wen2
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Ministry of Education Key Laboratory for Nonequilibrium Synthesis and Modulation of
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12 Condensed Matter, Department of Applied Physics, Xi’an Jiaotong University, Xi’an 710049,
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14 China
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16 Institute of Theoretical Physics and Astrophysics, Department of Physics, Xiamen University,
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18 Xiamen 361005, China
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20 ABSTRACT: The rapid development of electronic products has inspired scientists to design and
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22 explore novel electrode materials with ultra high-rate of charging/discharging capability, such as
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two-dimensional (2-D) nanostructures of graphene and MoS2. In this study, another 2-D nanosheet,
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25 that is borophene layer, has been predicted to be utilized as a promising anode material for
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27 high-performance Li ion battery based on density functional theory calculations. Our study has
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29 revealed that Li atom can combine strongly with borophene surface strongly and easily, and exist
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31 as a pure Li+ state. A rather small energy barrier (0.007 eV) of Li diffusion leads to an ultra-high
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33 diffusivity along uncorrugated direction of borophene, which is estimated to be 104 (105) times
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35 faster than that on MoS2 (graphene) at room temperature. A high Li storage capacity of 1239
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37 mAh/g can be achieved when Li content reaches to 0.5. A low average operating voltage of 0.466
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39 V and metallic properties result in that the borophene can be used as a possible anode material.
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Moreover, the properties of Li adsorption and diffusion on the borophene affected by Ag (111)
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42 substrate have been studied. It has been found that the influence of Ag (111) substrate is very weak.
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44 Li atom can still bind on the borophene with a strong binding energy of -2.648 eV. A small
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46 energy barrier of 0.033 eV can be retained for Li diffusion along the uncorrugated direction,
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48 which can give rise to a high Li diffusivity. Besides, the performances of borophene-based Na ion
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50 battery have been explored. Our results suggest that an extremely high-rate capability could be
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52 expected in borophene-based Li ion battery.
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Keywords: Borophene, Li diffusion, Energy barrier, Li storage capacity, Li ion battery
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1. INTRODUCTION
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5 With the rapid development of mobile devices and electric vehicles (EVs), rechargeable
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7 batteries with high energy and power densities are highly desired.1-3 Lithium ion battery, one of
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9 the most widely studied rechargeable batteries, is hoped to be a critical candidate for the next
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11 generation energy technology due to its great advantages of portability, energy efficiency, and
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13 non-pollution to the environment.4,5 However, to realize the application of Li ion battery in EVs,
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15 one great challenge is to simultaneously achieve high power and energy capacity with rapid
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17 charging/discharging rate for several seconds. Generally, using a bulk material such as layered
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graphite as an anode can achieve a high energy density,6-9 but suffer from a low power density,
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20 which critically depends on the diffusivity of Li+ ions and electrons through the electrode. By
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22 introducing large areas of surface and interface for storage of charged species on electrodes, a very
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24 high power rate can be achieved in electrochemical capacitors.10 Therefore, a promising strategy
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26 to create high-power Li ion battery is to develop new materials which behave high electrical
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28 conductivity for fast electron transport and a large surface area with a shallow diffusion barrier for
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30 fast Li ion diffusion.
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32 During the past decades, 2-D nanostructures have attracted extensive attention due to the large
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surface areas for Li storage and unique electronic properties. Graphene, one of the most
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well-studied 2-D materials, has been expected to be a good candidate as a high-power and
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37 high-energy electrode material due to its intrinsically superior electrical conductivity, excellent
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39 mechanical flexibility, large surface area, and the open and flexible porous structure of graphene
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41 powders.11-17 Owing to broad voltage windows,18 graphene has been utilized as both anode and
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43 cathode materials with great success.19-21 However, a relative high diffusion barrier (around 0.3 eV)
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45 significantly slows down the charging/discharging process.22,23 Meanwhile, others graphene-like
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47 2-D materials, such as MoS2 and VS2 have also been widely studied and exhibit relative high
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49 capacities (335 mAh/g for MoS2 and 466 mAh/g for VS2) and high-rate capability.24,25 Whereas,
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relative high energy barriers of MoS2 (0.25 eV) and VS2 (0.22 eV) restrict their potential
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52 applications for high power Li ion battery. Recently, phosphorene,26,27 a highly anisotropic
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54 monolayer isolated successfully from black phosphorus, has been excepted to be a promising
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56 anode material for advanced Li ion battery.28-33 It has been claimed that the performance of Li
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58 diffusion is highly anisotropic with the energy barriers of 0.08 and 0.68 eV along armchair and
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3 zigzag directions,28 respectively. Such a relative small barrier (0.08 eV) is quite lower than that on
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5 MoS2 (0.25 eV) and VS2 monolayer (0.22 eV),25 indicating an excellent rapid charging/charging
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7 capability. But, its theoretical capacity (433 mA h/g, Li0.5P) is low,30 which is comparable to that
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9 of VS2.25 Therefore, a satisfactory electrode with good conductivity, good cycle stability, and
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11 ultra-high speed capability still needs to be developed.
