二维锗醚在钠离子电池方面的理论研究

陈思钰; 叶小娟; 刘春生

doi:10.7498/aps.71.20220572

摘要

因为钠在地球中的储备更加充足, 而且生产成本也更低廉, 因此钠离子电池也成了继锂离子电池以后, 研究中最热门的储能系统. 然而, 缺少合适的阳极材料是钠离子电池商业化的主要瓶颈. 本文基于密度泛函理论, 通过第一性原理计算对锗醚作为钠离子电池阳极材料的电化学性能进行了充分研究. 计算结果表明钠离子能够均匀稳定地吸附在锗醚两侧, 吸附能达到了–1.32 eV. 即使在较低的钠吸附浓度下, 吸附之后的锗醚也呈现出金属性, 这表明锗醚的电子导电性良好. 钠在锗醚单层结构上有两条可能的扩散路径, 分别沿着之字形和扶手椅方向, 计算表明沿之字形方向的扩散势垒更低, 为0.73 eV. 同时锗醚具有合适的开路电压(1.12 V), 理论容量为167.1 mAh·g^–1, 体积变化率仅为10.8%, 以上结果表明单层锗醚具有作为钠离子电池阳极材料的潜力.

关键词:

Abstract

Because sodium is more abundant in earth’s reserves and the lower cost to produce, sodium-ion batteries (SIBs) have become the most popular energy storage system in research after lithium-ion batteries. However, the the lack of suitable anode materials is a major bottleneck for the commercialization of SIBs. Owing to their large specific surface area and high electron mobility, two-dimensional (2D) materials are considered as the promising anode materials. Some 2D materials have already demonstrated remarkable properties, such as 2D BP (1974 mAh·g^–1) and BC₇ (870.25 mAh·g^–1). However, most of the predicted 2D materials are difficult to satisfy the various requirements for high-performance battery materials. Therefore, it is still necessary to find a new 2D material with excellent properties as electrode material. Recently, Ye et al. [Ye X J, Lan Z S, Liu C S 2021 J. Phys. condens. Mat. 33 315301] predicted a potential 2D material named germanether. The germanether exhibits high electron mobility, which is higher than that of phosphine and MoS₂, indicating its great potential applications in Nano Electronics. Therefore, by first-principles calculations based on density functional theory (DFT), the electrochemical properties of germanether as an anode material for SIBs are fully investigated. The computation results reveal that Na atoms can be adsorbed on germanether without clustering, and the adsorbed energy of Na-ion on the germanether is –1.32 eV. Then the charge redistribution of the whole system is also investigated through Mulliken charge population. In the adsorption process, Na atom transfers 0.71e to germanether. Even at low intercalated Na concentration, the Na adsorbed germanether system demonstrates metallic characteristics, showing good electronic conductivity. Two possible diffusion paths of material are calculated: one is along the armchair direction and the other is along the zigzag direction. The diffusion barrier along the zigzag direction is 0.73 eV for the most likely diffusion path, which is slightly higher than the diffusion barrier of MoS₂, but still lower than many electrode materials used today. Meanwhile, germanether has a suitable specific energy capacity (167.1 mAh·g^–1) and open circuit voltage (1.12 V). The volume change rate is only 10.8 %, which is lower than that of phosphorene and graphite. Based on the above results, germanether can serve as a potential anode material for SIBs.

Keywords:

作者及机构信息

1.
南京邮电大学集成电路科学与工程学院, 南京　210023

2.
南京邮电大学电子与光学工程学院, 南京　210023

通信作者: 叶小娟, yexj@njupt.edu.cn

基金项目: 国家自然科学基金(批准号: 61974068)资助的课题.

Authors and contacts

1.
College of Integrated Circuit Science and Engineering, Nanjing University of Posts and Telecommunications, Nanjing 210023, China

2.
College of Electronic and Optical Engineering, Nanjing University of Posts and Telecommunications, Nanjing 210023, China

Corresponding author: Ye Xiao-Juan, yexj@njupt.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 61974068).

