固体电解质界面层锂合金相的高通量筛选与界面离子输运研究

doi:10.3866/PKU.WHXB202305039

Abstract

Abstract:

Solid electrolyte interphase (SEI) layers derived from the side reactions between Li metal anode and electrolyte, have great impacts on the electrochemical performance of lithium batteries. In solid-state batteries, SEI layers are also required as the electrical insulators but an ionic conductors, and the mechanical reinforcements for withstanding volume change and suppressing dendritic growth in Li metal anode. Introducing LiF substrates into SEI layers can significantly reduce the electron tunneling ability from Li anode to SEI layer, meanwhile providing the excellent interfacial mechanical strength. However, LiF has a very high energy barrier for ion diffusion, hindering the rapid lithium ion diffusion from SEI layer to lithium anode. Therefore, it is necessary to introduce lithium alloy phases with higher ionic conductivity into the LiF matrix to provide sufficient ion diffusion channels. By the data mining technology, high-throughput first-principle calculation and ab-initio molecular dynamics simulations, this work performed phase diagram and ion diffusion energy barrier calculations to evaluate the thermodynamic stabilities and lithium diffusion abilities of several lithium alloys. 27 lithium alloys that can be used as Li-ion conducting phases in the LiF-based artificial SEI layers are screened. Meanwhile, the structure-function relationship analysis of lithium alloys uncovers that the crystal structure type of lithium alloys has more significant impacts on lithium ion diffusion than alloy elements, that is, lithium alloy structures with the space group of I${\rm{\bar 4}}$3d and Fm${\rm{\bar 3}}$m have very excellent lithium ion transport performance, while the diffusion channels of lithium alloy structures with the space group of Pm${\rm{\bar 3}}$m and F4${\rm{\bar 3}}$m are narrow, leading to the poor lithium ion transport performance. In addition, this work uncovers a physical image of lithium ion transport in artificial SEI interface, that is, lithium ion diffusion in LiF crystal bulk is quite difficult, while the diffusion resistance at LiF grain boundaries and LiF/LiM alloy interfaces is small.

Key words: Solid-state battery, Artificial SEI interface, Lithium alloy, First-principle calculation, Interfacial ion diffusion

Zhi Dou, Huiyu Duan, Yixi Lin, Yinghui Xia, Mingbo Zheng, Zhenming Xu. High-Throughput Screening Lithium Alloy Phases and Investigation of Ion Transport for Solid Electrolyte Interphase Layer[J]. Acta Phys. -Chim. Sin. 2024, 40(3), 2305039. doi: 10.3866/PKU.WHXB202305039

Figures/Tables 7

Fig 1

Table 1

Structure, thermodynamic stability and lithium diffusion properties of 38 lithium alloy phases."