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13 Very recently, a new 2-D nanosheet of borophene has been successfully synthesized on the
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15 silver (111) surface.34 Similar to phosphorene, the borophene is also a puckered morphology with
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17 highly anisotropic corrugation, which results in the unique unidirectional conductivity along the
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uncorrugated direction. Furthermore, the mechanical properties of borophene are also anisotropic.
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20 It is found that the in-plane Young’s modulus along the uncorrugated direction is 398 GPa·nm,
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22 which potentially rivals graphene (340 GPa·nm).34 On the basis of these advantages above, the
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24 puckered borophene layer can be expected to use as a promising electrode material for Li ion
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26 battery. For exploring that, a detailed study on the Li adsorption and diffusion process on the
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28 borophene layer is indispensible.
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30 In this study, we will employ density functional theory (DFT) calculations to systematically
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32 investigate the behaviors of Li adsorption and diffusion on borophene layer. The binding process
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and various diffusion pathways are considered. The results show that Li atom adsorbs on the
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borophene with a rather low binding energy of -2.770 eV. Because of the anisotropic ripple
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37 structure, Li diffusion on the borophene is highly anisotropic with diffusion along the
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39 uncorrugated direction being highly energetically favorable, while that along the corrugated
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41 direction is relative difficult. At room temperature, the diffusion mobility of Li atom along the
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43 uncorrugated direction is estimated to be 104 ~ 105 times faster than other 2-D anode candidates
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45 such as MoS2 and graphene. Furthermore, the performance of electrical conductivity and operating
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47 voltage affected by Li intercalations is explored.
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51 2. COMPUTATIONAL DETAILS
52 All calculations were performed by using first-principles study based on the
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54 spin-polarized DFT within the projector augmented wave method,35,36 as implemented in
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56 Vienna ab initio simulation package (VASP).37,38 The generalized gradient approximation
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58 (GGA) with the functional of Perdew-Burke-Ernzerhof (PBE) was employed to describe
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3 the electron exchange-correlation interactions.39,40 The cut-off of plane-wave kinetic
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5 energy and the convergence of total energy were set to be 400 eV and 10-5 eV, which were
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7 tested to sufficiently achieve a high accuracy. All studied borophene layers with or without
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9 Li adsorption were modelled in a large rectangular supercell and located in the x-y plane.
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11 Because of the application of periodic boundary conditions, a vacuum region of at least 10
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13 Å was applied along the z-axis in order to eliminate the interactions between neighbour
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15 layers. For calculating the properties of Li adsorption and diffusion, a supercell containing
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17 3 × 4 primitive cells was adopted, which possesses the sizes of 8.614 and 6.479 Å. Thence,
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the brillouin zone integrations were approximated by 11×11×1 k-point meshes with
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20 Gamma centered grid. For exploring the effect of Li intercalation, 13×13×1 k-point meshes
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22 were employed because a relative small supercell was adopted. The structural relaxations
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24 were performed by computing the Hellmann-Feynman forces using conjugate gradient
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26 algorithm within a force convergence of 0.01 eV/Å.41 In order to search a minimal energy
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28 path of Li diffusion, the climbing image nudged elastic band method (CNEB, embedded in
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30 VASP) was employed.42,43
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34 3. RESULTS AND DISCUSSION
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3.1. Structures and Electronic Properties of Borophene Layer
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37 As illustrated in Figure 1, borophene layer has a highly anisotropic geometrical structure and
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39 belongs to orthogonal crystal system with space group of Pmmn. A corrugation structure like
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41 W-shape is presented along the x-axis, while along the y-axis, there is no corrugation. One
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43 primitive cell contains two B atoms located in two different planes, showing a buckling height of
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45 0.881 Å along the z-axis. The optimized lattice constants along the x- and y-axis are 2.866 and
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47 1.619 Å, respectively, which are in good agreement with theoretical and experimental data.34 The
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49 B-B bond length along the x-axis is 1.867 Å, while along the y-axis it is 1.619 Å, which results in
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anisotropic mechanical properties, such as the in-plane Young’s modulus and Poisson’s ratio.34
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52 Electronic band structure shows that the borophene layer is metallic with some bands occupied by
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54 the B p orbital crossing the Fermi level along the Г-X and Y-S directions, which parallel to the
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56 uncorrugated direction (i.e., y-axis). However, along the corrugated direction (i.e., x-axis), a large
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58 band gap is presented (see Figure S1). The electronic properties above infer that the borophene is a
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3 highly anisotropic metal and electrical conductivity is only confined along the uncorrugated B-B
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5 chains.
