基于ZIF-8的三维网络硅碳复合材料锂离子电池性能研究

doi:10.15541/jim20210739

无机材料学报 ›› 2022, Vol. 37 ›› Issue (9): 1016-1022.DOI: 10.15541/jim20210739

所属专题：【能源环境】金属有机框架材料

基于ZIF-8的三维网络硅碳复合材料锂离子电池性能研究

宿拿拿¹(), 韩静茹¹, 郭印毫¹, 王晨宇¹, 石文华¹, 吴亮¹, 胡执一¹^,², 刘婧¹, 李昱¹^,²(), 苏宝连¹^,³

1.武汉理工大学材料复合新技术国家重点实验室, 武汉 430070
2.武汉理工大学纳微结构研究中心, 武汉 430070
3.那慕尔大学无机材料化学实验室, 那慕尔 B-5000, 比利时

收稿日期:2021-12-03 修回日期:2022-02-08 出版日期:2022-09-20 网络出版日期:2022-02-21
通讯作者: 李昱, 教授. E-mail: yu.li@whut.edu.cn
作者简介:宿拿拿(1997-), 女, 硕士研究生. E-mail: nana.su@whut.edu.cn
基金资助:
国家重点研发计划(2016YFA0202602);国家重点研发计划(2021YFE0115800);国家自然科学基金(U20A20122);国家自然科学基金(52103285);111引智计划(B20002);湖北省自然科学基金(2020CFB416);中央高校专项基金(WUT: 2021III016GX)

ZIF-8-derived Three-dimensional Silicon-carbon Network Composite for High-performance Lithium-ion Batteries

SU Nana¹(), HAN Jingru¹, GUO Yinhao¹, WANG Chenyu¹, SHI Wenhua¹, WU Liang¹, HU Zhiyi¹^,², LIU Jing¹, LI Yu¹^,²(), SU Baolian¹^,³

1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
2. Nanostructure Research Centre (NRC), Wuhan University of Technology, Wuhan 430070, China
3. Laboratory of Inorganic Materials Chemistry (CMI), University of Namur, Namur B-5000, Belgium

Received:2021-12-03 Revised:2022-02-08 Published:2022-09-20 Online:2022-02-21
Contact: LI Yu, professor. E-mail: yu.li@whut.edu.cn
About author:SU Nana (1997-), female, Master candidate. E-mail: nana.su@whut.edu.cn
Supported by:
National Key R&D Program of China(2016YFA0202602);National Key R&D Program of China(2021YFE0115800);National Natural Science Foundation of China(U20A20122);National Natural Science Foundation of China(52103285);The 111 National Project(B20002);Natural Science Foundation of Hubei Province(2020CFB416);The Fundamental Research Funds for the Central Universities(WUT: 2021III016GX)

摘要/Abstract

摘要：

锂离子电池已广泛应用于各种便携式电子设备及新能源汽车等领域, 但随着电子设备的不断更新换代及电动汽车的快速发展, 理论比容量较低的传统石墨负极(372 mAh/g)已无法满足社会的需求。基于此, 本工作设计并制备了一种Zn基金属有机物框架(ZIF-8)衍生的三维网络状硅碳(Si@NC)复合材料用于锂离子电池性能研究。首先对纳米硅表面进行化学改性,然后在改性的硅表面原位生长ZIF-8小颗粒(Si@ZIF-8), 最后对Si@ZIF-8碳化得到Si@NC复合材料。研究表明, Si@NC复合材料的三维网络状多孔结构既可以很好地限制硅的体积膨胀, 又能极大地提升材料的电导率, 展现出稳定的循环性能和良好的倍率性能, 在5 A/g的大电流下能保持760 mAh/g的放电比容量。与商业三元正极材料组装的全电池也表现出较好的性能, 在0.4C (1C =160 mA/g)下循环50圈依然可以保持60.4%的比容量。这些研究结果说明该Si@NC复合材料具有较好的应用前景。

关键词: 负极, 硅/碳, 锂离子电池, 三维网络状

Abstract:

Lithium-ion batteries (LIBs) are widely applied to various portable electronic devices and new energy vehicles. However, the traditional graphite anode with low theoretical capacity (372 mAh/g) is unable to meet the need of the rapid development of economy and society. Herein, a zinc-based metallic organic framework (ZIF-8) derived three-dimensional network carbon coated silicon (Si@NC) composite was designed for lithium-ion battery. Firstly, the surface of nano-silicon was chemical modified; secondly, small size ZIF-8 was in situ grown on the silicon surface to form Si@ZIF-8; finally, the three-dimensional network Si@NC composite was obtained by carbonization. Results show that the three-dimensional network porous structure of the Si@NC composite not only limits the volume expansion of silicon, but greatly improves the conductivity of the materials, exhibiting excellent cycle stability and outstanding rate performance. As a result, a discharge specific capacity of 760 mAh/g is maintained at a high current density of 5 A/g. Using commercial material as cathode and Si@NC as anode, the assembled full LIBs demonstrate a capacity retention of 60.4% at 0.4C (1C =160 mA/g) for 50 cycles. These results indicate that the as-synthesized three-dimensional network porous structure of Si@NC composite has a potential practical application for LIBs.

