Janus Quasi-Solid Electrolyte Membranes with Asymmetric Porous Structure for High-Performance Lithium-Metal Batteries

Abstract

Abstract:

Quasi-solid electrolytes (QSEs) based on nanoporous materials are promising candidates to construct high-performance Li-metal batteries (LMBs). However, simultaneously boosting the ionic conductivity (σ) and lithium-ion transference number (t₊) of liquid electrolyte confined in porous matrix remains challenging. Herein, we report a novel Janus MOFLi/MSLi QSEs with asymmetric porous structure to inherit the benefits of both mesoporous and microporous hosts. This Janus QSE composed of mesoporous silica and microporous MOF exhibits a neat Li⁺conductivity of 1.5 × 10^-4S cm⁻¹witht₊of 0.71. A partially de-solvated structure and preference distribution of Li⁺near the Lewis base O atoms were depicted by MD simulations. Meanwhile, the nanoporous structure enabled efficient ion flux regulation, promoting the homogenous deposition of Li⁺. When incorporated in Li||Cu cells, the MOFLi/MSLi QSEs demonstrated a high Coulombic efficiency of 98.1%, surpassing that of liquid electrolytes (96.3%). Additionally, NCM 622||Li batteries equipped with MOFLi/MSLi QSEs exhibited promising rate performance and could operate stably for over 200 cycles at 1 C. These results highlight the potential of Janus MOFLi/MSLi QSEs as promising candidates for next-generation LMBs.

Key words:Metal-organic frameworks,Mesoporous silicas,Quasi-solid electrolytes,Janus structure,Lithium-metal battery

Zerui Chen, Wei Zhao, Qian Liu, Yifei Xu, Qinghe Wang, Jinmin Lin, Hao Bin Wu. Janus Quasi-Solid Electrolyte Membranes with Asymmetric Porous Structure for High-Performance Lithium-Metal Batteries[J]. Nano-Micro Letters, 2024, 16(1): 114-.

Zerui Chen, Wei Zhao, Qian Liu, Yifei Xu, Qinghe Wang, Jinmin Lin, Hao Bin Wu. [J]. Nano-Micro Letters, 2024, 16(1): 114-.

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URL:https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01325-4

