Materials Today Energy
Volume 17, September 2020, 100486
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Two-dimensional B3P monolayer as a superior anode material for Li and Na ion batteries: a first-principles study

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Highlights

  • First principles studies of a graphene like B3P monolayer.

  • Dynamic and thermal stability along with large cohesive energy are assurances for experimental synthesis.

  • High theoretical capacity for Li ions and Na ions.

  • Superior attributes of B3P monolayer makes it a promising candidate for high performance 2D anode material.

Abstract

The pursuit for increasing storage capacities of metal ion batteries is directly linked with the search for technologically superior next generation electrode materials. In this context, ab-initio first-principles calculations provide the means for exploring and designing novel 2D materials that can enhance energy storage capacities. In this work, we employ density functional theory calculations to draw a rationale for graphene-like B3P monolayer which shows high dynamical, thermal and mechanical stability. Our calculations predict larger cohesive energies of 2D B3P monolayer as compared to the well-known 2D boron-phosphide and recently predicted borophosphene, indicating its easy experimental synthesis as a graphene-like monolayer. Using both DFT and the thermodynamic energy decomposition scheme, we show that B3P with large lattice parameters and intrinsic metallicity is a potentially excellent 2D material for applications in energy storage devices. The results of our first-principles calculations designate B3P as a superior anode material owing to its high theoretical capacity for both Li and Na ion batteries combined with good open-circuit voltages and low metal ion migration barriers for Li and Na ions. Furthermore, sustained metallicity and thermal stability under loaded intermediate metal ion content indicates B3P monolayer to be a promising 2D material for extending battery operating cycles.

Introduction

Since the successful fabrication of graphene [1], two dimensional (2D) materials have developed into an exciting class of new age materials owing to their potential for increasing efficiency and performance of numerous device technologies. The monoatomic sheets of 2D materials with thicknesses in range of fraction of a nanometer provide unique electronic, optical and mechanical properties which are very distinct and often superior when compared with their bulk counterparts. In addition to many other fascinating features, unique electrochemical properties offered by 2D materials have driven their implementation in applications related to energy storage [2,3], photocatalysis [[4], [5], [6]], solar energy conversion [7,8] and electrocatalytic reactions [9,10]. In particular, the application of 2D materials in energy related applications such as electrochemical batteries have seen an upsurge in the past couple of decades.

Although various forms of electrochemical batteries have been in use since the middle of the nineteenth century, the increasing demands for a shift towards green sources of electrical energy have made lithium and sodium ion batteries most relevant solution for storing electrical energy. The most prominent features of lithium ion batteries, for example, include reversible storage capacity [11], high power density [12], and long life cycles. As a result, the employment of lithium ion batteries has rapidly grown since the first prototype developed in 1985, and they have now become an integral component of portable electronics as well as electric vehicles [[13], [14], [15]]. However, the high pace of advancements in electronic devices far exceeds the gradual progress in increasing the storage capacities of lithium ion batteries. Among other factors, the slow progress in increasing capacities of metal ion batteries can be ascribed in part to the fact that anode materials for lithium ion batteries have not seen a burgeoning development [16]. Consequently, graphite, despite its low capacity of 372 mAhg−1, is still the most commercially preferred anode material in lithium ion batteries owing to its relatively good cycling stability and low cost [[17], [18], [19], [20], [21], [22]].

Since minimal hindrance would be offered by the crystal structure of a reference metal to its isonuclear ion species during insertion (intercalation) and extraction (deintercalation) processes, intuitive choices of anode material in a rechargeable metal ion battery are the pure metal itself or its alloys. However, despite the highest capacities reported for alkali-metal anodes in non-aqueous Li-oxygen/Na-oxygen (Li–O2/Na–O2) batteries and Li-sulfur (Li–S) batteries, the unavoidable formation of dendrites in pure alkali-metal anodes and the resulting safety concerns make them commercially impractical [3,[23], [24], [25], [26]]. On the other hand, anodes materials based on alloys of lithium with silicon and tin oxide are plagued by the pulverization and performance decays incurred during large volume expansion of charging/discharging operations [11,[20], [21], [22]]. Consequently, tremendous research attention has been focused on 2D materials for applications as anodes in metal ion batteries [3,27]. In this context, monolayer graphene appears to be a promising solution owing to the availability of large surface area and shortened ion insertion channels in its honeycomb lattice [28]. However, graphene has poor Li ion absorption capacity [29,30] and is somewhat more problematic for cost effective Na ion batteries [31,32]. Some possible solutions to resolve these issues with pure monolayer graphene include creating point defects, implanting dopants and designing graphene-based composites [33,34]. However, the former two techniques for modifying monolayer graphene generally lead to undesired structural distortions and opening of band gap [[35], [36], [37]]. On the other hand, the electrochemical performance of graphene-based composite anodes has still not surpassed the performance benchmark set by the anodes based on pure alkali-metals and they also suffer from low volumetric energy density and a capacitor-like behaviour with undefined charging and discharging platform [3,26]. This has led researchers to explore rapidly expanding domain of 2D materials for identifying their applications as anode materials in metal ion batteries. In addition to monolayer graphene, other 2D materials explored for applications as anode in lithium and sodium ion batteries can broadly be categorized as elemental analogues of graphene (silicene, germanene, phosphorene, borophene and stanene), transition metal oxides (TMOs), transition metal dichalcogenides (TMDs), transition metal carbides/nitrides (MXenes) and boron-based 2D materials such as h-BN [3,26,27].

