氧缺位结构介孔二氧化钛/聚乙烯复合隔膜在锂硫电池中的应用

doi:10.7503/cjcu20200057

高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (7): 1661-1669.doi: 10.7503/cjcu20200057

氧缺位结构介孔二氧化钛/聚乙烯复合隔膜在锂硫电池中的应用

吴桐,丛丽娜,孙立群,谢海明^*()

东北师范大学化学学院, 动力电池与地方联合工程实验室, 吉林省锂离子电池材料科技创新中心, 长春 130024

收稿日期:2020-02-05 出版日期:2020-07-10 发布日期:2020-04-08
通讯作者: 谢海明 E-mail:xiehm136@nenu.edu.cn
基金资助:
吉林省重点技术研发专项资金(2018201097GX);国家自然科学基金青年科学基金(21905041);国家自然科学基金青年科学基金(2018M640274);中国博士后科学基金(JJKH20190265KJ);吉林省教育厅自然科学基金(2412020ZD002);吉林省教育厅自然科学基金(2412018QD006);中央高校基础研究基金(2019C042)

Application of Porous Black Titanium Dioxide with Oxygen Vacancy/Polyethylene as a Composite Separator for Lithium Sulfur Batteries^†

WU Tong,CONG Lina,SUN Liqun,XIE Haiming^*()

Faculty of Chemistry, National and Local United Engineering Laboratory for Power Batteries, Jilin Province Lithium Ion Battery Material Science and Technology Innovation Center, Northeast Normal University, Changchun 130024, China

Received:2020-02-05 Online:2020-07-10 Published:2020-04-08
Contact: Haiming XIE E-mail:xiehm136@nenu.edu.cn
Supported by:
† Special Fund of Key Technology Research and Development Projects of Jilin Province, China(2018201097GX);National Natural Science Foundation of China(21905041);Postdoctoral Science Foundation of China(2018M640274);Natural Science Foundation of the Jilin Province, China(JJKH20190265KJ);Fundamental Research Funds for the Cental Universities, China(2412020ZD002);Fundamental Research Funds for the Cental Universities, China(2412018QD006);Special Foundation of Industrial Technology Research and Development of Education department of Jilin Province, China(2019C042)

摘要/Abstract

摘要：

采用两步溶液法合成了一种具有高度氧缺位的黑色介孔二氧化钛, 并将其涂覆在隔膜表面作为锂硫电池复合隔膜, 研究了其在锂硫电池中的电化学性能. 结果表明, 氧缺位的黑色介孔二氧化钛材料不仅展现出良好的导电性, 还能加强对多硫化物的物理和化学吸附能力, 从而显著提高锂硫电池的放电比容量(0.1C倍率下首次放电比容量为1257 mA·h/g)和循环性能(循环100次后放电比容量为821 mA·h/g).

关键词: 锂硫电池, 复合隔膜, 二氧化钛, 多硫化物, 循环性能

Abstract:

In this work, a mesoporous black titanium dioxide(b-TiO₂) with highly ordered oxygen vacancy was synthesized by two-step solution method and coated on the surface of polyethylene separator to obtain the composite separator for lithium-sulfur(Li-S) battery. The electrochemical performance of the Li-S battery with this composite separator was studied. The results show that the mesoporous b-TiO₂ presents a good conductivity due to oxygen vacancy, and can enhance the physical and chemical adsorption of polysulfide, thus the obtained Li-S batteries possess excellent discharge specific capacities(1257 mA·h/g at 0.1C) and outstan-ding cycling performance(discharge specific capacity 821 mA·h/g after 100 cycles).

Key words: Lithium-sulfur battery, Composite separator, Titanium dioxide, Polysulfide, Cycling performance

中图分类号:

O646

吴桐, 丛丽娜, 孙立群, 谢海明. 氧缺位结构介孔二氧化钛/聚乙烯复合隔膜在锂硫电池中的应用[J]. 高等学校化学学报, 2020, 41(7): 1661-1669.