Composition	mp-ID	Space group	E_gap/(eV)^*	E_hull/(eV∙atom⁻¹)^*	N_Li	N_path	E_a/(eV)	D_{300 K}/(cm²∙s⁻¹)	σ_{300 K}/(mS∙cm⁻¹)	Calculation method
LiAl	mp-1067	Fd${\rm{\bar 3}}$m	0	0	1	1	0.373	1.59 × 10⁻¹⁰	0.03	NEB
LiAl₃	mp-10890	Pm${\rm{\bar 3}}$m	0	0	1	1	1.658	9.81 × 10⁻³²	~0	NEB
Li₂Al	mp-1210753	Cmcm	0	0	2	3	0.293	9.73 × 10⁻⁹	2.45	NEB
Li₃Al₂	mp-16506	R${\rm{\bar 3}}$m	0	0	2	3	0.169	5.26 × 10⁻⁶	> 1000	NEB
Li₃Al	mp-975868	I4/mmm	0	0.04	2	3	0.276	4.23 × 10⁻⁸	11.81	NEB
Li₉Al₄	mp-568404	C2/m	0	0	5	> 3	0.184	2.95 × 10⁻⁶	767.99	AIMD
LiGa₃	mp-867205	Pm${\rm{\bar 3}}$m	0	0.01	1	1	1.167	2.02 × 10⁻²³	~0	NEB
LiGa	mp-1307	Fd${\rm{\bar 3}}$m	0	0	1	1	0.326	9.41 × 10⁻¹⁰	0.20	NEB
Li₃Ga₇	mp-567306	R${\rm{\bar 3}}$m	0	0.01	1	1	0.288	1.41 × 10⁻⁹	0.15	NEB
Li₃Ga₁₄	mp-1222489	R3m	0	0.02	1	1	0.196	5.07 × 10⁻⁶	280.99	NEB
Li₃Ga	mp-976023	Fm${\rm{\bar 3}}$m	0	0.01	2	3	0.172	5.76 × 10⁻⁶	> 1000	NEB
Li₂Ga	mp-29210	Cmcm	0	0	2	2	0.205	3.20 × 10⁻⁷	87.84	NEB
LiGe	mp-9918	I4₁/a	0	0	1	1	0.284	1.36 × 10⁻⁹	0.25	NEB
Li₉Ge₄	mp-27932	Cmcm	0	0	5	> 3	0.358	3.70 × 10⁻⁹	1.03	AIMD
Li₃Ge	mp-867342	Fm${\rm{\bar 3}}$m	0	0.01	2	3	0.221	8.21 × 10⁻⁷	260.89	NEB
Li₁₅Ge₄	mp-1777	I${\rm{\bar 4}}$3d	0	0	2	3	0.128	1.23 × 10⁻⁴	> 1000	NEB
Li₁₁Ge₆	mp-29631	Cmcm	0	0.01	7	> 3	0.273	7.23 × 10⁻⁸	17.70	AIMD
LiIn₃	mp-867161	Pm${\rm{\bar 3}}$m	0	0	1	1	0.959	8.04 × 10⁻²⁰	~0	NEB
LiIn	mp-22460	Fd${\rm{\bar 3}}$m	0	0	1	1	0.218	7.69 × 10⁻⁸	12.05	NEB
Li₃In₂	mp-21293	R${\rm{\bar 3}}$m	0	0	2	2	0.212	1.12 × 10⁻⁶	221.48	NEB
Li₃In	mp-867226	Fm${\rm{\bar 3}}$m	0	0	2	3	0.212	1.33 × 10⁻⁶	346.44	NEB
Li₂In	mp-31324	Cmcm	0	0	2	3	0.327	2.80 × 10⁻⁹	0.63	NEB
Li₁₃In₃	mp-510430	Fd${\rm{\bar 3}}$m	0	0	4	> 3	0.131	8.76 × 10⁻⁴	> 1000	NEB
LiNi₃	mp-1185266	I4/mmm	0	0.02	1	1	2.431	4.32 × 10⁻⁴⁵	~0	NEB
LiSi	mp-795	I4₁/a	0	0.01	1	1	0.268	2.28 × 10⁻⁹	0.46	NEB
Li₁₅Si₄	mp-569849	I${\rm{\bar 4}}$3d	0	0	2	3	0.121	1.61 × 10⁻⁴	> 1000	NEB
Li₂Si	mp-27705	R${\rm{\bar 3}}$m	0	0.04	2	2	0.202	1.36 × 10⁻⁷	33.75	NEB
Li₂Sb	mp-9563	P${\rm{\bar 6}}$2c	0	0.01	2	3	0.273	2.19 × 10⁻⁷	45.39	NEB
Li₃Sb	mp-2074	Fm${\rm{\bar 3}}$m	0.71	0	2	3	0.166	7.87 × 10⁻⁶	> 1000	NEB
Li₇Sn₃	mp-30768	P2₁/m	0	0	7	> 3	0.297	4.51 × 10⁻⁸	10.84	AIMD
Li₇Sn₂	mp-30767	Cmmm	0	0	6	> 3	0.458	9.44 × 10⁻¹¹	0.03	AIMD
Li₅Sn₂	mp-30766	R${\rm{\bar 3}}$m	0	0	3	> 3	0.200	1.97 × 10⁻⁶	486.18	AIMD
Li₃Sn	mp-1185265	Fm${\rm{\bar 3}}$m	0	0	2	3	0.218	1.04 × 10⁻⁶	276.12	NEB
LiSn₃	mp-1185461	I4/mmm	0	0.03	1	1	0.745	2.27 × 10⁻¹⁶	~0	NEB
LiSn	mp-569073	P2/m	0	0	2	3	0.385	1.31 × 10⁻¹⁰	0.02	NEB
Li₂₂Sn₅	mp-1198729	F${\rm{\bar 4}}$3m	0	0.01	16	> 3	0.601	4.49 × 10⁻¹³	~0	AIMD
Li₁₇Sn₄	mp-573471	F${\rm{\bar 4}}$${\rm{\bar 3}}$m	0	0	13	> 3	1.068	9.68 × 10⁻¹⁹	~0	AIMD
Li₁₃Sn₅	mp-30769	P${\rm{\bar 3}}$m1	0	0	7	> 3	0.472	5.39 × 10⁻¹¹	0.01	AIMD

Table 1

Fig 2

Fig 3

Fig 4

Fig 5

Fig 6

References 34

1	Hu A. J. Beijing Univ. Technol. (Soc. Sci. Ed.) 2021, 21 (3), 1.
	胡鞍钢. 北京工业大学学报(社会科学版), 2021, 21 (3), 1. doi: 10.12120/bjutskxb202103001
2	Li H. ; Xu X. Energy Storage Sci. Technol. 2016, 5 (5), 607.
	李泓; 许晓雄. 储能科学与技术, 2016, 5 (5), 607. doi: 10.12028/j.issn.2095-4239.2016.0023
3	Lv L. ; Zhou L. ; Muhammad K. T. ; Yang L. ; Chen R. ; Yang W. Sci. Sin., Ser. B: Chem. 2020, 50 (9), 1031.
	吕璐; 周雷; MuhammadK. T.; 杨乐; 陈人杰; 杨文. 中国科学: 化学, 2020, 50 (9), 1031. doi: 10.1360/SSC-2020-0089
4	Liu L. ; Wu F. ; Li H. ; Chen L. J. Chin. Ceram. Soc. 2019, 47 (10), 1367.
	刘丽露; 吴凡; 李泓; 陈立泉. 硅酸盐学报, 2019, 47 (10), 1367. doi: 10.14062/j.issn.0454-5648.2019.10.04
5	Wang H. ; An H. ; Shan H. ; Zhao L. ; Wang J. Acta Phys. -Chim. Sin. 2021, 37 (11), 2007070.
	王晗; 安汉文; 单红梅; 赵雷; 王家钧. 物理化学学报, 2021, 37 (11), 2007070. doi: 10.3866/PKU.WHXB202007070
6	Zhao Y. ; Chen C. ; Liu W. ; Hu W. ; Liu J. Acta Phys. -Chim. Sin. 2023, 39 (8), 2211017.
	赵永智; 陈晨阳; 刘文燚; 胡伟飞; 刘金平. 物理化学学报, 2023, 39 (8), 2211017. doi: 10.3866/PKU.WHXB202211017
7	Xu L. ; Tang S. ; Cheng Y. ; Wang K. ; Liang J. ; Liu C. ; Cao Y.-C. ; Wei F. ; Mai L. Joule 2018, 2 (10), 1991. doi: 10.1016/j.joule.2018.07.009
8	Wang A. ; Kadam S. ; Li H. ; Shi S. ; Qi Y. Npj Comput. Mater. 2018, 4 (1), 15. doi: 10.1038/s41524-018-0064-0
9	Xiao Y. ; Wang Y. ; Bo S.-H. ; Kim J. C. ; Miara L. J. ; Ceder G. Nat. Rev. Mater. 2020, 5 (2), 105. doi: 10.1038/s41578-019-0157-5
10	Feng W. ; Wang F. ; Zhou X. ; Ji X. ; Han F. ; Wang C. Acta Phys. Sin. 2020, 69 (22), 137.
	冯吴亮; 王飞; 周星; 吉晓; 韩福东; 王春生. 物理学报, 2020, 69 (22), 137. doi: 10.7498/aps.66.168501
11	Wang J. ; Chen L. ; Li H. ; Wu F. Energy Environ. Mater. 2023, e12613. doi: 10.1002/eem2.12613
12	Wang Z. ; Li X. ; Chen Y. ; Pei K. ; Mai Y.-W. ; Zhang S. ; Li J. Chem 2020, 6 (11), 2878. doi: 10.1016/j.chempr.2020.09.005
13	Hu A. ; Chen W. ; Du X. ; Hu Y. ; Lei T. ; Wang H. ; Xue L. ; Li Y. ; Sun H. ; Yan Y. Energy Environ. Sci. 2021, 14 (7), 4115. doi: 10.1039/D1EE00508A
14	Luo L. ; Zheng F. ; Gao H. ; Lan C. ; Sun Z. ; Huang W. ; Han X. ; Zhang Z. ; Su P. ; Wang P. Nano Res. 2023, 16 (1), 1634. doi: 10.1007/s12274-022-5136-2
15	Blöchl P. E. Phys. Rev. B 1994, 50 (24), 17953. doi: 10.1103/PhysRevB.50.17953
16	Perdew J. P. ; Burke K. ; Ernzerhof M. Phys. Rev. Lett. 1996, 77 (18), 3865. doi: 10.1103/PhysRevLett.77.3865
17	Kohn W. ; Sham L. J. Phys. Rev. 1965, 140 (4A), A1133. doi: 10.1103/PhysRev.140.A1133
18	Wisesa P. ; McGill K. A. ; Mueller T. Phys. Rev. B 2016, 93 (15), 155109. doi: 10.1103/PhysRevB.93.155109
19	Henkelman G. ; Jónsson H. J. Chem. Phys. 2000, 113 (22), 9978. doi: 10.1063/1.1323224
20	Ong S. P. ; Richards W. D. ; Jain A. ; Hautier G. ; Kocher M. ; Cholia S. ; Gunter D. ; Chevrier V. L. ; Persson K. A. ; Ceder G. Comput. Mater. Sci. 2013, 68, 314. doi: 10.1016/j.commatsci.2012.10.028
21	Hoover W. G. Phys. Rev. A 1985, 31 (3), 1695. doi: 10.1103/PhysRevA.31.1695
22	He X. ; Zhu Y. ; Epstein A. ; Mo Y. Npj Comput. Mater. 2018, 4 (1), 18. doi: 10.1038/s41524-018-0074-y
23	Pan Y. Ceram. Int. 2019, 45 (15), 18315. doi: 10.1016/j.ceramint.2019.06.044
24	Gertsman V. Acta Crystallogr. Sect. A: Found. Crystallogr. 2001, 57 (6), 649. doi: 10.1107/S0108767301009102
25	Ren Y. ; Zou Z. ; Zhao Q. ; Wang D. ; Yu J. ; Shi S. Acta Phys. Sin. 2020, 69 (22), 226601.
	任元; 邹喆乂; 赵倩; 王达; 喻嘉; 施思齐. 物理学报, 2020, 69 (22), 226601. doi: 10.7498/aps.69.20201519
26	Chang D. ; Oh K. ; Kim S. J. ; Kang K. Chem. Mater. 2018, 30 (24), 8764. doi: 10.1021/acs.chemmater.8b03000
27	Oh K. ; Chang D. ; Lee B. ; Kim D.-H. ; Yoon G. ; Park I. ; Kim B. ; Kang K. Chem. Mater. 2018, 30 (15), 4995. doi: 10.1021/acs.chemmater.8b01163
28	Dobhal G. ; Walsh T. R. ; Tawfik S. A. ACS Appl. Mater. Interfaces 2022, 14 (50), 55471. doi: 10.1021/acsami.2c12192
29	Yildirim H. ; Kinaci A. ; Chan M. K. ; Greeley J. P. ACS Appl. Mater. Interfaces 2015, 7 (34), 18985. doi: 10.1021/acsami.5b02904
30	Modak P. ; Modak B. Comput. Mater. Sci. 2022, 202, 110977. doi: 10.1016/j.commatsci.2021.110977
31	Krauskopf T. ; Muy S. ; Culver S. P. ; Ohno S. ; Delaire O. ; Shao-Horn Y. ; Zeier W. G. J. Am. Chem. Soc. 2018, 140 (43), 14464. doi: 10.1021/jacs.8b09340
32	Uematsu, M. Self-Diffusion and Dopant Diffusion in Germanium (Ge) and Silicon–Germanium (SiGe) Alloys. In Silicon–Germanium (SiGe) Nanostructures; Woodhead: Cambridge, UK, 2011; pp. 299–337.
33	Chen Y. ; Ouyang C. ; Song L. ; Sun Z. J. Phys. Chem. C 2011, 115 (14), 7044. doi: 10.1021/jp112202s
34	Sata N. ; Eberman K. ; Eberl K. ; Maier J. Nature 2000, 408 (6815), 946. doi: 10.1038/35050047

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High-Throughput Screening Lithium Alloy Phases and Investigation of Ion Transport for Solid Electrolyte Interphase Layer

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