Single crystal metal-organic framework constructed by vertically self-pillared nanosheets and its derivative for oriented lithium plating

doi:10.1016/S1872-2067(20)63755-X

Chinese Journal of Catalysis ›› 2021, Vol. 42 ›› Issue (9): 1553-1560.DOI: 10.1016/S1872-2067(20)63755-X

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Single crystal metal-organic framework constructed by vertically self-pillared nanosheets and its derivative for oriented lithium plating

Xiaomin Jia^a^,^†, Shaowen Li^b^,^†, Tu Sun^c^,^†, Yanzhi Wang^a^,^†, Yaqi Fan^c, Chaochao Zhang^a, Yang Xu^a, Zuozhong Liang^a, Haitao Lei^a, Wei Zhang^a, Yuye Zhou^d, Yanhang Ma^c, Haoquan Zheng^a^,^*(), Yue Ma^b^,^#(), Rui Cao^a^,^$()

^aKey Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119, Shaanxi, China
^bCenter for Nano Energy Materials, State Key Laboratory of Solidification Processing, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi'an 710072, Shaanxi, China
^cSchool of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China
^dSchool of Engineering Sciences in Chemistry, Biotechnology and Health, Department of Chemistry, Division of Applied Physical Chemistry, Analytical Chemistry, KTH Royal Institute of Technology, SE-106 91, Stockholm, Sweden

Received:2020-12-11 Accepted:2021-01-11 Online:2021-09-18 Published:2021-05-16
Contact: Haoquan Zheng,Yue Ma,Rui Cao
About author:^$ E-mail: ruicao@snnu.edu.cn
^# E-mail: mayue04@nwpu.edu.cn;
^* E-mail: zhenghaoquan@snnu.edu.cn;
First author contact:
^† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21975148);National Natural Science Foundation of China(51602261);National Natural Science Foundation of China(51711530037);National Natural Science Foundation of China(21773146);National Natural Science Foundation of China(21835002);National Natural Science Foundation of China(21875140);National Natural Science Foundation of China(21601118);Fok Ying-Tong Education Foundation for Outstanding Young Teachers in University(21601118);Fundamental Research Funds for the Central Universities(GK201903033);Fundamental Research Funds for the Central Universities(3102019JC005);Shanghai Natural Science Fund(17ZR1418600)

Abstract

Abstract:

This vertically self-pillared (VSP) structure extends the application range of traditional porous materials with facile mass/ion transport and enhanced reaction kinetics. Here, we prepare a single crystal metal-organic framework (MOF), employing the ZIF-67 structure as a proof of concept, which is constructed by vertically self-pillared nanosheets (VSP-MOF). We further converted VSP-MOF into VSP-cobalt sulfide (VSP-CoS₂) through a sulfidation process. Catalysis plays an important role in almost all battery technologies; for metallic batteries, lithium anodes exhibit a high theoretical specific capacity, low density, and low redox potential. However, during the half-cell reaction (Li⁺+e=Li), uncontrolled dendritic Li penetrates the separator and solid electrolyte interphase layer. When employed as a composite scaffold for lithium metal deposition, there are many advantage to using this framework: 1) the VSP-CoS₂ substrate provides a high specific surface area to dissipate the ion flux and mass transfer and acts as a pre-catalyst, 2) the catalytic Co center favors the charge transfer process and preferentially binds the Li⁺ with the enhanced electrical fields, and 3) the VSP structure guides the metallic propagation along the nanosheet 2D orientation without the protrusive dendrites. All these features enable the VSP structure in metallic batteries with encouraging performances.

Key words: Vertically self-pillared structure, Metal organic framework, Pre-catalyst preparation, Lithium plating orientation, Metallic battery

Xiaomin Jia, Shaowen Li, Tu Sun, Yanzhi Wang, Yaqi Fan, Chaochao Zhang, Yang Xu, Zuozhong Liang, Haitao Lei, Wei Zhang, Yuye Zhou, Yanhang Ma, Haoquan Zheng, Yue Ma, Rui Cao. Single crystal metal-organic framework constructed by vertically self-pillared nanosheets and its derivative for oriented lithium plating[J]. Chinese Journal of Catalysis, 2021, 42(9): 1553-1560.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63755-X

https://www.cjcatal.com/EN/Y2021/V42/I9/1553

Figures/Tables 4

Fig. 1. Illustrating house-of-cards structure (a), selected area electron diffraction (SAED) pattern (b) and corresponding TEM image (c) along [111] of VSP-MOFs. Projection of reconstructed reciprocal lattice from 3D EDT data along [100] (d), [010] (e), [001] (f) directions, respectively. The crystal structural mode (g), experimental PXRD patterns (h) and N2 adsorption/desorption isotherm (i) of VSP-MOF and reference materials.

Fig. 2. TEM (a), HRTEM (b) images, EDS mapping (c), PXRD pattern (d), high-resolution XPS of Co 2p (e) and S 2p (f) of VSP-CoS2.

Fig. 3. Electrochemical characterization of the metallic batteries assembled by the VSP-CoS2 composite anodes. The discharge/charge profiles of (a) VSP-CoS2 electrode at the selected cycles between 0 and 3 V; (b) Voltage-time profiles of the Li plating/stripping of VSP-CoS2||VSP-CoS2 and Li||Li@1 mA cm-2 with the predetermined capacity of 1 mAh cm-2 for 510 h in symmetric cells; (c) The enlarged view of the voltage-time curve of the VSP-CoS2||VSP-CoS2 and Li||Li cells during 0 to 5 h symmetric cycling; (d) Voltage pro?les of the VSP-CoS2 electrode after activation process for different cycles with the upper cutoff voltage of 1.0 V at 5 mA cm-2; The inset in Fig. 3(d) presents the enlarged voltage pro?le. (e) CE of the VSP-CoS2 composite and the bare Cu foil for 100 cycles@0.5, 1, and 2 mA cm-2; (f) Galvanostatic discharge-charge curves of LMO||VSP-CoS2 full cell during different cycles.

Fig. 4. Schematic illustration of the Li plating in the VSP-CoS2 composite at different cycling states.

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Single crystal metal-organic framework constructed by vertically self-pillared nanosheets and its derivative for oriented lithium plating

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