WU Tong, CONG Lina, SUN Liqun, XIE Haiming. Application of Porous Black Titanium Dioxide with Oxygen Vacancy/Polyethylene as a Composite Separator for Lithium Sulfur Batteries^†[J]. Chemical Journal of Chinese Universities, 2020, 41(7): 1661-1669.

图/表 12

Scheme 1 Schematic of the Li-S battery with b-TiO2 modified separator

Fig.1 XRD patterns(A) and Raman spectra(B) of w-TiO2(a) and b-TiO2(b), N2 adsorption-desorption isotherm(C) and pore size distribution(D) of b-TiO2, XPS spectra at Ti2p of w-TiO2(a) and b-TiO2(b)(E) and deconvoluted Ti2p of b-TiO2 composites(F)

Fig.2 SEM images(A, B), TEM image(C), elemental mapping of Ti(D) and S(E) and HRTEM image(F) of the b-TiO2 composites

Fig.3 Photographs showing the Li2S6 adsorption by w-TiO2 and b-TiO2

Fig.4 TG curve of C/S composite

Fig.5 Initial charge-discharge curves of Li-S batteries with unmodified separator and b-TiO2 modified separator at 0.1C(A), charge-discharge curves of the Li-S batteries with unmodified separator(B) and b-TiO2 modified separator(C) at different cycles and rate performance of Li-S batteries with unmodified separator and b-TiO2 modified separator at 0.1C, 0.2C, 0.5C, 1C and 2C(D)

Fig.6 Long cycle performance of Li-S batteries with unmodified separator and b-TiO2 modified separator at 0.1C for 100 cycles

Fig.7 Nyquist plots of the cell with unmodified separator(A) and with b-TiO2 modified separator(B) after different cycles at 0.1C and equivalent circuit of the Nyquist plots of the cells before cycle(circuit 1) and after different cycles(circuit 2)(C) R0 is the ohmic resistance of the cell including electrolyte and electrode. Rct is associated to the charge-transfer. RSEI is the resistance associated to the solid-electrolyte interface. CPEct is the constant phase element of the charge-transfer. CPESEI is theconstant phase element associated to the solid-electrolyte interface.

Table 1 Fitting parameters of the equivalent circuit[Fig.7(C)] to reproduce the Nyquist plots of the cell without and with b-TiO2 modified separator after different cycles*

Cycle number	Unmodified separator			b-TiO₂ Modified separator
Cycle number	R₀/Ω	R_ct/Ω	R_SEI/Ω	R₀/Ω	R_ct/Ω	R_SEI/Ω
0	0.10	22.9	—	0.11	20.1	—
5	0.09	33.1	14.3	0.15	21.7	10.4
25	0.11	53.8	19.7	0.09	24.3	26.3
100	0.10	85.9	28.9	0.10	16.7	25.8

Fig.8 SEM images of b-TiO2 after 100 cycles with different magnifications

Fig.9 XPS survey spectrum of Ti2p(A) and XRD pattern(B) of the b-TiO2 modified separator after 100 cycles

Fig.10 SEM iamges of the Li anode in the cell with b-TiO2 modified separator(A, B) and unmodified separator(C, D) after 100 cycles at 0.1C

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氧缺位结构介孔二氧化钛/聚乙烯复合隔膜在锂硫电池中的应用

Application of Porous Black Titanium Dioxide with Oxygen Vacancy/Polyethylene as a Composite Separator for Lithium Sulfur Batteries^†

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氧缺位结构介孔二氧化钛/聚乙烯复合隔膜在锂硫电池中的应用

Application of Porous Black Titanium Dioxide with Oxygen Vacancy/Polyethylene as a Composite Separator for Lithium Sulfur Batteries†

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Application of Porous Black Titanium Dioxide with Oxygen Vacancy/Polyethylene as a Composite Separator for Lithium Sulfur Batteries^†