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22 Figure 1. Schematics of freestanding borophene layer viewed from (a) z, (b) x, and (c) y directions. Black solid
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24 rectangle and blue square dot in (a) denote the unit cell of borophene and the stable binding site of Li on
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26 borophene, respectively. Green and orange balls represent B atoms located in different planes.
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30 3.2. Li Adsorption and Diffusion on Borophene Surface
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32 Because of the corrugated structure, borophene itself might provide a transport facility for Li
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diffusion along the concave channel as shown in Figure 1c. For testing that, the structural stability
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of Li adsorption on borophene layer should be investigated first, which is also essential for the
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37 potential application of borophene-based Li ion battery. We have adopted a 3 × 4 supercell
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39 contained 24 B atoms to adsorb one Li atom which was placed at variety positions above the
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41 borophene surface with a initial height of 3.0 Å or so. After structural optimization, it has been
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43 found that the most stable binding site is just on the top of B atom in the concave side (TC) and
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45 depicted by the blue square dot in Figure 1a. The distance between Li and B1 is 2.776 Å, while the
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47 distances between Li and B2/B3/B4/B5 are 2.376 Å (see Figure S2a). From difference charge
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49 density or Bader charge analysis as displayed in Figure S2b, a strong ionic Li-B bond can be
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observed, resulting in that the B-B bond lengths around the Li atom have a slight expansion along
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52 the corrugated direction.
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54 In order to examine whether the Li atom can be easily adsorbed on the borophene layer, the
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56 corresponding binding process has been studied. By increasing the distance between Li atom and
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58 borophene, a relationship of total energy and the distance can be obtained (see Figure S2c).
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3 Obviously, the relative energy varies remarkably with the increasing distance. When the distance
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5 is beyond 7.0 Å or so, it keeps almost a constant value, indicating no interaction between Li atom
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7 and borophene. It should be noted that, during the binding process, no energy barrier is presented,
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9 which implies that the borophene surface can easily attract Li atom to form an ionic Li-B bond. To
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11 quantify the stability of the borophene adsorbed Li atom, the binding energy was calculated
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13 according to the following equation
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Eb = Etot − ( EBorophene + ELi )
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17 where Etot , EBorophene , and ELi are total energy of Li-adsorbed borophene, solo borophene,
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19 and a Li atom, respectively. According to this definition, a more negative binding energy
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21 implies a more energetically favourable reaction between the borophene and Li atom. It has
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23 been found that the binding energy at the site TC is -2.770 eV, which is quite smaller than
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25 those of graphene, MoS2, VS2, and phosphorus layers adsorbed one Li atom.23,25,28 It means
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27 that a relatively rapid binding process and strong combination between the borophene and
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Li atom could be achieved.
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30 As is well known, the performance of charging/discharging and circuit rates in Li ion battery is
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32 highly dependent on the diffusivity of Li atom on the electrode material. Therefore, the study of Li
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34 diffusion on borophene surface becomes significant. As depicted in Figure 2a-c, three diffusion
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36 pathways, i.e., path-x1, path-x2, and path-y are considered. Both the path-x1 and path-x2 are
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38 along the corrugated direction of borophene, while the path-y is along the uncorrugated one (or the
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40 concave channel). Clearly, if the Li diffusion can be carried out along the former way, overcoming
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42 the ripple between the neighbor concave channels (on the same side) should be indispensable. On
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44 the contrary, along the latter one, the diffusion would be easy because of the flat pathway. The
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binding energy of Li migrating on the borophene surface is shown in Figure 2d. For the path-x1
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47 and path-x2, the energy barriers are predicted to be 0.289 and 0.267 eV, respectively. Combining
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49 with the stable binding site TC (on the top of B atom in the concave channel), a possible pathway
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51 of Li diffusion along the corrugated direction can be derived along the B-B bond (depicted as blue
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53 arrows) owning to a relative small energy barrier of 0.274 eV. Whereas, a rather small energy
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55 barrier of 0.007 eV is observed for the diffusion pathway of path-y, which infers that the Li
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57 diffusion along the uncorrugated direction is much easier than that along the corrugated direction.
