AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Highly crystalline vinylene-linked covalent organic frameworks enhanced solid polycarbonate electrolyte for dendrite-free solid lithium metal batteries

Kaige Zhang1,2,§, Chaoqun Niu2,§, Chengbing Yu3( ), Li Zhang1( ), Yuxi Xu2( )
School of Materials and Engineering, Zhengzhou University, Zhengzhou 450001, China
School of Engineering, Westlake University, Hangzhou 310024, China
School of Materials Science and Engineering, Shanghai University, Shanghai 201800, China

§ Kaige Zhang and Chaoqun Niu contributed equally to this work.

Show Author Information

Graphical Abstract

We design novel covalent organic framework (COF)-based composite electrolyte films with chemical bond linked COFs to improve the ionic conductivity and mechanical strengths. The composite electrolyte films have an obvious effect on inhibiting the dendrites of lithium metal and the assembled full cell with LiFePO4 as the cathode exhibits superior rate capability and cycling stability.

Abstract

The development of solid-state electrolytes (SSEs) with high ionic conductivity, outstanding electrochemical window, and promising mechanical strength is a key factor in realizing the commercialization of high energy density solid-state lithium metal batteries (LMBs). Covalent organic frameworks (COFs) are a functional crystalline material with highly customizable molecular networks and one-dimensional channel structures, thus showing great potential applications in SSEs. Herein, we design flexible COF-poly(vinyl ethylene carbonate) (PVEC) (abbreviated as COF-PVEC) composite electrolyte films with excellent ionic conductivity and high mechanical strength, enabling dendrite-free and long-term running solid-state LMBs. Owing to the lithium-philic triazine and carbon–carbon double bonds groups in the COF skeleton, the obtained flexible COF-PVEC shows high ionic conductivity up to 1.11 × 10−4 S·cm−1 at 40 °C, and enlarged electrochemical window up to 4.6 V (vs. Li+/Li) compared with pure PVEC electrolyte. At the same time, the lithium dendrites are efficiently inhibited after discharge–charging cycles, due to the improved Young’s modulus (150 MPa) and ordered channels of COF. Using the various features of COF-PVEC, we assembled a solid-state full battery with LiFePO4 cathode, which showed superior rate capacity (151.8, 146.2, 139.2, 128.1, 113.7, and 100.8 mAh·g−1 at 0.1, 0.2, 0.5, 1, 1.5, and 2 C, respectively) and excellent long-term cycling stability (over 400 cycles at 1 C). We believe that the COF-based composite electrolyte can become one of the most promising high-performance SSEs for solid-state LMBs.

Keywords

solid-state electrolytescovalent organic frameworkslithium dendritessolid-state lithium metal batteries

Electronic Supplementary Material

Download File(s)
12274_2022_4480_MOESM1_ESM.pdf (519.1 KB)

References

1

Cheng, X. B.; Zhang, R.; Zhao, C. Z.; Zhang, Q. Toward safe lithium metal anode in rechargeable batteries: A review. Chem. Rev. 2017, 117, 10403–10473.
Crossref Google Scholar
2

Winter, M.; Barnett, B.; Xu, K. Before Li ion batteries. Chem. Rev. 2018, 118, 11433–11456.
Crossref Google Scholar
3

Dong, T. T.; Zhang, J. J.; Xu, G. J.; Chai, J. C.; Du, H. P.; Wang, L. L.; Wen, H. J.; Zang, X.; Du, A. B.; Jia, Q. M. et al. A multifunctional polymer electrolyte enables ultra-long cycle-life in a high-voltage lithium metal battery. Energy Environ. Sci. 2018, 11, 1197–1203.
Crossref Google Scholar
4

Xia, S. X.; Zhang, X.; Luo, L. L.; Pang, Y. P.; Yang, J. H.; Huang, Y. Z.; Zheng, S. Y. Highly stable and ultrahigh-rate Li metal anode enabled by fluorinated carbon fibers. Small 2021, 17, 2006002.
Crossref Google Scholar
5

Yu, Z.; Mackanic, D. G.; Michaels, W.; Lee, M.; Pei, A.; Feng, D. W.; Zhang, Q. H.; Tsao, Y.; Amanchukwu, C. V.; Yan, X. Z. et al. A dynamic, electrolyte-blocking, and single-ion-conductive network for stable lithium-metal anodes. Joule 2019, 3, 2761–2776.
Crossref Google Scholar
6

Niu, C. J.; Lee, H.; Chen, S. R.; Li, Q. Y.; Du, J.; Xu, W.; Zhang, J. G.; Whittingham, M. S.; Xiao, J.; Liu, J. High-energy lithium metal pouch cells with limited anode swelling and long stable cycles. Nat. Energy 2019, 4, 551–559.
Crossref Google Scholar
7