文章全文

参考文献

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施引文献

图 1 (a) 钠原子在锗醚结构上可能吸附的6个点位俯视图; (b) 吸附钠原子后锗醚的电荷差分密度图; (c) 原始锗醚的PDOS图; (d) 吸附钠原子之后锗醚的PDOS图

Fig. 1. (a) Top view of six possible adsorption sites of Na on the germanether; (b) the charge density difference of Na-adsorbed germanether; (c) the PDOS of pristine germanether; (d) the PDOS of Na-adsorbed germanether.

下载: 全尺寸图片幻灯片

图 2 (a) 钠在锗醚上的扩散路径俯视图; (b) 对应的钠在锗醚上的扩散势垒

Fig. 2. (a) Top view of the diffusion paths of a Na atom on the germanether surface; (b) the energy profiles of the corresponding Na diffusion pathways.

下载: 全尺寸图片幻灯片

图 3 (a) Na_0.5Ge₂O的俯视和侧视图; (b) NaGe₂O的俯视和侧视图; (c) 钠-锗醚体系的平均吸附能; (d) 钠-锗醚体系的开路电压

Fig. 3. Top and side views of: (a) Na_0.5Ge₂O; (b) NaGe₂O; (c) the average adsorption energy of Na_xGe₂O; (d) the Open circuit voltage of Na_xGe₂O.

下载: 全尺寸图片幻灯片

图 4 Na_0.056Ge₂O的能带图

Fig. 4. Band structure of the Na_0.056Ge₂O.

下载: 全尺寸图片幻灯片

图 5 (a)—(c) GeH₃-O-GeH₃分子在银(100)表面上三种不同的吸附位置; (d)—(f) GeH₃-O-GeH₃分子脱氢的初态、过渡态、末态的结构俯视图和侧视图; (h)—(j) 脱氢后的GeH₃-O-GeH₂扩散的初始状态、过渡状态以及最终状态的结构俯视图和侧视图; (g) GeH₃-O-GeH₃分子脱氢与(k)脱氢的GeH₃-O-GeH₂分子扩散的能量分布

Fig. 5. (a)–(c) Three different adsorption sites for digermyl ether adsorption on Ag (100). Optimized structures (top and side views) of the initial state (IS), transition state (TS), and final state (FS) during (d)–(f) dehydrogenation and (h)–(j) diffusion processes. Energy profiles of the (g) dehydrogenation and (k) diffusion processes.

下载: 全尺寸图片幻灯片

表 1 部分二维钠离子电池阳极材料的吸附能和扩散势垒(为了方便比较, 吸附能均取绝对值)

Table 1. Adsorption energies and diffusion barriers of some 2D Anode Materials for SIBs (For the convenience of comparison, the adsorption energies are taken as absolute values.)

材料类型	\|吸附能\|/eV	扩散势垒/eV	参考文献
锗醚	1.32	0.73	本文
Ca₂C	2.84	0.06	[30]
h-AlC	2.10	0.41	[31]
Metallic BP₂	3.84	0.03	[32]
Si₃C	0.72	0.34	[33]
2H-SiC	0.81	3.3	[34]
CuTe	1.04	0.31—0.72	[35]
g-GeC	1.26	0.06	[36]
SiC₇	1.64	0.8	[37]
MoN₂	1.64	0.56	[38]
TiOF	1.471	0.14	[39]
GeP₃	1.528	0.27	[40]

