Graphical Abstract
![](https://wqketang.oss-cn-beijing.aliyuncs.com/zip-unzip/zip-02bfedd0-c24c-4a64-9c42-9a3d3c7ab7d2/5406/files/5406-TOC.jpg?Expires=1725762376&OSSAccessKeyId=STS.NTLQiVhEqkan2WYuKGt6GGg6d&Signature=GOxKZVepP%2FrMHazllWLz7khVDnU%3D&security-token=CAISywJ1q6Ft5B2yfSjIr5f5GtPihZpQ3KOFMHHokUsSeLlrqKKdhjz2IHtKenhsBOsbtfk1mG5W5%2FgZlqJ9SptIAEfJa9d99Mz7X5RHltCT1fau5Jko1beHewHKeTOZsebWZ%2BLmNqC%2FHt6md1HDkAJq3LL%2Bbk%2FMdle5MJqP%2B%2FUFB5ZtKWveVzddA8pMLQZPsdITMWCrVcygKRn3mGHdfiEK00he8TouufTinpHMskGA1Aell7Mvyt6vcsT%2BXa5FJ4xiVtq55utye5fa3TRYgxowr%2Fwo0v0YpGya5YzHXwcPskvdKZbo78UqLQlla6w%2BGqFJqvPxr%2Fp8t%2Fx5fWJKAezhVgs8cVM8JOjIqKOscIsiZkw7znGqFV55c8Fdm%2BgUooJVgIMhTnduUfAPJAGOxzJitP%2BUVGGphr60TEnBL4rB5MUctfzRp0HAC4TUTzDnGoABGnGEyJ2778kKvMMPYR0FMvY7TYK4ERqLRaVA3Qbkq%2FmJxU1WPHaKZU59uu5paJhn%2Fjyq%2FeScistgE2M79iKmgNOx%2BlBhE%2BcT61Xx0r9Rc2jN8zzb7bYXqYj%2Fyo%2BCSvlpFs4Xds2mZ5IbiYZ52RZuZdIaJJz3lJ7br35g4mUa4h8gAA%3D%3D)
Discover the SciOpen Platform and Achieve Your Research Goals with Ease.
The polyethylene oxide (PEO) based solid-state batteries are considered as promising candidates for the next-generation Li metal batteries with high energy density and safety. However, the low Li-ion conductivity and high-voltage endurability hinder the further applications of PEO-based electrolytes. To overcome these issues, herein two-dimensional (2D) CeF3 nanoplates with maximally exposed [001] crystal faces are introduced into the PEO matrix to expand the electrochemical window and improve Li-ion conduction and transport. The optimized crystal shape and crystal face anisotropy of CeF3 nanoplate filler reduce the crystallinity of composite solid polymer electrolyte (CSPE) via its Lewis acid-base interaction with ether oxygen of PEO. The Li-affinity [100] and Li-repellent [001] crystal faces of CeF3 nanoplates synergistically realize the dissociation of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), fast Li-adsorption/desorption, and Li+ migration. The optimized CSPE-0.1CeF3 membrane enables the achievement of Li metal batteries with high endurability and stability, from the kinetically favorable Li/Li symmetric cells with long-term cycling over 8000 h. The highly reversible Li/LiFePO4 cells exhibit a capacity retention of 109.2 mAh·g−1 after 1000 cycles at 1 C, corresponding to a low capacity fading rate of 0.026% per cycle. The conversion-type all-solid-state Li/CSPE-0.1CeF3/FeF3 cells show a high reversible capacity of 201.9 mAh·g−1 after long-term 600 cycles and of 231.1 mAh·g−1 at an ultra-high rate of 5 C.
Guo, Y.; Wu, S. C.; He, Y. B.; Kang, F. Y.; Chen, L. Q.; Li, H.; Yang, Q. H. Solid-state lithium batteries: Safety and prospects. eScience 2022, 2, 138–163.
Yang, Q. F.; Li, C. L. Li metal batteries and solid state batteries benefiting from halogen-based strategies. Energy Storage Mater. 2018, 14, 100–117.
Li, Y. J.; Guo, K.; Zhao, J. T.; Li, C. L. Anode interface modification of lithium metal batteries: Benefiting from functional additives and conformal coatings. Chin. Sci. Bull. 2021, 66, 2971–2990.