Zhao, Q.; Liu, X. T.; Stalin, S.; Khan, K.; Archer, L. A. Solid-state polymer electrolytes with in-built fast interfacial transport for secondary lithium batteries. Nat. Energy 2019, 4, 365–373.
Crossref Google Scholar
8

Zhao, Q.; Stalin, S.; Zhao, C. Z.; Archer, L. A. Designing solid-state electrolytes for safe, energy-dense batteries. Nat. Rev. Mater. 2020, 5, 229–252.
Crossref Google Scholar
9

Etacheri, V.; Marom, R.; Elazari, R.; Salitra, G.; Aurbach, D. Challenges in the development of advanced Li-ion batteries: A review. Energy Environ. Sci. 2011, 4, 3243–3262.
Crossref Google Scholar
10

Lee, Y. G.; Fujiki, S.; Jung, C.; Suzuki, N.; Yashiro, N.; Omoda, R.; Ko, D. S.; Shiratsuchi, T.; Sugimoto, T.; Ryu, S. et al. High-energy long-cycling all-solid-state lithium metal batteries enabled by silver-carbon composite anodes. Nat. Energy 2020, 5, 299–308.
Crossref Google Scholar
11

Tang, W. J.; Tang, S.; Zhang, C. J.; Ma, Q. T.; Xiang, Q.; Yang, Y. W.; Luo, J. Y. Simultaneously enhancing the thermal stability, mechanical modulus, and electrochemical performance of solid polymer electrolytes by incorporating 2D sheets. Adv. Energy Mater. 2018, 8, 1800866.
Crossref Google Scholar
12

Bachman, J. C.; Muy, S.; Grimaud, A.; Chang, H. H.; Pour, N.; Lux, S. F.; Paschos, O.; Maglia, F.; Lupart, S.; Lamp, P. et al. Inorganic solid-state electrolytes for lithium batteries: Mechanisms and properties governing ion conduction. Chem. Rev. 2016, 116, 140–162.
Crossref Google Scholar
13

Wang, C. W.; Gong, Y. H.; Liu, B. Y.; Fu, K.; Yao, Y. G.; Hitz, E.; Li, Y. J.; Dai, J. Q.; Xu, S. M.; Luo, W. et al. Conformal, nanoscale ZnO surface modification of garnet-based solid-state electrolyte for lithium metal anodes. Nano Lett. 2017, 17, 565–571.
Crossref Google Scholar
14

Luo, W.; Gong, Y. H.; Zhu, Y. Z.; Li, Y. J.; Yao, Y. G.; Zhang, Y.; Fu, K.; Pastel, G.; Lin, C. F.; Mo, Y. F. et al. Reducing interfacial resistance between garnet-structured solid-state electrolyte and Li-metal anode by a germanium layer. Adv. Mater. 2017, 29, 1606042.
Crossref Google Scholar
15

Chen, X. Z.; He, W. J.; Ding, L. X.; Wang, S. Q.; Wang, H. H. Enhancing interfacial contact in all solid state batteries with a cathode-supported solid electrolyte membrane framework. Energy Environ. Sci. 2019, 12, 938–944.
Crossref Google Scholar
16

Arya, A.; Sharma, A. L. A glimpse on all-solid-state Li-ion battery (asslib) performance based on novel solid polymer electrolytes: A topical review. J. Mater. Sci. 2020, 55, 6242–6304.
Crossref Google Scholar
17

Xiao, Y. H.; Wang, Y.; Bo, S. H.; Kim, J. C.; Miara, L. J.; Ceder, G. Understanding interface stability in solid-state batteries. Nat. Rev. Mater. 2020, 5, 105–126.
Crossref Google Scholar
18

Zheng, Y.; Yao, Y. Z.; Ou, J. H.; Li, M.; Luo, D.; Dou, H. Z.; Li, Z. Q.; Amine, K.; Yu, A. P.; Chen, Z. W. A review of composite solid-state electrolytes for lithium batteries: Fundamentals, key materials and advanced structures. Chem. Soc. Rev. 2020, 49, 8790–8839.
Crossref Google Scholar
19

Liu, L. H.; Mo, J. S.; Li, J. R.; Liu, J. X.; Yan, H. J.; Lyu, J.; Jiang, B.; Chu, L. H.; Li, M. C. Comprehensively-modified polymer electrolyte membranes with multifunctional PMIA for highly-stable all-solid-state lithium-ion batteries. J. Energy Chem. 2020, 48, 334–343.
Crossref Google Scholar
20

Polu, A. R.; Rhee, H. W.; Kim, D. K. New solid polymer electrolytes (PEO20-LiTDI-SN) for lithium batteries: Structural, thermal and ionic conductivity studies. J. Mater. Sci.: Mater. Electron. 2015, 26, 8548–8554.
Crossref Google Scholar
21