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3 Such an anisotropic diffusion behavior is mainly ascribed to the anisotropic structure of the
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5 borophene layer.
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22 Figure 2. Top (left panel) and side (right panel) views of Li diffusion on borophene surface along (a) path-x1, (b)
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24 path-x2, and (c) path-y. Corresponding binding energy along the diffusion pathways is shown in (d). Blue arrows
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26 in (a) denote the possible pathway of Li diffusion along the corrugated direction. Some typical binding sites in
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28 each pathway are labeled by B1 and S1 for the path-x1, B2' and S2' for the path-x2, and B1 and B2' for the path-y. B1
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30 is a stable binding site, the rest is unstable. Along the diffusion path-y (parallel to the uncorrugated direction), B2'
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is a saddle point, while S1 is a saddle point for the diffusion pathway along the corrugated direction.
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According to the Arrhenius equation, the diffusion constant (D) of Li atom on borophene
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37 surface can be evaluated by the following equation
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39 -E 
D ∝ exp a  ,
40  k BT 
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42 where Ea and kB are the diffusion energy barrier and Boltzmann constant, T is the environmental
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44 temperature. By using this approach, the temperature-dependent diffusivity of Li atom in electrode
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materials can be estimated correctly.28,31,44-48 At room temperature, the diffusion mobility of Li on
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47 borophene surface along the uncorrugated direction is estimated to be about 3.1×104 times faster
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49 than that along the corrugated direction. For the case of the diffusion along the corrugated
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51 direction, the saddle point is above the ripple and just on the top of B atom (denoted as S2' in
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53 Figure 2b), which gives rise to a large energy barrier (0.274 eV) of Li diffusion. Whereas, for the
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55 diffusion along the uncorrugated direction, the saddle point is at the bridge of B-B bond in the
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57 concave channel (denoted as B2' in Figure 2c) resulting in a negligible energy barrier of 0.007 eV.
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3 The performance of Li diffusion along the corrugated direction is much worse than that along the
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5 uncorrugated direction, but still better than that of graphene (energy barrier 0.327 eV).23
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7 Furthermore, in other 2-D nanostructures, such as MoS2, VS2, and phosphorene, the energy
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9 barriers of Li diffusion on them are 0.25, 0.22, and 0.08 eV,25,28,31,44 respectively, which are much
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11 larger than that on the borophene layer. Obviously, the diffusion mobility of Li atom on the
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13 borophene surface at room temperature is estimated to be 1.2×104 and 2.4×105 times faster than
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15 that on MoS2 and graphene, respectively. Such a rapid Li diffusion rate cannot be achieved by
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17 existing anode materials.
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The anisotropic structure of borophene also results in substantial mechanical anisotropy. For
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20 instance, the in-plane Young’s modulus along the uncorrugated direction is much lower than that
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22 along the uncorrugated direction.34 The anisotropic mechanical properties imply that structural
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24 deformation of borophene can be caused easily along the corrugated direction, which would affect
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26 the Li diffusion on the borophene surface. For confirming that, an in-plane uniaxial strain was
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28 applied to a 3 × 4 supercell along the corrugated direction. It has been found that under the strain
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30 loading, the ripple structure of borophene can still be maintained. Then, we put one Li atom on the
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32 strained borophene surface, and find that the stable binding site does not change. The diffusion
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energy barrier along the uncorrugated direction enlarges and reduces slightly under the tension and
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compression strain, respectively. For example, the tension strain of 5 % leads to the energy barrier
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37 increasing from 7.0 to 8.6 meV, while the compression strain of -5 % results in it decreasing from
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39 7.0 to 5.7 meV (see Figure S3). Thus, a high-performance of Li diffusion can be expected in
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41 borophene layer, even in the strained one.