https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/114

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1.	H . Furukawa , K.E . Cordova , M . O’Keeffe , O.M . Yaghi , The chemistry and applications of metal-organic frameworks. Science 341, 1230444 2013). https://doi.org/10.1126/science.1230444
2.	J.L.C . Rowsell , O.M . Yaghi , Metal-organic frameworks: a new class of porous materials. Microporous Mesoporous Mater. 73, 3-14 ( 2004). https://doi.org/10.1016/j.micromeso.2004.03.034
3.	S.-Y . Ding , W . Wang , Covalent organic frameworks (COFs): from design to applications. Chem. Soc. Rev. 42, 548-568 ( 2013). https://doi.org/10.1039/C2CS35072F
4.	X . Feng , X . Ding , D . Jiang , Covalent organic frameworks. Chem. Soc. Rev. 41, 6010-6022 ( 2012). https://doi.org/10.1039/c2cs35157a
5.	K . Geng , T . He , R . Liu , S . Dalapati , K.T . Tan et al., Covalent organic frameworks: design, synthesis, and functions. Chem. Rev. 120, 8814-8933 ( 2020). https://doi.org/10.1021/acs.chemrev.9b00550
6.	U . Olsbye , S . Svelle , M . Bjørgen , P . Beato , T.V . Janssens et al., Conversion of methanol to hydrocarbons: How zeolite cavity and pore size controls product selectivity. Angew. Chem. Int. Ed. 51, 5810-5831 ( 2012). https://doi.org/10.1002/anie.201103657
7.	Z . Chang , H . Yang , X . Zhu , P . He , H . Zhou , A stable quasi-solid electrolyte improves the safe operation of highly efficient lithium-metal pouch cells in harsh environments. Nat. Commun. 13, 1510 ( 2022). https://doi.org/10.1038/s41467-022-29118-6
8.	L . Shen , H.B . Wu , F . Liu , J.L . Brosmer , G . Shen et al., Creating lithium-ion electrolytes with biomimetic ionic channels in metal-organic frameworks. Adv. Mater. 30, e1707476 ( 2018). https://doi.org/10.1002/adma.201707476
9.	B.M . Wiers , M.-L . Foo , N.P . Balsara , J.R . Long , A solid lithium electrolyte via addition of lithium isopropoxide to a metal-organic framework with open metal sites. J. Am. Chem. Soc. 133, 14522-14525 ( 2011). https://doi.org/10.1021/ja205827z
10.	S . Bai , X . Liu , K . Zhu , S . Wu , H . Zhou , Metal-organic framework-based separator for lithium-sulfur batteries. Nat. Energy 1, 16094 2016). https://doi.org/10.1038/nenergy.2016.94
11.	H . Chen , H . Tu , C . Hu , Y . Liu , D . Dong et al., Cationic covalent organic framework nanosheets for fast Li-ion conduction. J. Am. Chem. Soc. 140, 896-899 ( 2018). https://doi.org/10.1021/jacs.7b12292
12.	X . Li , Q . Hou , W . Huang , H.-S . Xu , X . Wang et al., Solution-processable covalent organic framework electrolytes for all-solid-state Li-organic batteries. ACS Energy Lett. 5, 3498-3506 ( 2020). https://doi.org/10.1021/acsenergylett.0c01889
13.	X . Chi , M . Li , J . Di , P . Bai , L . Song et al., A highly stable and flexible zeolite electrolyte solid-state Li-air battery. Nature 592, 551-557 ( 2021). https://doi.org/10.1038/s41586-021-03410-9
14.	Y . Xu , L . Gao , Q . Liu , Q . Liu , Z . Chen et al., Segmental molecular dynamics boosts Li-ion conduction in metal-organic solid electrolytes for Li-metal batteries. Energy Storage Mater. 54, 854-862 ( 2023). https://doi.org/10.1016/j.ensm.2022.11.029
15.	H . Yang , B . Liu , J . Bright , S . Kasani , J . Yang et al., A single-ion conducting UiO-66 metal-organic framework electrolyte for all-solid-state lithium batteries. ACS Appl. Energy Mater. 3, 4007-4013 ( 2020). https://doi.org/10.1021/acsaem.0c00410
16.	F . Zhu , H . Bao , X . Wu , Y . Tao , C . Qin et al., High-performance metal-organic framework-based single ion conducting solid-state electrolytes for low-temperature lithium metal batteries. ACS Appl. Mater. Interfaces 11, 43206-43213 ( 2019). https://doi.org/10.1021/acsami.9b15374
17.	Z . Chang , Y . Qiao , H . Deng , H . Yang , P . He et al., A liquid electrolyte with de-solvated lithium ions for lithium-metal battery. Joule 4, 1776-1789 ( 2020). https://doi.org/10.1016/j.joule.2020.06.011