Yang, L. Y.; Wei, D. X.; Xu, M.; Yao, Y. F.; Chen, Q. Transferring lithium ions in nanochannels: A PEO/Li+ solid polymer electrolyte design. Angew. Chem. 2014, 126, 3705–3709.
Crossref Google Scholar
22

Nitzan, A.; Ratner, M. A. Conduction in polymers: Dynamic disorder transport. J. Phys. Chem. 1994, 98, 1765–1775.
Crossref Google Scholar
23

Borodin, O.; Smith, G. D. Mechanism of ion transport in amorphous poly(ethylene oxide)/LiTFSI from molecular dynamics simulations. Macromolecules 2006, 39, 1620–1629.
Crossref Google Scholar
24

Cao, J.; Wang, L.; He, X. M.; Fang, M.; Gao, J.; Li, J. J.; Deng, L. F.; Chen, H.; Tian, G. Y.; Wang, J. L. et al. In situ prepared nano-crystalline TiO2-poly(methyl methacrylate) hybrid enhanced composite polymer electrolyte for Li-ion batteries. J. Mater. Chem. A 2013, 1, 5955–5961.
Crossref Google Scholar
25

Wang, Q. J.; Song, W. L.; Fan, L. Z.; Shi, Q. Effect of alumina on triethylene glycol diacetate-2-propenoic acid butyl ester composite polymer electrolytes for flexible lithium ion batteries. J. Power Sources 2015, 279, 405–412.
Crossref Google Scholar
26

Gomez, E. D.; Panday, A.; Feng, E. H.; Chen, V.; Stone, G. M.; Minor, A. M.; Kisielowski, C.; Downing, K. H.; Borodin, O.; Smith, G. D. et al. Effect of ion distribution on conductivity of block copolymer electrolytes. Nano Lett. 2009, 9, 1212–1216.
Crossref Google Scholar
27

Zhai, H. W.; Xu, P. Y.; Ning, M. Q.; Cheng, Q.; Mandal, J.; Yang, Y. A flexible solid composite electrolyte with vertically aligned and connected ion-conducting nanoparticles for lithium batteries. Nano Lett. 2017, 17, 3182–3187.
Crossref Google Scholar
28

Wan, J. Y.; Xie, J.; Kong, X.; Liu, Z.; Liu, K.; Shi, F. F.; Pei, A.; Chen, H.; Chen, W.; Chen, J. et al. Ultrathin, flexible, solid polymer composite electrolyte enabled with aligned nanoporous host for lithium batteries. Nat. Nanotechnol. 2019, 14, 705–711.
Crossref Google Scholar
29

Dirican, M.; Yan, C. Y.; Zhu, P.; Zhang, X. W. Composite solid electrolytes for all-solid-state lithium batteries. Mater. Sci. Eng.: R: Rep. 2019, 136, 27–46.
Crossref Google Scholar
30

Tu, Z. Y.; Kambe, Y.; Lu, Y. Y.; Archer, L. A. Nanoporous polymer-ceramic composite electrolytes for lithium metal batteries. Adv. Energy Mater. 2014, 4, 1300654.
Crossref Google Scholar
31

Jung, S.; Kim, D. W.; Lee, S. D.; Cheong, M. C.; Nguyen, D. Q.; Cho, B. W.; Kim, H. S. Fillers for solid-state polymer electrolytes: Highlight. Bull. Korean Chem. Soc. 2009, 30, 2355–2361.
Crossref Google Scholar
32

Xiong, H. M.; Wang, Z. D.; Xie, D. P.; Cheng, L.; Xia, Y. Y. Stable polymer electrolytes based on polyether-grafted ZnO nanoparticles for all-solid-state lithium batteries. J. Mate. Chem. 2006, 16, 1345–1349.
Crossref Google Scholar
33

Chua, S.; Fang, R. P.; Sun, Z. H.; Wu, M. J.; Gu, Z.; Wang, Y. Z.; Hart, J. N.; Sharma, N.; Li, F.; Wang, D. W. Hybrid solid polymer electrolytes with two-dimensional inorganic nanofillers. Chem. -Eur. J. 2018, 24, 18180–18203.
Crossref Google Scholar
34

He, Z. J.; Chen, L.; Zhang, B. C.; Liu, Y. C.; Fan, L. Z. Flexible poly(ethylene carbonate)/garnet composite solid electrolyte reinforced by poly(vinylidene fluoride-hexafluoropropylene) for lithium metal batteries. J. Power Sources 2018, 392, 232–238.
Crossref Google Scholar
35

Jeong, K.; Park, S.; Jung, G. Y.; Kim, S. H.; Lee, Y. H.; Kwak, S. K.; Lee, S. Y. Solvent-free, single lithium-ion conducting covalent organic frameworks. J. Am. Chem. Soc. 2019, 141, 5880–5885.
Crossref Google Scholar
36