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map

[1]	Tarascon J M, Armand M 2001 Nature 414 359 Google Scholar
[2]	Panwar N L, Kaushik S C, Kothari S 2011 Renewable Sustainable Energy Rev. 15 1513 Google Scholar
[3]	Kong L, Li C, Jiang J, Pecht M 2018 Energies 11 2191 Google Scholar
[4]	Bauer A, Song J, Vail S, Pan W, Barker J, Lu Y 2018 Adv. Energy Mater. 8 1702869 Google Scholar
[5]	Luo W, Shen F, Bommier C, Zhu H, Ji X, Hu L 2016 Acc. Chem. Res. 49 231 Google Scholar
[6]	Kubota K, Dahbi M, Hosaka T, Kumakura S, Komaba S 2018 Chem. Rec. 18 459 Google Scholar
[7]	Chayambuka K, Mulder G, Danilov D L, Notten P H 2020 Adv. Energy Mater. 10 2001310 Google Scholar
[8]	K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, Grigorieva I V, Firsov A A 2004 Science 306 666 Google Scholar
[9]	Zhang X, Hou L, Ciesielski A, Samorì P 2016 Adv. Energy Mater. 6 1600671 Google Scholar
[10]	Luo B, Liu G, Wang L 2016 Nanoscale 8 6904 Google Scholar
[11]	Li Y, Guo S 2019 Nano Today 28 100774 Google Scholar
[12]	Ling C, Mizuno F 2014 Phys. Chem. Chem. Phys. 16 10419 Google Scholar
[13]	Kulish V V, Malyi O I, Persson C, Wu P 2015 Phys. Chem. Chem. Phys. 17 13921 Google Scholar
[14]	Meng Q, Ma J, Zhang Y, Li Z, Hu A, Kai J J, Fan J 2018 J. Mater. Chem. A 6 13652 Google Scholar
[15]	Mortazavi M, Wang C, Deng J, Shenoy V B, Medhekar N V 2014 J. Power Sources 268 279 Google Scholar
[16]	Belasfar K, El Kenz A, Benyoussef A 2021 Mater. Chem. Phys. 257 123751 Google Scholar
[17]	Sun W C, Wang S S, Dong S 2021 J. Mater. Sci. 56 13763 Google Scholar
[18]	Zhang J, Zhang Y F, Li Y, Ren Y R, Huang S, Lin W, Chen W K 2021 Phys. Chem. Chem. Phys. 23 5143 Google Scholar
[19]	Ye X J, Lan Z S, Liu C S 2021 J. Phys. Condens. Matter 33 315301 Google Scholar
[20]	Qiao J, Kong X, Hu Z X, Yang F, Ji W 2014 Nat. Commun. 5 4475 Google Scholar
[21]	Radisavljevic B, Radenovic A, Brivio J, Giacometti V, Kis A 2011 Nat. Nanotechnol. 6 147 Google Scholar
[22]	Ye X J, Zhu G L, Meng L, Guo Y D, Liu C S 2021 Phys. Chem. Chem. Phys. 23 12371 Google Scholar
[23]	Clark S J, Segall M D, Pickard C J, Hasnip P J, Probert M I J, Refson K, Payne M C 2005 Cryst. Mater. 220 567 Google Scholar
[24]	Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865 Google Scholar
[25]	Tkatchenko A, Scheffler M 2009 Phys. Rev. Lett. 102 073005 Google Scholar
[26]	Govind N, Petersen M, Fitzgerald G, King-Smith D, Andzelm J 2003 Comput. Mater. Sci. 28 250 Google Scholar
[27]	Chan K T, Neaton J B, Cohen M L 2008 Phys. Rev. B 77 235430 Google Scholar
[28]	Sannyal A, Zhang Z, Gao X, Jang J 2018 Comput. Mater. Sci. 154 204 Google Scholar
[29]	Ling C, Mizuno F 2013 Chem. Mater. 25 3062 Google Scholar
[30]	Rajput K, Kumar V, Thomas S, Zaeem M A, Roy D R 2021 2D Mater. 8 035015 Google Scholar