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43 3.3. Effect of Li Intercalation and Average Open Circuit Voltage
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45 To further understand the performance of borophene-based Li ion battery, the structural
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47 stability and electronic properties of LixB with respect to the Li content x should be explored. Here,
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49 a series of higher configurations with stoichiometry of LixB are considered. By employing
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2 × 2 , 2 × 2, 2 × 3, 2 × 4, and 2 × 5 supercells with one Li atom adsorbed on borophene, the
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52 LixB with various Li concentrations can be constructed (the corresponding x = 0.25, 0.125, 0.083,
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54 0.0625, and 0.05, respectively) as shown in Figure 3a-d. All the LixB are predicted to be stable
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56 with low binding energies. But, due to the electrostatic repulsive interactions among the neighbor
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58 Li cations, the binding energy of LixB increases dramatically from -2.718 to -2.027 eV as the Li
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3 content x increases from 0.05 to 0.25, indicating that the LixB with a higher Li concentration
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5 exhibits lower structural stability. Even so, the binding energy of Li0.25B is still much lower than
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7 that (-1.606 eV) of metallic Li bcc bulk, which implies that the embedded Li atoms cannot be
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9 assembled easily on the borophene surface. As an attempt, we have intercalated 16 Li atoms to the
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11 borophene surface within a large 4 × 4 supercell (i.e., Li0.5B) and found that the Li0.5B with all Li
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13 atoms adsorbed on one side of borophene is unstable. Its binding energy is -0.278 eV, which is
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15 much higher than that of metallic Li bulk. When the 16 Li atoms are embedded evenly on two
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17 sides of borophene to guarantee a maximum Li-Li distance, the binding energy is predicted to be
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-1.976 eV, exhibiting a much better structural stability than the system of phosphorene with 0.25
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20 Li content intercalation.30 Furthermore, the borophene layer with x = 0.5 Li concentration
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22 possesses a negligible expansion of surface areas (-0.104 %), which guarantees the safety of
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24 borophene-based Li ion battery during the charging/discharging process.
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40 Figure 3. Geometrical configurations of LixB with various Li contents (a) - (d) on one side of borophene. Binding
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42 energy as a functional of the Li content x is shown in (e).
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Figure 4 shows the electronic band structures of LixB complexes, as well as the spatial charge
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47 density at the Fermi-level. It is clear to see, no matter how many Li atoms are intercalated to the
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49 borophene, the metallic behaviors are always presented, even during the process of Li diffusion
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51 (see Figure S4). From the partial charge density at the Fermi-level, the conducting electrons of all
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53 studied LixB spread in the whole borophene layer except for Li atom, exhibiting a good
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55 conductive performance. Such a good conductive performance is mainly attributed to the p orbital
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57 of B atoms. Besides, open circuit voltage (OCV) is another key factor to characterize the
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3 performance of Li ion battery, which can be derived directly from the energy difference before
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5 and after Li intercalation. Considering that the charging/discharging processes of borophene-based
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7 anode can be assumed as
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9 Li x1 B + ( x2 - x1 )Li+ + ( x2 - x1 )e - ↔ Li x2 B ,
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thence, the average OCV of LixB can be evaluated as the following formula
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13 ELi x1B + ( x2-x1 ) ELi - ELi x 2 B ,
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x2-x1
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16 where ELi B , ELi B , and ELi are the potential energy of Lix1B, Lix2B, and metallic Li bulk,
x1 x2
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respectively. Based on this measurement above, various electrochemical properties correlated to
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20 Li ion Battery can be predicted accurately, such as the average insertion potential,45,46 and the
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22 charging/discharging voltage of Li intercalation in metal oxides and metal dichalcogenides.48-50
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37 Figure 4. Electronic band structures of LixB: (a) x = 0.05, (b) x = 0.083, and (c) x = 0.125. Corresponding spatial
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electronic distribution (the isosurface value is 0.005 e/Å3) at Fermi-level is shown as the insets. Dash line denotes
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the Fermi-level.
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44 The average voltage of LixB with respect to the Li content x in the range of 0 to 0.25 is shown
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46 in Figure 5. In the low range (0 ≤ x ≤ 0.05), the average voltage is predicted to be 1.11 V. Similar
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48 to other electrode materials,28 a sharp drop of voltage is observed when 0.05 ≤ x ≤ 0.125.
