石墨烯层间距调控抑制锂枝晶生长的第一性原理研究

doi:10.11949/0438-1157.20220477

摘要/Abstract

摘要：

抑制锂枝晶生长是锂金属电池中亟需解决的关键问题之一。电极表面涂覆石墨烯可以有效抑制锂枝晶生长。然而，目前对石墨烯层间距影响锂枝晶生长的机制尚不明晰。采用第一性原理计算方法从吸附和扩散两个角度考察了石墨烯层间距对锂枝晶生长的影响。结果表明，石墨烯的层间距为0.45 ~ 0.55 nm时，电极表面对锂原子的吸附较弱，锂原子扩散性能最好，有利于抑制锂枝晶的生长。若小于该层间距，锂原子在层间的扩散较难。反之，锂原子则会在石墨烯层上吸附聚集，导致锂枝晶的快速生长。此外，在最佳层间距下，B掺杂和N掺杂改性的石墨烯，能促进锂原子在石墨烯层间的扩散，避免锂的不均匀沉积，从而抑制锂枝晶的形成。

关键词: 石墨烯, 层间距, 锂枝晶, 吸附, 第一性原理

Abstract:

Inhibiting the growth of lithium dendrites is one of the key problems to be solved in lithium metal batteries (LMBs). Coating graphene on the electrode surface can effectively prevent lithium dendrites growth. However, the effect of graphene layer spacings on lithium dendrites growth is not clear. In this paper, the first principal calculation was employed to explore it from adsorption and diffusion of lithium atoms on the graphene. The calculation results show that the layer spacings section of 0.45—0.55 nm can obviously inhibit the lithium dendrites growth, which exhibits the lower binding energy and diffusion energy barrier of lithium atoms. When the layer spacings are smaller than 0.45 nm, the diffusion of lithium atoms is difficult. For the larger layer spacings (> 0.55 nm), lithium atoms prefer to adsorb and aggregate between the graphene layers, leading to the lithium dendrites growth. Besides, the doping effect of graphene with layer spacing of 0.45 nm on the lithium dendrites growth was investigated. Under the optimal interlayer spacing, the B-doped and N-doped graphene can promote the diffusion of lithium atoms between the graphene layers and avoid the uneven deposition of lithium, thereby suppressing the formation of lithium dendrites.

Key words: graphene, layer spacings, lithium dendrites, adsorption, first principle

中图分类号:

O 646

黄凯, 王思洁, 苏海萍, 练成, 刘洪来. 石墨烯层间距调控抑制锂枝晶生长的第一性原理研究[J]. 化工学报, 2022, 73(8): 3501-3510.

Kai HUANG, Sijie WANG, Haiping SU, Cheng LIAN, Honglai LIU. First principle study on inhibition of lithium dendrites growth by regulating graphene layer spacings[J]. CIESC Journal, 2022, 73(8): 3501-3510.

图/表 11

图1 计算构型示意图（图中灰色、粉色、蓝色、紫色和绿色的球分别代表C、B、N、P和Cl原子）

Fig. 1 The schematic diagram of calculation configurations (the gray, pink, blue, purple and green ball represent C, B, N, P and Cl atom, respectively)

图2 锂原子在层间距为0.75 nm的石墨烯不同吸附位点的结合能、差分电荷密度和Hirshfeld电荷（红色和蓝色的区域分别代表电子云密度的减少和增加，等值面的值为± 0.02 e/Å3）

Fig. 2 The configuration, difference charge density and Hirshfeld charge of lithium atom adsorbed on different sites of graphene with d = 0.75 nm (red and blue isosurface denote the decrease and increase of electron density, respectively, and the value is ± 0.02 e/Å3)

表1 锂原子在不同层间距石墨烯上不同吸附位点的结合能

Table 1 The binding energy of Li atom at different sites on graphene with different layer spacings

层间距/nm	顶位结合能/eV	桥位结合能/eV	空位结合能/eV
0.35	-0.90	-1.10	-1.90
0.45	-1.63	-1.64	-1.68
0.55	-1.15	-1.17	-1.32
0.65	-0.92	-0.97	-1.24
0.75	-0.86	-0.86	-1.19

图3 锂原子在不同层间距石墨烯上的空位结合能、电荷密度和吸附状态（红色和蓝色的区域分别代表电子云密度的减少和增加，等值面的值为± 0.02 e/Å3）

Fig. 3 The binding energy, charge density and adsorption state of lithium atom on graphene hollow site with different layer spacings (red and blue isosurface denote the decrease and increase of electron density, respectively, and the value is ± 0.02 e/Å3)

图4 锂原子在不同层间距石墨烯上的扩散能量图

Fig.4 The diffusion energy profiles of Li atom on the graphene with different layer spacings

图5 锂原子在不同层间距石墨烯上的扩散路径和相对能量

Fig.5 The diffusion paths and relative energy of lithium atom on graphene with different layer spacings

图6 锂原子在掺杂石墨烯上的结合能及其与掺杂原子之间的距离

Fig. 6 Binding energy of lithium atom on doped-graphene and its distance from doped-atom

图7 不同掺杂石墨烯上的电荷密度（电荷密度等值面的值为-1.5 e/Å3）

Fig.7 The charge density of different doped-graphene(the value of isosurface is -1.5 e/Å3)

图8 锂原子在不同掺杂石墨烯上的扩散能量图

Fig.8 The diffusion energy profiles of Li atom on the different doped-graphene

图9 锂原子在不同掺杂石墨烯上的扩散路径和相对能量

Fig.9 The diffusion paths and relative energy of lithium atom on different doped-graphene

表2 锂原子在不同掺杂量的掺杂石墨烯上路径1和路径3的扩散活化能

Table 2 Diffusion activation energy of lithium atom on doped-graphene （path1 and path3） with different doping amount

掺杂原子	扩散活化能/eV
	5.3%		2.9%		1.1%
	路径1	路径3	路径1	路径3	路径1	路径3
B	0.126	-0.040	0.078	-0.073	0.090	-0.054
N	-0.091	0.197	-0.069	0.053	-0.012	0.224
P	-0.118	0.639	-0.192	0.529	-0.077	0.712
Cl	-0.113	0.553	-0.040	0.698	-0.034	0.691

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