18.	Z . Chang , Y . Qiao , H . Yang , X . Cao , X . Zhu et al., Sustainable lithium-metal battery achieved by a safe electrolyte based on recyclable and low-cost molecular sieve. Angew. Chem. Int. Ed. 60, 15572-15581 ( 2021). https://doi.org/10.1002/anie.202104124
19.	Z . Chang , H . Yang , Y . Qiao , X . Zhu , P . He et al., Tailoring the solvation sheath of cations by constructing electrode front-faces for rechargeable batteries. Adv. Mater. 34, e2201339 ( 2022). https://doi.org/10.1002/adma.202201339
20.	H.J.S . Sand III ., On the concentration at the electrodes in a solution, with special reference to the liberation of hydrogen by electrolysis of a mixture of copper sulphate and sulphuric acid. Lond. Edinb Dublin Philos. Mag. J. Sci. 1, 45-79 ( 1901). https://doi.org/10.1080/14786440109462590
21.	P . Dong , X . Zhang , W . Hiscox , J . Liu , J . Zamora et al., Toward high-performance metal-organic-framework-based quasi-solid-state electrolytes: tunable structures and electrochemical properties. Adv. Mater. 35, e2211841 ( 2023). https://doi.org/10.1002/adma.202211841
22.	M.L . Aubrey , R . Ameloot , B.M . Wiers , J.R . Long , Metal-organic frameworks as solid magnesium electrolytes. Energy Environ. Sci. 7, 667-671 ( 2014). https://doi.org/10.1039/C3EE43143F
23.	W . He , D . Li , S . Guo , Y . Xiao , W . Gong et al., Redistribution of electronic density in channels of metal-Organic frameworks for high-performance quasi-solid lithium metal batteries. Energy Storage Mater. 47, 271-278 ( 2022). https://doi.org/10.1016/j.ensm.2022.02.003
24.	T . Hou , W . Xu , X . Pei , L . Jiang , O.M . Yaghi et al., Ionic conduction mechanism and design of metal-organic framework based quasi-solid-state electrolytes. J. Am. Chem. Soc. 144, 13446-13450 ( 2022). https://doi.org/10.1021/jacs.2c03710
25.	Z . Miao , F . Zhang , H . Zhao , M . Du , H . Li et al., Tailoring local electrolyte solvation structure via a mesoporous molecular sieve for dendrite-free zinc batteries. Adv. Funct. Mater. 32, 2111635 ( 2022). https://doi.org/10.1002/adfm.202111635
26.	L . Han , Z . Wang , D . Kong , L . Yang , K . Yang et al., An ordered mesoporous silica framework based electrolyte with nanowetted interfaces for solid-state lithium batteries. J. Mater. Chem. A 6, 21280-21286 ( 2018). https://doi.org/10.1039/C8TA08875F
27.	K . Wang , C . Li , Y . Liang , T . Han , H . Huang et al., Rational construction of defects in a metal-organic framework for highly efficient adsorption and separation of dyes. Chem. Eng. J. 289, 486-493 ( 2016). https://doi.org/10.1016/j.cej.2016.01.019
28.	Z . Li , Q . Liu , L . Gao , Y . Xu , X . Kong et al., Quasi-solid electrolyte membranes with percolated metal-organic frameworks for practical lithium-metal batteries. J. Energy Chem. 52, 354-360 ( 2021). https://doi.org/10.1016/j.jechem.2020.04.013
29.	Y . Xu , L . Gao , L . Shen , Q . Liu , Y . Zhu et al., Ion-transport-rectifying layer enables Li-metal batteries with high energy density. Matter 3, 1685-1700 ( 2020). https://doi.org/10.1016/j.matt.2020.08.011
30.	G . Wang , J . Gao , Y . Fu , Z . Ren , J . Huang et al., Implantable composite fibres with Self-supplied H ₂O ₂for localized chemodynamic therapy. Chem. Eng. J. 388, 124211 ( 2020). https://doi.org/10.1016/j.cej.2020.124211
31.	L . Valenzano , B . Civalleri , S . Chavan , S . Bordiga , M.H . Nilsen et al., Disclosing the complex structure of UiO-66 metal organic framework: a synergic combination of experiment and theory. Chem. Mater. 23, 1700-1718 ( 2011). https://doi.org/10.1021/cm1022882
32.	G.C . Shearer , S . Chavan , S . Bordiga , S . Svelle , U . Olsbye et al., Defect engineering: tuning the porosity and composition of the metal-organic framework UiO-66 via modulated synthesis. Chem. Mater. 28, 3749-3761 ( 2016). https://doi.org/10.1021/acs.chemmater.6b00602
33.	S . Mohebbi , M . Shariatipour , B . Shafie , M.M . Amini , Encapsulation of tamoxifen citrate in functionalized mesoporous silica and investigation of its release. J. Drug Deliv. Sci. Technol. 62, 102406 ( 2021). https://doi.org/10.1016/j.jddst.2021.102406