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50 Subsequently, a low average voltage of 0.177 V is still maintained as x = 0.25. The overall average
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52 voltage profile is 0.466 V (0 ≤ x ≤ 0.25), which is much lower than 0.93 V of VS2,25 and higher
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54 than 0.312 V of phosphorene.29 Moreover, this average voltage is in the moderate range for the
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application in anode materials where the suitable operating voltage is lower than 1.5 V.51 Notably,
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the borophene layer is able to provide a much higher capacity of 620 mAh/g when Li content is
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3 0.25 (i.e., Li0.25B), which cannot be achieved by phosphorene (433 mAh/g, Li0.5P),30 VS2 (466
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5 mAh/g, Li2VS2),25 and MoS2 (335 mAh/g, Li2MoS2).25 Furthermore, an ultra-high capacity of
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7 1239 mAh/g can be observed in the Li0.5B which is predicted to be stable with the binding energy
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9 of -1.976 eV.
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Figure 5. Average voltage as a functional of Li content x in LixB.
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32 3.4. Li Adsorption and Diffusion on Borophene Affected by Ag (111) Substrate
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34 Since 2-D borophene has been synthesized successfully on the Ag (111) surface and its
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36 freestanding form is not very stable because of some imaginary frequency phonon spectrum,34
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38 the performances of Li adsorption and diffusion on the borophene affected by Ag (111) substrate
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40 need to be further explored. For fabricating the hybridized system of borophene & Ag substrate, 1
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42 × 3 sized borophene and 1 × 3 sized Ag (111) surface contained four Ag layers have been
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44 adopted, which possesses the smallest lattice mismatch. The optimized lattice constants of
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46 borophene along the x- and y-axis are 2.889 and 1.644 Å, which are well consistent with the
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48 experimental results.34 Next, a large 3 × 6 supercell of borophene (the corresponding size of Ag
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50 (111) substrate is 3 × 2 3 ) has been utilized to explore the performances of Li adsorption and
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52 diffusion. Two possible pathways of Li diffusion and the corresponding energy barriers are
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54 displayed in Figure 6. The results show that the effects of Ag substrate on the Li adsorption are
55
56 very small. The corresponding binding energy is -2.648 eV, slightly larger than -2.770 eV of
57
58 the freestanding borophene adsorbed one Li atom. However, the performances of Li diffusion
59
60 11

1
2
3 on borophene affected by the Ag substrate are significantly. The energy barrier of Li
4
5 diffusion along path-x (corrugated direction) is 0.192 eV, which is much smaller than 0.274
6
7 eV of the freestanding borophene. On the contrary, the energy barrier of along path-y
8
9 (uncorrugated direction) is 0.033 eV, which is much larger than 0.007 eV of the freestanding
10
11 borophene. In spite of that, anisotropic characteristics of Li diffusion on the borophene
12
13 with Ag (111) substrate can also be preserved, which is similar to those on the freestanding
14
15 borophene. Furthermore, the behaviors of Li adsorption and diffusion on borophene affected by
16
17 Ag (111) substrate are still better than those of graphene and MoS2. Thus, one can propose that an
18
extremely high-rate capability can be expected in borophene-based Li ion battery because of the
19
20 rather small energy barrier of Li diffusion, good performance of electrical conductivity, low
21
22 operating voltage and high capacity.
23
24
25
26
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28
29
30
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33
34
35
36
37
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43
44
45
46
47 Figure 6. Two possible pathways of Li diffusion along (a) corrugated (path-x) and (b) uncorrugated (path-y)
48
directions of borophene layer fabricated on Ag (111) surface. The corresponding energy along these two pathways
49
50
is shown in (c). Green, orange, purple, and grey balls represent B (lower layer), B (upper layer), Li, and Ag atoms,
51
52 respectively.
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54
55
56 3.5. Properties of Na Adsorption and Diffusion on Borophene Surface
57
58 The properties of Na adsorption and diffusion on borophene layer are explored and
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60 12

1
2
3 summarized in Table 1. For comparison, the corresponding performances of Li atom are also listed
4
5 in this table. The results show that the stable binding site of Na atom is TC point with a low
6
7 binding energy of -2.318 eV which is much smaller than that (-1.083 eV) of Na bcc bulk. Quite
8
9 similar to the behaviors of Li atom, Na diffusion on the borophene layer is also highly anisotropic.