Huang, N.; Wang, P.; Jiang, D. L. Covalent organic frameworks: A materials platform for structural and functional designs. Nat. Rev. Mater. 2016, 1, 16068.
Crossref Google Scholar
37

Kandambeth, S.; Biswal, B. P.; Chaudhari, H. D.; Rout, K. C.; Kunjattu, H. S.; Mitra, S.; Karak, S.; Das, A.; Mukherjee, R.; Kharul, U. K. Selective molecular sieving in self-standing porous covalent-organic-framework membranes. Adv. Mater. 2017, 29, 1603945.
Crossref Google Scholar
38

Ma, W. D.; Zheng, Q.; He, Y. T.; Li, G. R.; Guo, W. J.; Lin, Z.; Zhang, L. Size-controllable synthesis of uniform spherical covalent organic frameworks at room temperature for highly efficient and selective enrichment of hydrophobic peptides. J. Am. Chem. Soc. 2019, 141, 18271–18277.
Crossref Google Scholar
39

Xu, Q.; Tao, S. S.; Jiang, Q. H.; Jiang, D. L. Designing covalent organic frameworks with a tailored ionic interface for ion transport across one-dimensional channels. Angew. Chem., Int. Ed. 2020, 59, 4557–4563.
Crossref Google Scholar
40

Niu, C. Q.; Luo, W. J.; Dai, C. M.; Yu, C. B.; Xu, Y. X. High-voltage-tolerant covalent organic framework electrolyte with holistically oriented channels for solid-state lithium metal batteries with nickel-rich cathodes. Angew. Chem., Int. Ed. 2021, 60, 24915–24923.
Crossref Google Scholar
41

Sun, Q.; Aguila, B.; Perman, J.; Earl, L. D.; Abney, C. W.; Cheng, Y. C.; Wei, H.; Nguyen, N.; Wojtas, L.; Ma, S. Q. Postsynthetically modified covalent organic frameworks for efficient and effective mercury removal. J. Am. Chem. Soc. 2017, 139, 2786–2793.
Crossref Google Scholar
42

Lin, Z. Y.; Guo, X. W.; Wang, Z. C.; Wang, B. Y.; He, S. M.; O'Dell, A.; Huang, J.; Li, H.; Yu, H. J.; Chen, L. Q. A wide-temperature superior ionic conductive polymer electrolyte for lithium metal battery. Nano Energy 2020, 73, 104786.
Crossref Google Scholar
43

Xu, Q.; Tao, S. S.; Jiang, Q. H.; Jiang, D. L. Ion conduction in polyelectrolyte covalent organic frameworks. J. Am. Chem. Soc. 2018, 140, 7429–7432.
Crossref Google Scholar
44

Zhou, B.; Jiang, J. N.; Zhang, F. F.; Zhang, H. N. Crosslinked poly(ethylene oxide)-based membrane electrolyte consisting of polyhedral oligomeric silsesquioxane nanocages for all-solid-state lithium ion batteries. J. Power Sources 2020, 449, 227541.
Crossref Google Scholar
45

Li, X. W.; Zheng, Y. W.; Li, C. Y. Dendrite-free, wide temperature range lithium metal batteries enabled by hybrid network ionic liquids. Energy Storage Mater. 2020, 29, 273–280.
Crossref Google Scholar
46

Wang, Y. X.; Zhang, K.; Jiang, X. Z.; Liu, Z. Y.; Bian, S. Y.; Pan, Y. Y.; Shan, Z.; Wu, M. M.; Xu, B. Q.; Zhang, G. Branched poly(ethylene glycol)-functionalized covalent organic frameworks as solid electrolytes. ACS Appl. Energy Mater. 2021, 4, 11720–11725.
Crossref Google Scholar
47

Xia, S. X.; Yang, B. B.; Zhang, H. B.; Yang, J. H.; Liu, W.; Zheng, S. Y. Ultrathin layered double hydroxide nanosheets enabling composite polymer electrolyte for all-solid-state lithium batteries at room temperature. Adv. Funct. Mater. 2021, 31, 2101168.
Crossref Google Scholar
Nano Research
Volume 15 Issue 9,
September 2022
Pages 8083-8090
DOI: 10.1007/s12274-022-4480-6
Cite this article:
Zhang K, Niu C, Yu C, et al. Highly crystalline vinylene-linked covalent organic frameworks enhanced solid polycarbonate electrolyte for dendrite-free solid lithium metal batteries. Nano Research, 2022, 15(9): 8083-8090. https://doi.org/10.1007/s12274-022-4480-6
Topics:
Lithium batteries

1122

Views

28

Crossref

26

Web of Science

26

Scopus

0

CSCD

Altmetrics
Received: 05 March 2022
Revised: 20 April 2022
Accepted: 28 April 2022
Published: 18 June 2022
© Tsinghua University Press 2022
Return