Among the various categories of 2D materials mentioned above, boron-based anodes have recently started to garner attention of materials research community. This can be ascribed to the fact that these 2D materials offer a slightly expanded graphene-like honeycomb structure, which is a key design feature for realizing high energy density 2D anode materials [[38], [39], [40], [41]]. In this context, B2S monolayer has recently been proposed as a promising anode material using density functional theory (DFT) calculations and thermodynamic adsorption energy decomposition scheme based on Hess's law [42]. In addition to showing high theoretical capacity, an electronic structure similar to graphene and flexible bonding in a relatively low symmetry honeycomb structure of B2S has been shown to offer enhanced Li adsorption comparable to monolayer graphene under a tensile strain of greater than 4% [38,42]. Similar design strategies have lead researchers to the prediction of B3S [38], g-SiC2 [39] and g-SiC3 [39] as novel 2D anode materials. Since inorganic 2D materials having large lattice parameters and distorted honeycomb structure can mimic strained graphene, borophosphene (BP) has also recently been proposed as an anode material, which exhibit Dirac cone in its electronic structure and high anisotropic metallic character [43]. The metallic characters of borophosphene is distinct from the well-known monolayer boron-phosphide (h-BP) allotrope, where full filling lattice gives rise to a small band gap [[44], [45], [46]]. Comparison of the influence of structure (i.e. h-BP vs BP) [45,47] and composition (i.e. B3S vs B2S) [38,42] on alkali-metal absorption capacities in boron-based 2D materials clearly implies that an increased boron contexnt in form of B3P monolayer would result in p-type metallic character that could provide better capacities than BP (1282 mAhg−1) and enhanced anodic performance for Li and Na ion batteries [47]. Hence, motivated by the bonding flexibility available in 2D monolayers composed of light elements B and P [43,48], in this work we have performed a systematic analysis of a novel B3P monolayer using ab-initio first-principles calculations to draw a rationale for its potential applications as anode material in metal ion batteries.

Section snippets

Computational method

We have performed all the first-principles calculations using the Vienna ab-initio Simulation Package (VASP) package [49,50]. The projector-augmented wave (PAW) [51,52] method has been employed to describe the electron-ion interaction, while the exchange-correlation potentials are modeled using the generalized gradient approximation parameterization proposed by Perdew et al. (PBE) [50]. Throughout the whole of these calculations, van der Waals (vdW) corrections are applied on top of the PBE

Structure and stability

To confirm the stability of 2D material in graphene-like honeycomb structure, we first show that B3P monolayer can form very stable planar structure. The primitive unit cell was optimized with a Pmma space group, composed of two formula units (B6P2) as shown in Fig. 1a. The optimized lattice parameters are a = 5.31 Å, b = 6.173 Å, and α = β = 90°. A comparison of structural properties with h-BP (Boron phosphide) [44] and BP (Borophosphene) monolayers [43] in Table 1 clearly shows largest

Conclusions

In conclusion, we have carried out a systematic investigation of B3P monolayer using First principles calculations and ab-initio MD simulations for examining its potential as a novel 2D anode material in metal ion batteries. Our results indicate that the intrinsic metallicity of B3P monolayer and its low symmetry honeycomb structure makes this material both stable and suitable for anode applications. The dynamically and thermally stability of B3P monolayer has been ascribed to its large lattice

Credit author statement

Conceptualization and Software, Ghulam Abbas: Conceptualization, Methodology, Software. Data curation, Writing- Original draft preparation. Syed Muhammad Alay e Abbas.: Writing- Reviewing and Editing. Amel Laref: Visualization, discussions. Validation. Yu Li∗: Supervision, Software.: Wen-Xing Zhang: Supervision.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This work is supported by the Science and Technology Innovation Commission of Shenzhen (Grant No. JCYJ20190808112401659). The author also acknowledged support from Clean Energy Instituet of Shenzhen and the instrumental Analysis Center Shenzhen University (Xili Campus). Furthermore, we also like to acknowledge research support grant from the “Research Centre of Female Scientific and Medical Colleges”, Deanship of Scientific Research, King Saud University.

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