Wu, Q. P.; Zheng, Y. J.; Guan, X.; Xu, J.; Cao, F. H.; Li, C. L. Dynamical SEI reinforced by open-architecture MOF film with stereoscopic lithiophilic sites for high-performance lithium-metal batteries. Adv. Funct. Mater. 2021, 31, 2101034.
Zhang, Y.; Meng, J. W.; Chen, K. Y.; Wu, H.; Hu, J. L.; Li, C. L. Garnet-based solid-state lithium fluoride conversion batteries benefiting from eutectic interlayer of superior wettability. ACS Energy Lett. 2020, 5, 1167–1176.
Lei, M.; Fan, S. S.; Yu, Y. F.; Hu, J. L.; Chen, K. Y.; Gu, Y. P.; Wu, C. L.; Zhang, Y.; Li, C. L. NASICON-based solid state Li-Fe-F conversion batteries enabled by multi-interface-compatible sericin protein buffer layer. Energy Storage Mater 2022, 47, 551–560.
Wu, X. X.; Zheng, Y. J.; Li, W. B.; Liu, Y. Y.; Zhang, Y.; Li, Y. J.; Li, C. L. Solid electrolytes reinforced by infinite coordination polymer nano-network for dendrite-free lithium metal batteries. Energy Storage Mater. 2021, 41, 436–447.
Hu, J. L.; Chen, K. Y.; Yao, Z. G.; Li, C. L. Unlocking solid-state conversion batteries reinforced by hierarchical microsphere stacked polymer electrolyte. Sci. Bull. 2021, 66, 694–707.
Liu, Q. Y.; Yang, G. J.; Li, X. Y.; Zhang, S. M.; Chen, R. J.; Wang, X. F.; Gao, Y. R.; Wang, Z. X.; Chen, L. Q. Polymer electrolytes based on interactions between [solvent-Li+] complex and solvent-modified polymer. Energy Storage Mater. 2022, 51, 443–452.
Liang, J. Y.; Zeng, X. X.; Zhang, X. D.; Zuo, T. T.; Yan, M.; Yin, Y. X.; Shi, J. L.; Wu, X. W.; Guo, Y. G.; Wan, L. J. Engineering Janus interfaces of ceramic electrolyte via distinct functional polymers for stable high-voltage Li-metal batteries. J. Am. Chem. Soc. 2019, 141, 9165–9169.
Wei, S. Y.; Ma, L.; Hendrickson, K. E.; Tu, Z. Y.; Archer, L. A. Metal–sulfur battery cathodes based on PAN-sulfur composites. J. Am. Chem. Soc. 2015, 137, 12143–12152.
Wu, H. L.; Wang, J. L.; Zhao, Y.; Zhang, X. Q.; Xu, L.; Liu, H.; Cui, Y. X.; Cui, Y. H.; Li, C. L. A branched cellulose-reinforced composite polymer electrolyte with upgraded ionic conductivity for anode stabilized solid-state Li metal batteries. Sustainable Energy Fuels 2019, 3, 2642–2656.
Zhang, D. C.; Xu, X. J.; Qin, Y. L.; Ji, S. M.; Huo, Y. P.; Wang, Z. S.; Liu, Z. B.; Shen, J. D.; Liu, J. Recent progress in organic–inorganic composite solid electrolytes for all-solid-state lithium batteries. Chem. —Eur. J. 2020, 26, 1720–1736.
Su, Y.; Rong, X. H.; Gao, A.; Liu, Y.; Li, J. W.; Mao, M. L.; Qi, X. G.; Chai, G. L.; Zhang, Q. H.; Suo, L. M. et al. Rational design of a topological polymeric solid electrolyte for high-performance all-solid-state alkali metal batteries. Nat. Commun. 2022, 13, 4181.
Jaumaux, P.; Liu, Q.; Zhou, D.; Xu, X. F.; Wang, T. Y.; Wang, Y. Z.; Kang, F. Y.; Li, B. H.; Wang, G. X. Deep-eutectic-solvent-based self-healing polymer electrolyte for safe and long-life lithium-metal batteries. Angew. Chem., Int. Ed. 2020, 59, 9134–9142.
