Blue Phosphorene Heterostructure as A

Sep 25, 2018 - Combining blue-P and hexagonal boron nitride (h-BN) together to construct h-BN/blue-P heterostructure (BN/P) can break the limitation o...
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Hexagonal Boron Nitride/Blue Phosphorene Heterostructure as a Promising Anode Material for Li/Na-Ion Batteries Jinna Bao,† Linsheng Zhu,† Haochi Wang,† Shufeng Han,† Yuhang Jin,† Guoqiang Zhao,† Yiheng Zhu,† Xin Guo,† Jianhua Hou,*,† Hong Yin,*,‡ and Jian Tian*,† †

J. Phys. Chem. C 2018.122:23329-23335. Downloaded from pubs.acs.org by UNIV OF NEW ENGLAND on 10/19/18. For personal use only.

School of Materials Science and Engineering, Changchun University of Science and Technology, Changchun, 130022, PR China ‡ State Key Laboratory of Superhard Materials, Jilin Univesity, Changchun, 130012, PR China S Supporting Information *

ABSTRACT: Blue phosphorene (blue-P), an allotrope of black phosphorene, is prone to oxidize under ambient conditions, which significantly hinders its incorporation in anode for Li/Na ion batteries (LIBs/NIBs). Combining blue-P and hexagonal boron nitride (h-BN) together to construct h-BN/blue-P heterostructure (BN/P) can break the limitation of the restricted properties of blue-P. By means of first-principles computations, we explored the potential of using BN/P as anode material for LIBs/NIBs. Our computations show that the adsorption energies of Li/Na in BN/P are stronger than those in blue-P. Interestingly, although Li has similar chemical properties to Na, their the most energetically favorable sites on BN/P are different. Li prefers to insert into the interlayer of BN/P while Na prefers to absorb on the blue-P surface of BN/P. Furthermore, BN/P can achieve high theoretical specific capacities 801 and 541 mAh/g and low diffusion barriers 0.08 and 0.07 eV for LIBs and NIBs, respectively. All these characteristics suggest that the BN/P could be an ideal candidate used as promising anode material for high-performance LIBs/NIBs.

1. INTRODUCTION In view of safe and effective applications of renewable energy sources, such as solar, geothermal, water, tidal, and wind power,1,2 high-performance electrical energy storage (EES) devices have been under great and urgent demand.3,4 As a successful EES device, owing to their high energy density, long cycle life, little self-discharge, no memory effect and good environmental friendliness,5,6 Li-ion batteries (LIBs) have been used widely for portable electronic devices and electric vehicles since the first commercialization in 1991. In recent years, sharing a storage mechanism similar to LIBs and possessing abundant and low-cost Na resources, Na-ion batteries (NIBs) have received extensive attention and been regarded as prime candidate in nextgeneration EES devices.7,8 Because the material properties of the anodes determine the crucial LIBs/NIBs characteristics, such as capacity, charge/ discharge rate, and cycling life, extensive research efforts have been devoted to developing appropriate anode materials. Graphite is the most commonly used and well-developed anode material for LIBs/NIBs. However, its limited theoretical capacity (372 mAh/g) significantly hampers its progress in high power density or long-term applications.9 Compared to graphite, hard carbon has much better performance in LIBs/NIBs because of its good conductivity and random intercalation sites.10,11 In addition to carbon materials, some metal oxides12−14 are used as anode owing to their superior electrochemical capabilities when compared to graphite. For example, the LIBs/ NIBs with Co3O4 anode displayed high specific capacity 850 mAh/g15 and 447 mAh/g,16 respectively. © 2018 American Chemical Society

To further enhance the energy and power densities of LIBs/ NIBs, two-dimensional (2D) materials have been adopted as anodes due to their high specific surface area and unique geometric structure. Graphene, the most well-known 2D material, exhibited specific capacity 540 mAh/g in LIBs.17 Subsequently, a maximum capacity of 140 mAh/g was achieved by reduced graphene oxide annealed at 500 °C for NIBs.18 Inspired by graphene, researchers have investigated theoretically and experimentally other graphene-like 2D materials, including silicene,19 germanene,20 2D electride,21 transition metal dichalcogenides (TMDs),22,23 and transition metal carbides (MXenes),24,25 as potential anode materials for LIBs/NIBs. Although these 2D material exhibit a high specific capacity and superior rate capability, there are still significant challenges to find high-performance anode materials for LIBs/NIBs. Black phosphorene (black-P), a new and promising 2D semiconductor, has been the focus of rapidly expanding research activities since its first fabrication by exfoliation in 2014.26,27 Some systematic theoretical studies predicted that black phosphorene can present great opportunities for high-performance LIBs/NIBs.28−30 Soon after that, excellent experimental work have confirmed these theoretical predictions.31,32 Very recently, blue phosphorene (blue-P) which is black-P allotrope and was predicted by Zhu and Tomanek in 201433 has been synthesized successfully by the molecular beam expitaxy Received: July 23, 2018 Revised: September 18, 2018 Published: September 25, 2018 23329

