Theoretical study on effect of Ge-S/F co-doping on crystal structure and properties of Li2MSiO4(M = Mn, Fe)

姓名
邮箱
手机号码
标题
留言内容
验证码

Abstract

The effects of Ge-S/F co-doping on the structural stability and electrochemical properties of Li ₂ MSiO ₄( M= Mn, Fe) crystal are systematically studied by the first-principle calculations based on density functional theory combined with the generalized gradient approximation (GGA) + Umethod. The calculation results show that the Ge-S/F co-doping Li ₂ MSiO ₄( M= Mn, Fe) system undergoes the site exchange between Li and M in the delithiation process. Compared with Li ₂ MSiO ₄( M= Mn, Fe), the doped system has good toughness, and lithium ions migrate easily in the doped system. And the doped system with site exchange is more stable in the process of delithium, especially the volume change of Li ₂Mn _0.5Ge _0.5SiO _3.5S _0.5is very small, indicating that it has good structural cyclic stability. Moreover, the theoretical average deintercalation voltages of Li ₂ MSiO ₄( M= Mn, Fe) are reduced by Ge-S/F co-doping. The combination of the density of states with magnetic moment shows that the Ge-S/F co-doping can improve the conductivity of Li ₂MnSiO ₄and delay the appearance of the Jahn-Teller effect in the Li ₂MnSiO ₄system, which is beneficial to the improvement of the structural cycling stability of Li ₂MnSiO ₄. Meanwhile, the Ge-S/F co-doping can not only improve the conductivity of Li ₂FeSiO ₄, but also facilitate the removal of more Li ⁺from Li ₂FeSiO ₄system, especially the complete delithium of Ge-F co-doping system is expected to be achieved.

Keywords:

Authors and contacts

Corresponding author:Hou Yu-Hua,hyhhyl@163.com

Funds:Project supported by the Jiangxi Provincial Key R&D Program, China (Grant No. 20192ACB50020), the Natural Science Foundation of Jiangxi Province, China (Grant No. 20202BABL204022), and the Jiangxi Postgraduate Innovation Fund, China (Grant No. YC2021-S657).

FullText HTML: translate this paragraph

References

[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]

Cited By

DownLoad: Full-Size Img PowerPoint

	Mn-S	Mn-F	Fe-S	Fe-F
特征值	12.00	23.56	16.17	13.52
	19.08	28.85	20.12	22.87
	29.87	37.69	20.76	36.42
	37.22	53.05	39.82	53.41
	62.41	73.17	53.52	68.55
	207.87	209.12	222.90	225.26
ΔE_f/eV	–17.39	–17.88	–17.02	–17.30

DownLoad: CSV

	B/GPa	G/GPa	B/G	ν	E/ GPa	θ_D/K
Li₂Mn_0.5Ge_0.5SiO_3.5S_0.5	56.06	21.52	2.60	0.33	57.24	387
Li₂Mn_0.5Ge_0.5SiO_3.5F_0.5	67.03	30.37	2.21	0.30	79.15	462
Li₂Fe_0.5Ge_0.5SiO_3.5S_0.5	63.91	21.15	3.02	0.35	57.15	383
Li₂Fe_0.5Ge_0.5SiO_3.5F_0.5	68.85	25.65	2.68	0.33	68.45	426

DownLoad: CSV

	M—O	M—R	Ge—O	Ge—R	Si1—O	Si1—R	Si2—O	Si2—R
Mn—S (x= 2)	2.220	2.473	2.216	—	1.638	2.156	1.667	—
Mn—S (x= 1∶SE)	2.092	—	1.810	2.196	1.633	2.178	1.657	—
Mn—S (x= 0∶SE)	1.826	—	1.794	2.200	1.644	2.131	1.639	—
Mn—F (x= 2)	2.108	—	2.163	2.892	1.656	—	1.644	1.725
Mn—F (x= 1∶SE)	2.010	—	1.863	—	1.656	—	1.624	1.658
Mn—F (x= 0∶SE)	1.938	—	1.817	—	1.628	—	1.708	1.666
Fe—S (x= 2)	2.146	2.450	2.214	—	1.666	—	1.642	2.137
Fe—S (x= 1∶SE)	1.982	2.350	1.804	—	1.654	—	1.703	2.057
Fe—S (x= 0∶SE)	1.852	—	1.784	2.239	1.639	—	1.626	2.179
Fe—F (x= 2)	2.058	—	2.180	2.396	1.658	—	1.647	2.646
Fe—F (x= 1∶SE)	1.900	—	1.975	2.793	1.651	—	1.626	1.661
Fe—F (x= 0∶SE)	1.863	—	1.755	1.983	1.644	—	1.612	1.817