Yue, L. P.; Ma, J.; Zhang, J. J.; Zhao, J. W.; Dong, S. M.; Liu, Z. H.; Cui, G. L.; Chen, L. Q. All solid-state polymer electrolytes for high-performance lithium ion batteries. Energy Storage Mater. 2016, 5, 139–164.
Khurana, R.; Schaefer, J. L.; Archer, L. A.; Coates, G. W. Suppression of lithium dendrite growth using cross-linked polyethylene/poly(ethylene oxide) electrolytes: A new approach for practical lithium-metal polymer batteries. J. Am. Chem. Soc. 2014, 136, 7395–7402.
Choi, B. K.; Kim, Y. W.; Shin, H. K. Ionic conduction in PEO-PAN blend polymer electrolytes. Electrochim. Acta 2000, 45, 1371–1374.
Zeng, X. X.; Yin, Y. X.; Li, N. W.; Du, W. C.; Guo, Y. G.; Wan, L. J. Reshaping lithium plating/stripping behavior via bifunctional polymer electrolyte for room-temperature solid Li metal batteries. J. Am. Chem. Soc. 2016, 138, 15825–15828.
Zhang, H. R.; Huang, L.; Xu, H. T.; Zhang, X. H.; Chen, Z.; Gao, C. H.; Lu, C. L.; Liu, Z.; Jiang, M. F.; Cui, G. L. A polymer electrolyte with a thermally induced interfacial ion-blocking function enables safety-enhanced lithium metal batteries. eScience 2022, 2, 201–208.
Hu, J. L.; Yao, Z. G.; Chen, K. Y.; Li, C. L. High-conductivity open framework fluorinated electrolyte bonded by solidified ionic liquid wires for solid-state Li metal batteries. Energy Storage Mater. 2020, 28, 37–46.
Wang, Y. J.; Pan, Y.; Kim, D. Conductivity studies on ceramic Li1.3Al0.3Ti1.7(PO4)3-filled PEO-based solid composite polymer electrolytes. J. Power Sources 2006, 159, 690–701.
Zheng, J.; Tang, M. X.; Hu, Y. Y. Lithium ion pathway within Li7La3Zr2O12-polyethylene oxide composite electrolytes. Angew. Chem., Int. Ed. 2016, 55, 12538–12542.
Wu, J. F.; Guo, X. MOF-derived nanoporous multifunctional fillers enhancing the performances of polymer electrolytes for solid-state lithium batteries. J. Mater. Chem. A 2019, 7, 2653–2659.
Wu, X. X.; Chen, K. Y.; Yao, Z. G.; Hu, J. L.; Huang, M. S.; Meng, J. W.; Ma, S. P.; Wu, T.; Cui, Y. H.; Li, C. L. Metal–organic framework reinforced polymer electrolyte with high cation transference number to enable dendrite-free solid state Li metal conversion batteries. J. Power Sources 2021, 501, 229946.
Lin, D. C.; Liu, W.; Liu, Y. Y.; Lee, H. R.; Hsu, P. C.; Liu, K.; Cui, Y. High ionic conductivity of composite solid polymer electrolyte via in situ synthesis of monodispersed SiO2 nanospheres in poly(ethylene oxide). Nano Lett. 2016, 16, 459–465.
Sheng, O. W.; Jin, C. B.; Luo, J. M.; Yuan, H. D.; Huang, H.; Gan, Y. P.; Zhang, J.; Xia, Y.; Liang, C.; Zhang, W. K. et al. Mg2B2O5 nanowire enabled multifunctional solid-state electrolytes with high ionic conductivity, excellent mechanical properties, and flame-retardant performance. Nano Lett. 2018, 18, 3104–3112.
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.
Shim, J.; Kim, H. J.; Kim, B. G.; Kim, Y. S.; Kim, D. G.; Lee, J. C. 2D boron nitride nanoflakes as a multifunctional additive in gel polymer electrolytes for safe, long cycle life and high rate lithium metal batteries. Energy Environ. Sci. 2017, 10, 1911–1916.
Hu, J. L.; Tian, J.; Li, C. L. Nanostructured carbon nitride polymer-reinforced electrolyte to enable dendrite-suppressed lithium metal batteries. ACS Appl. Mater. Interfaces 2017, 9, 11615–11625.