10
11 Along the uncorrugated direction, the diffusion is energetically favorable with a rather small
12
13 energy barrier of 0.002 eV. Whereas, along the corrugated direction, it is relative difficult with
14
15 the energy barrier of 0.198 eV, which is still superior than graphene, MoS2, and VS2.23,25 At room
16
17 temperature, the diffusion mobility of Na atom along the uncorrugated direction is estimated to be
18
2.9×105 times faster than that of graphene. In addition, we have employed a 2 × 2 supercell of
19
20 borophene adsorbed one Na atom (i.e., Na0.25B) to study the effect of Na intercalation,
21
22 qualitatively. It has been found that the binding energy of Na0.25B is -1.370 eV and much smaller
23
24 than that of Na bcc bulk, indicating that Na atoms cannot be easily assembled and metalized at
25
26 room temperature. Of particular interest is that the average OCV of NaxB complexe is 0.287 V in
27
28 the range of Na content (0 ≤ x ≤ 0.25), which is a suitable voltage for anode material. The
29
30 advantages above indicate that an extremely high-rate capability can also be expected in
31
32 borophene-based Na ion battery.
33
34
35 Table 1. Properties of Li and Na atoms adsorption and diffusion on borophene surface: stable binding site
36
37 (BT), binding energy Eb (eV), diffusion energy barriers (unit in eV) along corrugated Ec and uncorrugated Eu
38
39 directions of borophene, the multiple number of diffusion mobility compared to graphene M, and average
40
41 open circuit voltage U (V) in the range of Li or Na content (0 ≤ x ≤ 0.25).
42
43 Atoms BT Eb Ec Eu M U
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45 Na TC -2.318 0.198 0.002 2.9×105 0.287
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47 Li TC -2.770 0.274 0.007 2.4×105 0.466
48
49
50
51 4. CONCLUSION
52
53 In summary, by employing the spin-polarized density function theory calculations, we have
54
systematically investigated the Li adsorption and diffusion on borophene surface. Our results
55
56 indicate that Li atoms can strongly bind with the borophene layer, and no energy barrier is
57
58
59
60 13

1
2
3 observed during the binding process. Both the borophene layer and adsorbed complexes exhibit
4
5 metallic properties, which is essential for use as an electrode. Because of the ripple structure, the
6
7 diffusion of Li on borophene is highly anisotropic with diffusion along the uncorrugated direction
8
9 being highly energetically favorable, while that along the corrugated direction is relative difficult.
10
11 Such anisotropic behaviors are attributed to a large energy barrier of 0.274 eV along the
12
13 corrugated direction and a rather small one of 0.007 eV along the uncorrugated direction.
14
15 Furthermore, the overall average voltage of LixB in the range of 0 ~ 0.25 is 0.466 V. A high
16
17 capacity up to 1239 mAh/g can be achieved in Li0.5B, much higher than that phosphorene and
18
MoS2 which are the promising anode candidates for Li ion battery. In addition, a rather small
19
20 diffusion energy barrier of 0.002 eV along the uncorrugated direction and low average operating
21
22 voltage of 0.287 V have been predicted in borophene-based Na ion battery. Our results suggest
23
24 that the borophene layer can be expected to utilize as a promising anode material of Li (Na) ion
25
26 battery with ultra-high rate capability.
27
28
29
30 ASSOCIATED CONTENT
31
32 Supporting Information
33
Main structural parameters, difference charge density, band structure of borophene layer, and
34
35
energy barriers of Li diffusion effected by in-plane uniaxial strain.
36
37
38
39 AUTHOR INFORMATION
40
41 Corresponding Authors
42
*
43 E-mail: yzhang520@mail.xjtu.edu.cn (Y. Zhang).
44
*
45 E-mail: zhangsl@mail.xjtu.edu.cn (S.-L Zhang).
46
47 Notes
48
49 The authors declare no competing ﬁnancial interest.
50
51
52
ACKNOWLEDGMENT
53
54 This work was supported by the National Natural Science Foundation of China (Grant Nos.
55
56 11204232, 11374237, 11474234, and 51271156).
57
58
59
60 14

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3 Graphical Abstract
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23 A rather small energy barrier of 7.0 (2.0) meV is observed for Li (Na) diffusion along the
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25 uncorrugated direction of borophene layer, which indicates that an ultra-high charging/discharging
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27 capability could be achieved in borophene-based Li (Na) ion battery.
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