DownLoad: CSV

	M	Ge	Si1	Si2
Mn—S (x= 2)	1.42	1.23	3.81	3.56
Mn—S (x= 1∶SE)	1.77	3.60	3.81	3.68
Mn—S (x= 0∶SE)	3.35	3.70	3.83	3.85
Mn—F (x= 2)	1.70	1.01	3.67	3.52
Mn—F (x= 1∶SE)	2.28	2.20	3.70	3.82
Mn—F (x= 0∶SE)	2.50	3.35	3.96	3.21
Fe—S (x= 2)	1.44	1.18	3.57	3.83
Fe—S (x= 1∶SE)	2.14	3.45	3.72	3.67
Fe—S (x= 0∶SE)	3.12	3.66	3.85	3.85
Fe—F (x= 2)	1.68	1.08	3.65	2.88
Fe—F (x= 1∶SE)	2.74	1.67	3.72	3.78
Fe—F (x= 0∶SE)	3.02	3.37	3.82	3.65

DownLoad: CSV

结构	磁矩M(初始)/ M(位置交换)	氧化态M(初始)/ M(位置交换)
Mn—S (x= 2)	4.64/4.64	+2(3d⁵)/+2(3d⁵)
Mn—S (x= 1)	4.61/4.65	+2(3d⁵)/+2(3d⁵)
Mn—S (x= 0)	3.78/3.41	+(3 +δ)(3d^(4–δ))/ +(3 +φ)(3d^(4–φ))
Mn—F (x= 2)	4.65/4.65	+2(3d⁵)/+2(3d⁵)
Mn—F (x= 1)	4.64/4.17	+2(3d⁵)/ +(2 + α)(3d^(5–α))
Mn—F (x= 0)	3.87/3.98	+3(3d⁴)/+3(3d⁴)
Fe—S (x= 2)	3.73/3.73	+2(3d⁶)/+2(3d⁶)
Fe—S (x= 1)	3.71/3.68	+2(3d⁶)/+2(3d⁶)
Fe—S (x= 0)	4.02/4.14	+(3 +τ)(3d^(5–τ))/ +(3 +ψ)(3d^(5–ψ))
Fe—F (x= 2)	3.73/3.73	+2(3d⁶)/+2(3d⁶)
Fe—F (x= 1)	4.23/4.23	+3(3d⁵)/+3(3d⁵)
Fe—F (x= 0)	4.25/4.26	+3(3d⁵)/+3(3d⁵)

DownLoad: CSV

[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]