[31]	Chodvadiya D, Jha U, Śpiewak P, Kurzydłowski K J, Jha P K 2022 Appl. Surf. Sci. 593 153424 Google Scholar
[32]	Ye X J, Xu J, Guo Y D, Liu C S 2021 Phys. Chem. Chem. Phys. 23 4386 Google Scholar
[33]	Wang Y, Li Y 2020 J. Mater. Chem. A 8 4274 Google Scholar
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[35]	Ling F, Liu X, Li L, Zhou X, Tang X, Li Y, Jing C, Wang Y, Xiang G, Jiang S 2022 Appl. Surf. Sci. 573 151550 Google Scholar
[36]	Khossossi N, Banerjee A, Essaoudi I, Ainane A, Jena P, Ahuja R 2021 J. Power Sources 485 229318 Google Scholar
[37]	Yadav N, Chakraborty B, Dhilip Kumar T J 2020 J. Phys. Chem. C 124 11293 Google Scholar
[38]	Zhang X, Yu Z, Wang S S, Guan S, Yang H Y, Yao Y, Yang S 2016 J. Mater. Chem. A 4 15224 Google Scholar
[39]	Wu Y, Wang S, Xie Y, Ye X, Sun S 2022 Appl. Surf. Sci. 574 151296 Google Scholar
[40]	Deng X, Chen X, Huang Y, Xiao B, Du H 2019 J. Phys. Chem. C 123 4721 Google Scholar
[41]	Jiang H R, Shyy W, Liu M, Wei L, Wu M C, Zhao T S 2017 J. Mater. Chem. A 5 672 Google Scholar
[42]	Khossossi N, Banerjee A, Benhouria Y, Essaoudi I, Ainane A, Ahuja R 2019 Phys. Chem. Chem. Phys. 21 18328 Google Scholar
[43]	Putungan D B, Lin S H, Kuo J L 2016 ACS Appl. Mater. Interfaces 8 18754 Google Scholar
[44]	Yu D, Pang Q, Gao Y, Wei Y, Wang C, Chen G, Du F 2018 Energy Stor. Mater. 11 1 Google Scholar
[45]	Sun Q, Dai Y, Ma Y, Jing T, Wei W, Huang B 2016 J. Phys. Chem. Lett. 7 937 Google Scholar
[46]	Shukla V, Jena N K, Naqvi S R, Luo W, Ahuja R 2019 Nano Energy 58 877 Google Scholar
[47]	Liu J, Zhang C, Xu L, Ju S 2018 RSC Adv. 8 17773 Google Scholar
[48]	Dua H, Deb J, Paul D, Sarkar U 2021 ACS Appl. Nano Mater. 4 4912 Google Scholar
[49]	Bhatt M D, O'Dwyer C 2015 Phys. Chem. Chem. Phys. 17 4799 Google Scholar
[50]	Yang Z, Choi D, Kerisit S, Rosso K M, Wang D, Zhang J, Graff G, Liu J 2009 J. Power Sources 192 588 Google Scholar
[51]	Yu T, Zhao Z, Liu L, Zhang S, Xu H, Yang G 2018 J. Am. Chem. Soc. 140 5962 Google Scholar
[52]	Alptekin H, Au H, Jensen A C S, Olsson E, Goktas M, Headen T F, Adelhelm P, Cai Q, Drew A J, Titirici M M 2020 ACS Appl. Energy Mater. 3 9918 Google Scholar
[53]	Zhang W J 2011 J. Power Sources 196 13 Google Scholar
[54]	Khan M H, Moradi M, Dakhchoune M, Rezaei M, Huang S, Zhao J, Agrawal K V 2019 Carbon 153 458 Google Scholar
[55]	Wang B, König M, Bromley C J, Yoon B, Treanor M J, Garrido Torres J A, Caffio M, Grillo F, Früchtl H, Richardson N V, Esch F, Heiz U, Landman U, Schaub R 2017 J. Phys. Chem. C 121 9413 Google Scholar
[56]	Kang B, Kim Y, Cho J H, Lee C 2017 2 D Mater. 4 025014 Google Scholar
[57]	Zhan L, Wan W, Zhu Z, Shih T M, Cai W 2017 J. Phys. Conf. Ser. 864 012037 Google Scholar
[58]	Zhao B, Shen D, Zhang Z, Lu P, Hossain M, Li J, Li B, Duan X 2021 Adv. Funct. Mater. 31 2105132 Google Scholar

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