Li, C. X.; Liu, X. M.; Yang, P. P.; Zhang, C. M.; Lian, H. Z.; Lin, J. LaF3, CeF3, CeF3: Tb3+, and CeF3: Tb3+@LaF3 (core–shell) nanoplates: Hydrothermal synthesis and luminescence properties. J. Phys. Chem. C 2008, 112, 2904–2910.
Hu, J. L.; Zhang, Y.; Cao, D. P.; Li, C. L. Dehydrating bronze iron fluoride as a high capacity conversion cathode for lithium batteries. J. Mater. Chem. A 2016, 4, 16166–16174.
Chai, R. T.; Lian, H. Z.; Li, C. X.; Cheng, Z. Y.; Hou, Z. Y.; Huang, S. S.; Lin, J. In situ preparation and luminescent properties of CeF3 and CeF3:Tb3+ nanoparticles and transparent CeF3:Tb3+/PMMA nanocomposites in the visible spectral range. J. Phys. Chem. C 2009, 113, 8070–8076.
Zhang, Y.; Chen, J. Controllable preparation of CeF3: Tb3+ nanostructures with different morphologies from an ionic liquid-based extraction system. Colloids Surf. A Physicochem. Eng. Aspects 2015, 470, 130–136.
Wu, H.; Wu, Q. P.; Chu, F. L.; Hu, J. L.; Cui, Y. H.; Yin, C. L.; Li, C. L. Sericin protein as a conformal protective layer to enable air-endurable Li metal anodes and high-rate Li-S batteries. J. Power Sources 2019, 419, 72–81.
Yang, Q. F.; Hu, J. L.; Meng, J. W.; Li, C. L. C–F-rich oil drop as a non-expendable fluid interface modifier with low surface energy to stabilize a Li metal anode. Energy Environ. Sci. 2021, 14, 3621–3631.
Liu, J.; Shen, X. W.; Zhou, J. Q.; Wang, M. F.; Niu, C. Q.; Qian, T.; Yan, C. L. Nonflammable and high-voltage-tolerated polymer electrolyte achieving high stability and safety in 4.9 V-class lithium metal battery. ACS Appl. Mater. Interfaces 2019, 11, 45048–45056.
Dey, A.; Karan, S.; De, S. K. Molecular interaction and ionic conductivity of polyethylene oxide-LiClO4 nanocomposites. J. Phys. Chem. Solids 2010, 71, 329–335.
Wang, Z. N.; Wang, S.; Wang, A. L.; Liu, X.; Chen, J.; Zeng, Q. H.; Zhang, L.; Liu, W.; Zhang, L. Y. Covalently linked metal–organic framework (MOF)-polymer all-solid-state electrolyte membranes for room temperature high performance lithium batteries. J. Mater. Chem. A 2018, 6, 17227–17234.
Wieczorek, W.; Raducha, D.; Zalewska, A.; Stevens, J. R. Effect of salt concentration on the conductivity of PEO-based composite polymeric electrolytes. J. Phys. Chem. B 1998, 102, 8725–8731.
Lammert, M.; Wharmby, M. T.; Smolders, S.; Bueken, B.; Lieb, A.; Lomachenko, K. A.; Vos, D. D.; Stock, N. Cerium-based metal–organic frameworks with UiO-66 architecture: Synthesis, properties and redox catalytic activity. Chem. Commun. 2015, 51, 12578–12581.
Lin, Y.; Wang, X. M.; Liu, J.; Miller, J. D. Natural halloysite nano-clay electrolyte for advanced all-solid-state lithium-sulfur batteries. Nano Energy 2017, 31, 478–485.
Huo, H. Y.; Wu, B.; Zhang, T.; Zheng, X. S.; Ge, L.; Xu, T. W.; Guo, X. X.; Sun, X. L. Anion-immobilized polymer electrolyte achieved by cationic metal–organic framework filler for dendrite-free solid-state batteries. Energy Storage Mater. 2019, 18, 59–67.
Chen, N.; Dai, Y. J.; Xing, Y.; Wang, L. L.; Guo, C.; Chen, R. J.; Guo, S. J.; