Electronic structures and Li diffusion in cathode material Li<sub>2</sub>FeO<sub>2</sub> of Li-ion batteries

Lin Chuan-Jin; Zheng Feng; Zhu Zi-Zhong

doi:10.7498/aps.68.20190213

Abstract

The electronic structures and lithium diffusion in the cathode material Immm-Li₂FeO₂ of lithium-ion batteries are calculated by the first-principles method based on the density functional theory. The calculated results show that Immm-Li₂FeO₂ is ferromagnetic, and the band structure indicates a semi-metal character. The d-electrons of Fe ions are in the low spin state, with a spin polarization of 8.01%. The spin-up and spin-down band structure are also analyzed by using the l-decomposed electronic density of states. Furthermore, the energy barriers for the lithium ion diffusion in different directions are calculated by the nudged elastic band method. For comparison, the potential barriers for the Li₂MO₂ (M = Co, Ni, Cu) are also calculated. The results suggest that it is easier for Li ion to diffuse in the c-axis directionof Li₂FeO₂, with an energy barrier of only 0.1 eV. The energy barrier is 0.21 eV for Li to diffuse in the ab-axis direction, while the diffusion barrier is 0.39 eV along the a-axis direction of Li₂FeO₂. All these values of energy barriers are lower than those in other Fe-based cathodes mentioned, indicating that the Li diffusion coefficient in Immm-Li₂FeO₂ should be larger than those of other materials, which also indicates that the Li₂FeO₂ is of great importance as cathode material.

Keywords:

Authors and contacts

1.
College of Physics and Information Engineering, Minnan Normal University, Zhangzhou 363000, China
2.
Jiujiang Research Institute, College of Physical Science and Technology, Xiamen University, Xiamen 361005, China

Corresponding author: Zhu Zi-Zhong, zzhu@xmu.edu.cn

Funds: Project supported by the National Key R&D Program of China (Grant No. 2016YFA0202601) and the Education and Research Project of Young and Middle-aged Teachers of Fujian Province (Science and Technology Class), China (Grant No. JT180302).

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References

[1]	Goodenough J B, Park K S 2013 J. Am. Chem. Soc. 135 1167 Google Scholar
[2]	Goodenough J B, Kim Y 2010 Chem. Mater. 22 587 Google Scholar
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Cited By

图 1 Immm-Li₂FeO₂的3 × 3 × 1超原胞及Li迁移路径示意图

Figure 1. The 3 × 3 × 1 supercell and the Li migration paths of Immm-Li₂FeO₂.

DownLoad: Full-Size Img PowerPoint

图 2 Immm-Li₂FeO₂的声子谱

Figure 2. Phonon-dispersions of Immm-Li₂FeO₂.

DownLoad: Full-Size Img PowerPoint

图 3 Li₂FeO₂ $\left( {1\bar 11} \right)$面的总电荷密度图

Figure 3. Total charge densities of Li₂FeO₂ $\left( {1\bar 11} \right)$.

DownLoad: Full-Size Img PowerPoint

图 4 Li₂FeO₂ $\left( {1\bar 11} \right)$面的差分电荷密度图

Figure 4. Deformation charge densities of Li₂FeO₂ $\left( {1\bar 11} \right)$.

DownLoad: Full-Size Img PowerPoint

图 5 Li₂FeO₂自旋向上(a)和自旋向下(b)的能带结构图

Figure 5. (a) Spin-up and (b) spin-down band structures of Li₂FeO₂.

DownLoad: Full-Size Img PowerPoint

图 6 Li₂FeO₂的总态密度和O, Fe的分波态密度图

Figure 6. Total density of states (DOS) of Li₂FeO₂ and partial density of states of O and Fe.

DownLoad: Full-Size Img PowerPoint

图 7 Li₂MO₂ (M = Fe, Co, Ni, Cu)中Li⁺离子不同迁移路径的势垒　(a) Path A; (b) path AB; (c) path C (P1—P2)

Figure 7. Energy barriers for different Li⁺ migration paths in Li₂MO₂ (M = Fe, Co, Ni, Cu): (a) Path A; (b) path AB; (c) path C (P1–P2).

DownLoad: Full-Size Img PowerPoint

图 8 Li₂FeO₂中(a) path AB和(b) path A方向Li⁺离子扩散系数随温度的变化

Figure 8. Temperature dependence of Li ion diffusion coefficients along (a) path AB and (b) path A in Li₂FeO₂.

DownLoad: Full-Size Img PowerPoint

表 1 GGA和GGA + U下Li₂NiO₂的扩散势垒

Table 1. Li₂NiO₂ diffusion barriers under GGA and GGA + U.

		跃迁路径
		Path A	Path AB	Path C
Li₂NiO₂迁移势垒/eV	GGA	0.40	0.41	0.69
Li₂NiO₂迁移势垒/eV	GGA + U	0.46	0.41	0.89

DownLoad: CSV

表 2 Immm-Li₂FeO₂的结构参数与键长

Table 2. Structural parameters and the bond lengths of Immm-Li₂FeO₂.

	a/Å	b/Å	c/Å	Bond length/Å
	a/Å	b/Å	c/Å	Fe—O	Li—O_A	Li—O_B
Li₂FeO₂	2.923	3.713	9.514	2.010	2.016	1.954
Li₂NiO₂^[11]	2.808	3.803	8.936	—	—	—
Li₂CuO₂^[9]	2.789	3.662	9.573	—	—	—

DownLoad: CSV

表 3 不同电子自旋组态的Li₂FeO₂的总结合能与Fe²⁺磁矩

Table 3. Total cohesive energies and magnetic moments under different spin configurations of Li₂FeO₂.

电子自旋组态	Li₂FeO₂结合能(eV/分子式)	Fe²⁺磁矩/μ_B
高自旋	–3.29	3.92
低自旋	–3.30	2.01
非自旋	–3.22	0

DownLoad: CSV

表 4 不同跃迁路径的Li₂MO₂(M = Fe, Co, Ni, Cu)的跃迁势垒与跃迁步长

Table 4. Energy barriers and distance for different Li⁺ migration paths in Li₂FeO₂

		Li₂FeO₂	Li₂CoO₂	Li₂NiO₂	Li₂CuO₂
Path A	跃迁势垒/eV	0.39	0.45	0.40	0.61
Path A	跃迁步长/Å	3.60	2.98	2.98	3.32
Path AB	跃迁势垒/eV	0.21	0.43	0.41	0.36
Path AB	跃迁步长/Å	3.04	2.76	2.70	2.84
Path C	跃迁势垒/eV	0.10	0.51	0.69	0.78
Path C	跃迁步长/Å	4.32	3.50	3.62	4.12

DownLoad: CSV

[1]	Goodenough J B, Park K S 2013 J. Am. Chem. Soc. 135 1167 Google Scholar
[2]	Goodenough J B, Kim Y 2010 Chem. Mater. 22 587 Google Scholar
[3]	Xu L, Tang S, Cheng Y, Wang K, Liang J, Liu C, Cao Y C, Wei F, Mai L Q 2018 Joule 2 1991 Google Scholar
[4]	Goodenough J B 2018 Nature Electron. 1 204 Google Scholar
[5]	Yamada A 2014 Mater. Res. Soc. 39 423 Google Scholar
[6]	Robert A, Daniel W T, Fabio L M, Novak P, Bruce P G 2008 J. Am. Chem. Soc. 130 3554 Google Scholar
[7]	Guo S P, Ma Z, Li J C, Xue H G 2017 J. Mater. Sci. 52 1469 Google Scholar
[8]	Ramos-Sanchez G, Romero-Ibarra I C, Vazquez-Arenas J, Tapia C, Aguilar-Eseiza N, Gonzalez I 2017 Solid State Ionics 303 89 Google Scholar
[9]	Kordatos A, Kuganathan N, Kelaidis N, Iyngaran P, Chroneos A 2018 Sci. Rep. 8 6754 Google Scholar
[10]	Back C K, Yin R Z, Shin S J, Lee Y S, Choi W, Kim Y S 2012 J. Electrochem. Soc. 159 A887 Google Scholar
[11]	Kang K, Morgan D, Ceder G 2009 Phys. Rev. B 79 014305 Google Scholar
[12]	Lee H, Chang S K, Goh E Y, Jeong J Y, Lee J H, Kim H J, Cho J J, Hong S T 2008 Chem. Mater. 20 5 Google Scholar
[13]	Rose E R, Pandian A S, Yan P F, Weker J N, Wang C M, Nanda J 2017 Chem. Mater. 29 2997 Google Scholar
[14]	Perdew J P, Chevary J A, Vosko S H, Jackson K A, Pederson M R, Singh D J, Fiolhais C 1992 Phys. Rev. B 46 6671 Google Scholar
[15]	Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865 Google Scholar
[16]	Kresse G, Jobert D 1999 Phys. Rev. B 59 1758
[17]	Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188 Google Scholar
[18]	Anisimov V I, Zaanen J, Andersen O K 1991 Phys. Rev. B 44 943 Google Scholar
[19]	Zhou F, Cococcioni M, Marianetti C A, Morgan D, Ceder G 2004 Phys. Rev. B 70 235121 Google Scholar
[20]	Henkelman G, Uberuaga B P, Jónsson H 2000 J. Chem. Phys. 113 9901
[21]	Morgan D, van der Ven A, Ceder G 2004 Electrochem. Solid-State Lett. 7 A30 Google Scholar
[22]	Urban A, Seo D H, Ceder G 2016 njp Computat. Mater. 2 16002
[23]	Zhao Y Q, Ma Q R, Liu B, Yu Z L, Yang J L, Cai M Q 2018 Nanoscale 10 8677 Google Scholar
[24]	Yu Z L, Ma Q R, Zhao Y Q, Liu B, Cai M Q 2018 J. Phys. Chem. C 112 9275
[25]	Zhao Y Q, Ma Q R, Liu Biao, Yu Z L, Cai M Q 2018 Phys. Chem. Chem. Phys. 20 14718 Google Scholar
[26]	徐光宪, 王祥云 2010 物质结构 (北京: 科学出版社) 第725−727页 Xu G X, Wang X Y 2010 Material Structure (Beijing: Science Press) pp725−727 (in Chinese)
[27]	Huang Z F, Meng X, Wang C Z, Sun Y, Chen G 2006 J.Power Sources 158 1394 Google Scholar
[28]	Ramesha K, Seshadri R, Ederer C, He T, Subramanian M A 2004 Phys. Rev. B 70 214409 Google Scholar
[29]	Krishna G, Dathar P, Sheppard D, Stevenson K J, Henkelman G 2011 Chem. Mater. 23 4032 Google Scholar
[30]	Ouyang C, Shi S, Wang Z, Huang X, Chen L 2004 Phys. Rev. B 69 104303 Google Scholar
[31]	Armstrong A R, Kuganathan N, Islam M S, Bruce P G 2011 J. Am. Chem. Soc. 133 13031 Google Scholar
[32]	Kutner R 1981 Phys. Lett. A 81 239 Google Scholar
[33]	Vineyard G H 1957 J. Phys. Chem. Solids 3 121 Google Scholar

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Electronic structures and Li diffusion in cathode material Li₂FeO₂ of Li-ion batteries

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Corresponding author: Zhu Zi-Zhong, zzhu@xmu.edu.cn

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Electronic structures and Li diffusion in cathode material Li2FeO2 of Li-ion batteries

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Corresponding author: Zhu Zi-Zhong, zzhu@xmu.edu.cn

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Electronic structures and Li diffusion in cathode material Li₂FeO₂ of Li-ion batteries