DOI: 10.1021/acs.jpcc.8b07062 J. Phys. Chem. C 2018, 122, 23329−23335

Article

The Journal of Physical Chemistry C

Figure 1. Top and side views of (a) optimized unit cell structure for the BN/P and the possible M absorption sites of (b) M/BN/P, (c) BN/M/P, and (d) BN/P/M.

technique.34 Although blue-P is an indirect band gap material, it is nearly as thermally stable as black-P with distinct properties.33,34 Moreover, different from black-P, blue-P has slightly flatter “zigzag” edges than the “armchair” edges of black-P, which can provide more diffusion space for Li/Na ions. Computations showed that blue-P has high storage capacity and low diffusion barrier for Li/Na ions and is a suitable anode material for LIBs/NIBs.35,36 However, despite its stellar properties, blue-P is prone to oxidize under ambient conditions,37 which significantly hinders its incorporation in anode for LIBs/NIBs. Similar to black-P,38−41 chemically stable 2D materials may be used as capping layer to protect blue-P. At present, blue-P capped by with graphene42 or MS2 (M = Nb, Ta)43 has been demonstrated theoretically to be good anode for LIBs. It is well-known that hexagonal boron nitride (h-BN) containing a similar structure to the graphene is chemically stable in air at temperatures as high as 1000 °C.44,45 Hence, it is highly desirable to examine the performance of h-BN/blue-P heterostructure (BN/P) as anode material for LIBs/NIBs. In this work, we perform density functional theory (DFT) computations to investigate the Li/Na adsorption and diffusion properties in the BN/P. Our computations show that the BN/P has large adsorption energy, low diffusion barrier and high theoretical specific capacity for Li/Na. In particular, for Li, the adsorption energy and theoretical specific capacity of BN/P are 2.95 eV and 801 mAh/g, respectively, which are better than those of h-BN/black-P,41 graphene/blue-P,42 and MS2/blue-P.43 All these characteristics suggest that the BN/P could be a promising anode material for LIBs/NIBs.

Figure 2. Band structures and partial density of states of (a) blue-P, (b) BN/P, (c) BN/Li/P, and (d) BN/P/Na.

2. COMPUTATIONAL DETAILS Our calculations have been carried out based on all-electron DFT as implemented in the DMol3 code.46 The exchangecorrelation interactions were described by the generalized gradient approximation (GGA) within the Perdew−Burke− Ernzerhof (PBE) functional.47 And the double numerical atomic orbital plus polarization (DNP) was chosen as the basis set. Especially, to accurately account for the interlayer van der Waals (vdW) interactions, PBE functional with the DFT-D 23330

DOI: 10.1021/acs.jpcc.8b07062 J. Phys. Chem. C 2018, 122, 23329−23335

Article

The Journal of Physical Chemistry C

comparable to the lattice mismatches (Δ = 0.09 Å) in the h-BN/β-BiAs.52 The interaction between h-BN and blue-P can be evaluated in terms of the binding energy (Ebind). The Ebind is calculated as

correction with Grimme methods was chosen. The convergence tolerances for the geometric optimization were set as follows: energy of 10−5 Ha, force of 0.002 Ha/Å and displacement of 0.005 Å. To ensure high-quality numerical results, we chose the real-space global orbital cutoff radius as high as 5.2 Å in all the computations. The Brillouin zone was sampled using a 4 × 4 × 1 Monkhorst−Pack grid for the structural optimization and a 8 × 8 × 1 grid for the electronic structure calculations. The thickness of the vacuum region is set to 25 Å. The transition states were located by computing the minimumenergy path (MEP) for the Li/Na diffusion processes using the linear synchronous transition/quadratic synchronous transit (LST/QST) tools,48 which starts with LST maximization, followed by energy minimization in directions conjugate to the reaction pathway, and then performs QST maximization. Charge transfer between Li/Na and BN/P are computed using Bader charge population analyses.49

Ebind = (EBN / P − EBN − EP )/N

where EBN/P, EBN and EP are the total energy of the combined structure, monolayer h-BN and blue-P, respectively. The N denotes number of phosphorus atoms in the unit cell of the BN/P. After a full relaxation of the atomic positions, we find that the BN-P unit cell with the lattice parameter of 10.00 Å is more stable than others. Besides, another two different stacking patterns (see Figure S2d,e) are also investigated. And the results show that the BN/P shown in Figure S2a is the most stable among them with slightly lower relative energy and slightly larger binding energy. Thus, we mainly consider it in the following studies. The optimized structure of the BN/P unit cell is shown in Figure 1a. The B−N bond length (1.44 Å) changes little while the P−P bond length (2.29 Å) is slightly longer than that (2.27 Å) in blue-P. The equilibrium interlayer distance (3.30 Å) is slightly shorter than that (3.34 Å) in the h-BN/black-P heterostructure (BN/P′)41 and the Ebind (−296 meV/P) is larger than that (−77 meV/P) in BN/P′,41 which indicates that the interaction between h-BN and blue-P is stronger than that between h-BN and black-P. The energies varied with interlayer distance between h-BN and blue-P and are shown in Figure S3, suggesting that the optimized structure of BN/P is really the minimum energy configuration. The band structures and partial density of states (PDOS) of monolayer blue-P and BN/P are shown in Figure 2a,b. The band gap of blue-P is1.92 eV, which agrees well with the previous result (1.95 eV) of blue-P.36 When the blue-P is capped with h-BN, its band gap decreases to 1.85 eV, which is mainly attributed to B-2p and N-2p contribution to valence band. 3.2. Single Li/Na Atom Adsorption on BN/P. To check the ability of BN/P to adsorb M (M = Li and Na) atom, we have explored three different cases: M/BN/P, BN/M/P, and

3. RESULTS AND DISCUSSION 3.1. Optimized Structure and Stability. First, the optimized geometrical structures of monolayer h-BN and blue-P are elucidated in Figure S1. For h-BN, it has hexagonal planar-layered structure with a lattice parameter of 2.50 Å and its B−N bond length and the BNB (NBN) bond angle are 1.44 Å and 120°, respectively. However, for blue-P, it has a puckered structure with a lattice parameter of 3.29 ,Å and its P−P bond length and PPP bond angle are 2.27 Å and 92.5°, respectively. These calculated results are in good agreement with previous results.36,50,51 And then, we construct the unit cell of BN/P by combining a 4 × 4 supercell of h-BN and 3 × 3 supercell of black-P. Three lattice parameters of the combined unit cell are chosen (see Figure S2a−c): (1) 10.00 Å, corresponding to keeping the h-BN lattice fixed and stretching the blue-P system slightly; (2) 9.86 Å, corresponding to keeping the blue-P lattice fixed and shrinking the h-BN system slightly; (3) 9.93 Å, corresponding to the mean value of 10.00 and 9.86 Å. The lattice mismatches (Δ = 0.07−0.15 Å) in the three unit cell are 4, a Li/Na atom is randomly added to the ground state previously found and then optimized. The ground state geometries of BN/P/Lin(Nan) are shown in Figure S4. We find that Lin atoms will tend to aggregate into a cluster at n = 7, while Nan atoms will tend to aggregate into a cluster at n = 5. 3.3. M Atom Diffusion on the BN/P. The charging/ discharging rate of an anode material depends largely on the M mobility. Thus, it is necessary to estimate the diffusion of M atom on the BN/P. Considering the Ead (Li = 1.21−1.52 eV and Na = 0.98−1.12 eV) of M absorption on the h-BN side of M/BN/P is lower than the cohesive energies of the corresponding metals (Li = 1.63 eV and Na = 1.13 eV),41 which may lead to M cluster formation, we only investigate two cases: BN/P/M, corresponding to M diffusion on the blue-P surface of the BN/P, and BN/M/P, corresponding to M diffusion in the interlayer of the BN/P. Parts a and b of Figure 3 show two migration pathways and corresponding energy profiles of BN/M/P. The calculated energy barriers along path I4 → I4 are 0.26 eV for Li and 0.15 eV for Na and those along path I2 → I3 are 0.26 eV for Li and 0.14 eV for Na. The barriers of Li diffusion in the interlayer of the BN/P are comparable to those in graphene/blue-P.42 However, the calculated energy barriers of BN/P/M along path BPt → BPh → BPt are 0.08 eV for Li and 0.07 eV for Na, which are shown in Figure 3. The barrier of Na diffusion on BN/P/M is the same as that (0.07 eV) on BN/P′/M while the barrier of Li diffusion on BN/P/M is lower than that (0.11 eV) on BN/P′/M41 (see Table 2). 3.4. Open Circuit Voltage and Theoretical Specific Capacity. During the charging/discharging process, the polyatomic adsorption on BN/P can affect its theoretical specific capacity (TSC) and open circuit voltage (OCV). To calculate the TSC and OCV, M atoms are added to the most energetically favorable sites of BN/P layer by layer. Because the charge/discharging processes of BN/P follow the common half-cell reaction vs M/M+:

TSC = xmaxF /(M B16N16P18 + xmaxMM)e

where xmax represents the maximum number of M absorption on the B16N16P18, F is the Faraday constant (26.810 Ah/mol), MB16N16P18 means the weight of BN/P and MM refers to the mole weight of the M atom. The calculated OCV as a function of the adatom concentrations and the corresponding optimized configurations are shown in Figure 4. As can be seen from Figure 4,

Figure 4. Calculated open circuit voltage (OCV) as a function of (a) Li and (b) Na concentration and the corresponding optimized configurations.

the OCV of M decreases as M concentrations increases. When the OCV decreases to zero, the adatom concentration reaches its maximum. Consequently, the TSC of M absorption on BN/P can be determined. From Figure 4, we can estimate the maximum adatom concentration to be 36 for Li and Na. As a result, the TSC of Li and Na are calculated to be 801 and 541 mAh/g, respectively, which is higher than the TSC of BN/P′ (607 mAh/g for Li and 445 mAh/g for Na)41 (see Table 2). From the summary of theoretical performance of BN/P and BN/P′ listed in Table 2, we can find that BN/P is more suitable for LIBs/NIBs anodes than BN/P′.

(x 2 − x1)M+ + (x 2 − x1)e− + B16N16P18M x1 ↔ B16N16P18M x2

With volume and entropy effects both neglected, the OCV for M absorption on BN/P can be computed from the energy difference based on the equation below: OCV = ((x 2 − x1)EM + E B16N16P18M x − E B16N16P18M x ) 1

2

/(x 2 − x1)e

where x1 and x2 represent the number of M+ absorption on the B16N16P18. And the TSC is given by 23333

DOI: 10.1021/acs.jpcc.8b07062 J. Phys. Chem. C 2018, 122, 23329−23335

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The Journal of Physical Chemistry C

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4. CONCLUSION In summary, we have investigated the possibility of using h-BN/blue phosphorene heterostructure as Li/Na-ion batteries anode material by means of the first-principles computations. The single Li/Na atom adsorption energy, diffusion barrier, and the maximum theoretical specific capacity as well as open circuit voltage of h-BN/blue phosphorene are systematically examined. Our computations show that capping blue phosphorene with h-BN can reduce the band gap of blue phosphorene and improve significantly the adsorption energy of Li/Na on blue phosphorene. Besides, the h-BN/blue phosphorene heterostructure owns low diffusion barriers of 0.08 eV for Li and 0.07 eV for Na, and high theoretical specific capacity of 801 mAh/g for Li and 541 mAh/g for Na. All these excellent characteristics indicate that the h-BN/blue phosphorene heterostructure is rather promising as anode material for Li/Na-ion batteries.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.8b07062. (I) Optimized structures of h-BN and blue phosphorene, (II) unit cell of the h-BN/blue phosphorene with different lattice parameters and different stack patterns, (III) the energy evolution as a function of interlayer distance between h-BN and blue phosphorene, and (IV) the most stable structures of multiple Li/Na atoms on blue phosphorene side of BN/P (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*(J.H.) E-mail: [email protected]. *(H.Y.) E-mail: [email protected]. *(J.T.) E-mail: [email protected]. ORCID

Jianhua Hou: 0000-0002-9751-4109 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work is financially supported by the Open Project of State Key Laboratory of Superhard Materials (Jilin University) Project No. 201712, National Natural Science Foundation of China (Grants No. 51572105 and 61504046), the Jilin Science and Technology Development Plan (20180520012JH), the “13th Five-Year Plan ” Science and Technology and Research of Jilin Provincial Department of Education (JJKH20181120KJ), and the “Program of Youth Talents” of Jilin Association of Science and Technology (181906). H.Y. is grateful to the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry.

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REFERENCES

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DOI: 10.1021/acs.jpcc.8b07062 J. Phys. Chem. C 2018, 122, 23329−23335

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The Journal of Physical Chemistry C

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DOI: 10.1021/acs.jpcc.8b07062 J. Phys. Chem. C 2018, 122, 23329−23335