[1]	Yan Zhi, Fang Cheng, Wang Fang, Xu Xiao-Hong.First-principles calculations of structural and magnetic properties of SmCo₃alloys doped with transition metal elements. Acta Physica Sinica, 2024, 73(3): 037502.doi:10.7498/aps.73.20231436
[2]	Yu Yue, Yang Heng-Yu, Zhou Wu-Xing, Ouyang Tao, Xie Guo-Feng.First-principles study of thermoelectric performance of monolayer Ge₂X₄S₂(X= P, As). Acta Physica Sinica, 2023, 72(7): 077201.doi:10.7498/aps.72.20222244
[3]	Luan Li-Jun, He Yi, Wang Tao, Liu Zong-Wen.First-principles study of e interface interaction and photoelectric properties of the solar cell heterojunction CdS/CdMnTe. Acta Physica Sinica, 2021, 70(16): 166302.doi:10.7498/aps.70.20210268
[4]	Liang Ting, Wang Yang-Yang, Liu Guo-Hong, Fu Wang-Yang, Wang Huai-Zhang, Chen Jing-Fei.First-principles investigations on gas adsorption properties of V-doped monolayer MoS₂. Acta Physica Sinica, 2021, 70(8): 080701.doi:10.7498/aps.70.20202043
[5]	Zhong Shu-Lin, Qiu Jia-Hao, Luo Wen-Wei, Wu Mu-Sheng.First-principles study of properties of rare-earth-doped LiFePO₄. Acta Physica Sinica, 2021, 70(15): 158203.doi:10.7498/aps.70.20210227
[6]	Wang Yan, Chen Nan-Di, Yang Chen, Zeng Zhao-Yi, Hu Cui-E, Chen Xiang-Rong.Thermoelectric transport properties of two-dimensional materialsXTe₂(X= Pd, Pt) via first-principles calculations. Acta Physica Sinica, 2021, 70(11): 116301.doi:10.7498/aps.70.20201939
[7]	Peng Lin-Feng, Zeng Zi-Qi, Sun Yu-Long, Jia Huan-Huan, Xie Jia.Facile synthesis and electrochemical properties of Na-rich anti-perovskite solid electrolytes. Acta Physica Sinica, 2020, 69(22): 228201.doi:10.7498/aps.69.20201227
[8]	Hu Qian-Ku, Hou Yi-Ming, Wu Qing-Hua, Qin Shuang-Hong, Wang Li-Bo, Zhou Ai-Guo.Theoretical calculations of stabilities and properties of transition metal borocarbidesTM₃B₃C andTM₄B₃C₂compound. Acta Physica Sinica, 2019, 68(9): 096201.doi:10.7498/aps.68.20190158
[9]	Yan Xiao-Tong, Hou Yu-Hua, Zheng Shou-Hong, Huang You-Lin, Tao Xiao-Ma.First-principles study of effects of Ga, Ge and As doping on electrochemical properties and electronic structure of Li₂CoSiO₄serving as cathode material for Li-ion batteries. Acta Physica Sinica, 2019, 68(18): 187101.doi:10.7498/aps.68.20190503
[10]	Chen Mei-Na, Zhang Lei, Gao Hui-Ying, Xuan Yan, Ren Jun-Feng, Lin Zi-Jing.DFT+U calculation of Sm3+ and Sr2+ co-doping effect on performance of CeO2-based electrolyte. Acta Physica Sinica, 2018, 67(8): 088202.doi:10.7498/aps.67.20172748
[11]	Yang Xiu-Tao, Liang Zhong-Guan, Yuan Yu-Jia, Yang Jun-Liang, Xia Hui.Preparation and electrochemical performance of porous carbon nanosphere. Acta Physica Sinica, 2017, 66(4): 048101.doi:10.7498/aps.66.048101
[12]	Bai Jing, Wang Xiao-Shu, Zu Qi-Rui, Zhao Xiang, Zuo Liang.Defect stabilities and magnetic properties of Ni-X-In (X= Mn, Fe and Co) alloys: a first-principle study. Acta Physica Sinica, 2016, 65(9): 096103.doi:10.7498/aps.65.096103
[13]	Chen Chang, Ru Qiang, Hu She-Jun, An Bo-Nan, Song Xiong.Preparation and electrochemical properties of Co2SnO4/graphene composites. Acta Physica Sinica, 2014, 63(19): 198201.doi:10.7498/aps.63.198201
[14]	Li Rong, Luo Xiao-Ling, Liang Guo-Ming, Fu Wen-Sheng.First-principles study of influence of dopants Fe on the dehydrogenation properties of VH2. Acta Physica Sinica, 2011, 60(11): 117105.doi:10.7498/aps.60.117105
[15]	Bai Ying, Ding Ling-Hong, Zhang Wei-Feng.Investigation of electrochemical performances of ZnFe2O4 prepared by solid state and hydrothermal method. Acta Physica Sinica, 2011, 60(5): 058201.doi:10.7498/aps.60.058201
[16]	Gu Mu, Lin Ling, Liu Bo, Liu Xiao-Lin, Huang Shi-Ming, Ni Chen.Fist-principle calculation for electronic structure of M’-GdTaO4. Acta Physica Sinica, 2010, 59(4): 2836-2842.doi:10.7498/aps.59.2836
[17]	Tan Xing-Yi, Jin Ke-Xin, Chen Chang-Le, Zhou Chao-Chao.Electronic structure of YFe2B2by first-principles calculation. Acta Physica Sinica, 2010, 59(5): 3414-3417.doi:10.7498/aps.59.3414
[18]	Wu Hong-Li, Zhao Xin-Qing, Gong Sheng-Kai.Effect of Nb doping on electronic structure of TiO2/NiTi interface: A first-principle study. Acta Physica Sinica, 2008, 57(12): 7794-7799.doi:10.7498/aps.57.7794
[19]	Hou Qing-Yu, Zhang Yue, Chen Yue, Shang Jia-Xiang, Gu Jing-Hua.Effects of the concentration of oxygen vacancy of anatase on electric conducting performance studied by frist principles calculations. Acta Physica Sinica, 2008, 57(1): 438-442.doi:10.7498/aps.57.438
[20]	Sun Bo, Liu Shao-Jun, Duan Su-Qing, Zhu Wen-Jun.First-principles calculations of structures, properties and high pressures effects of Fe. Acta Physica Sinica, 2007, 56(3): 1598-1602.doi:10.7498/aps.56.1598

Catalog

Vol. 71, Issue 17 - 2022-09-05

Metrics

Abstract views:3452
PDF Downloads:51
Cited By:0

Search

Article