Key words: anode, silicon/carbon, lithium-ion battery, three-dimensional network

中图分类号:

TQ152

宿拿拿, 韩静茹, 郭印毫, 王晨宇, 石文华, 吴亮, 胡执一, 刘婧, 李昱, 苏宝连. 基于ZIF-8的三维网络硅碳复合材料锂离子电池性能研究[J]. 无机材料学报, 2022, 37(9): 1016-1022.

SU Nana, HAN Jingru, GUO Yinhao, WANG Chenyu, SHI Wenhua, WU Liang, HU Zhiyi, LIU Jing, LI Yu, SU Baolian. ZIF-8-derived Three-dimensional Silicon-carbon Network Composite for High-performance Lithium-ion Batteries[J]. Journal of Inorganic Materials, 2022, 37(9): 1016-1022.

图/表 11

图1 三维网络结构Si@NC的(a)合成过程示意图和(b)锂化/脱锂示意图

Fig. 1 Schematics of (a) synthetic process and (b) lithiation-delithiation process for Si@NC

图2 (a, b)Si@NC和(c, d)Si@PC样品的FESEM照片

Fig. 2 FESEM images of (a, b) Si@NC and (c, d) Si@PC White circles in (b, d): Si nano particles

图3 Si@NC样品的(a)TEM, (b)HRTEM, (c) HAADF-STEM, (d) SAED照片和(e~f) EDX元素分布图

Fig. 3 (a) TEM, (b) HRTEM, (c) HAADF-STEM images, (d) SAED pattern (rectangular area in (c)), and (e-f) corresponding EDX elemental maps of Si@NC (d) Rectangular area in (c); (e-f) Corresponding area in (c), Si (green), C (yellow), N (blue), O (cyan) and Zn (red)

图4 Si@NC和Si@PC样品的(a)XRD图谱和(b)拉曼光谱图, Si@NC的(c)氮气吸/脱附等温线和(d)孔径分布图

Fig. 4 (a) XRD patterns and (b) Raman spectra of Si@NC and Si@PC, (c) nitrogen adsorption-desorption isotherm and (d) pore size distribution of Si@NC

图5 Si@NC的(a) CV曲线和(b)在0.2 A/g电流密度下前三圈的充放电曲线, Si@NC和Si@PC的(c)倍率性能和(d)在0.5 A/g电流密度下的循环性能, (e) Si@NC、NC和Si@PC在1 A/g电流密度下的长循环性能(黑色圆圈表示Si@NC的库仑效率)

Fig. 5 (a) CV curves at a scanning rate of 0.2 mV/s and (b) charge-discharge curves for initial 3 cycles at 0.2 A/g of Si@NC, (c) rate performances and (d) cycling performances at 0.5 A/g of Si@NC and Si@PC, and (e) long cycling performances of Si@NC, NC and Si@PC at 1 A/g (black circles showing Coulombic efficiencies of Si@NC)

图6 Si@NC//NCM622全电池(a)在1~4.5 V范围的充放电曲线和(b)0.4C下的循环性能

Fig. 6 (a) Charge-discharge profiles in the range of 1~4.5 V, and (b) cycle performance at 0.4C of Si@NC//NCM622 full-cell

图S1 (a)Si@NC和(b)NC的TG-DSC曲线

Fig. S1 TG-DSC curves of (a) Si@NC and (b) NC

图S2 Si@NC材料的XPS谱图

Fig. S2 XPS spectra of Si@NC composite (a) Survey spectrum; High-resolution spectra of (b) Si2p, (c) C1s and (d) N1s

图S3 (a)纯Si、Si@NC和Si@PC的电化学阻抗谱图, (b) Si@NC和纯Si前5圈的库仑效率, (c)纯Si在1 A/g下的长循环性能

Fig. S3 EIS plots of pure Si, Si@NC and Si@PC, (b) Coulombic efficiencies of Si@NC and pure Si for the first 5 cycles, (c) cycle performance of pure Si at 1 A/g

图S4 半电池中Si@NC电极(a)循环前、循环(b)50和(c)200圈后的截面及表面SEM照片

Fig. S4 Cross section and surface SEM images of Si@NC electrodes for half-cell (a) before the cycle, after (b)50 and (c) 200 cycles

表S1 Si/C复合材料电化学性能比较

Table S1 Comparison of electrochemical performance for Si/C composite materials

Anode material	Cycle performance/(mAh·g^-1) (Cycle number)	Current density/ (A·g^-1)	Rate capability/(mAh·g^-1) (Current density/(A·g^-1))	Ref.
Three-dimensional Network Si/C	666 (500th)	1	760 (5)	This work
MHR-Si/rGO	530 (400th)	1	513 (5)	[1]
Si@C/Co/CNTs	700 (500th)	1	480 (5)	[2]
Pseudographite/Si/Ni	800 (500th)	1	271 (5)	[3]
Si@void@C/C-2	450 (500th)	1	410 (3.2)	[4]
Yolk-shell structured Si-based anode	657 (200th)	1	350 (5)	[5]
Si@C-ZIF@carbon Nanofibers	760 (500th)	1	523.9 (5)	[6]

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基于ZIF-8的三维网络硅碳复合材料锂离子电池性能研究

ZIF-8-derived Three-dimensional Silicon-carbon Network Composite for High-performance Lithium-ion Batteries

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