34.	M . Taddei , When defects turn into virtues: the curious case of zirconium-based metal-organic frameworks. Coord. Chem. Rev. 343, 1-24 ( 2017). https://doi.org/10.1016/j.ccr.2017.04.010
35.	L . Cai , H . Ying , P . Huang , Z . Zhang , H . Tan et al., In-situ grown Ti ₃C ₂T @CoSe ₂heterostructure as trapping-electrocatalyst for accelerating polysulfides conversion in lithium-sulfur battery. Chem. Eng. J. 474, 145862 ( 2023). https://doi.org/10.1016/j.cej.2023.145862
36.	L . Liu , Z . Chen , J . Wang , D . Zhang , Y . Zhu et al., Imaging defects and their evolution in a metal-organic framework at sub-unit-cell resolution. Nat. Chem. 11, 622-628 ( 2019). https://doi.org/10.1038/s41557-019-0263-4
37.	Q . Han , L . Cai , P . Huang , S . Liu , C . He et al., Fast ionic conducting hydroxyapatite solid electrolyte interphase enables ultra-stable zinc metal anodes. ACS Appl. Mater. Interfaces 15, 48316-48325 ( 2023). https://doi.org/10.1021/acsami.3c11649
38.	Z . Wang , W . Huang , J . Hua , Y . Wang , H . Yi et al., An anionic-MOF-based bifunctional separator for regulating lithium deposition and suppressing polysulfides shuttle in Li-S batteries. Small Meth. 4, 2000082 ( 2020). https://doi.org/10.1002/smtd.202000082
39.	Y . Sun , T . Yang , H . Ji , J . Zhou , Z . Wang et al., Boosting the optimization of lithium metal batteries by molecular dynamics simulations: a perspective. Adv. Energy Mater. 10, 2002373 ( 2020). https://doi.org/10.1002/aenm.202002373
40.	S . Bai , Y . Sun , J . Yi , Y . He , Y . Qiao et al., High-power Li-metal anode enabled by metal-organic framework modified electrolyte. Joule 2, 2117-2132 ( 2018). https://doi.org/10.1016/j.joule.2018.07.010
41.	S . Yuan , J.L . Bao , J . Wei , Y . Xia , D.G . Truhlar et al., A versatile single-ion electrolyte with a Grotthuss-like Li conduction mechanism for dendrite-free Li metal batteries. Energy Environ. Sci. 12, 2741-2750 ( 2019). https://doi.org/10.1039/C9EE01473J
42.	M.F . Döpke , J . Lützenkirchen , O.A . Moultos , B . Siboulet , J.-F . Dufrêche et al., Preferential adsorption in mixed electrolytes confined by charged amorphous silica. J. Phys. Chem. C 123, 16711-16720 ( 2019). https://doi.org/10.1021/acs.jpcc.9b02975
43.	K . Qian , S . Seifert , R.E . Winans , T . Li , Understanding solvation behavior of the saturated electrolytes with small/wide-angle X-ray scattering and Raman spectroscopy. Energy Fuels 35, 19849-19855 ( 2021). https://doi.org/10.1021/acs.energyfuels.1c03328
44.	L . Cao , D . Li , T . Deng , Q . Li , C . Wang , Hydrophobic organic-electrolyte-protected zinc anodes for aqueous zinc batteries. Angew. Chem. Int. Ed. 59, 19292-19296 ( 2020). https://doi.org/10.1002/anie.202008634
45.	H . Gan , J . Wu , F . Zhang , R . Li , H . Liu , Uniform Zn ²⁺distribution and deposition regulated by ultrathin hydroxyl-rich silica ion sieve in zinc metal anodes. Energy Storage Mater. 55, 264-271 ( 2023). https://doi.org/10.1016/j.ensm.2022.11.044
46.	X.-X . Wang , X.-W . Chi , M.-L . Li , D.-H . Guan , C.-L . Miao et al., Metal-organic frameworks derived electrolytes build multiple wetting interfaces for integrated solid-state lithium-oxygen battery. Adv. Funct. Mater. 32, 2113235 ( 2022). https://doi.org/10.1002/adfm.202113235
47.	B.G . Lee , Y.J . Park , Enhanced electrochemical performance of lithia/Li ₂RuO ₃cathode by adding tris(trimethylsilyl)borate as electrolyte additive. Sci. Rep. 10, 13498 ( 2020). https://doi.org/10.1038/s41598-020-70333-2
48.	H . Ma , D . Hwang , Y.J . Ahn , M.-Y . Lee , S . Kim et al., In situ interfacial tuning to obtain high-performance nickel-rich cathodes in lithium metal batteries. ACS Appl. Mater. Interfaces 12, 29365-29375 ( 2020). https://doi.org/10.1021/acsami.0c06830
49.	H.Q . Pham , M . Mirolo , M . Tarik , M. El Kazzi , S . Trabesinger , Multifunctional electrolyte additive for improved interfacial stability in Ni-rich layered oxide full-cells. Energy Storage Mater. 33, 216-229 ( 2020). https://doi.org/10.1016/j.ensm.2020.08.026

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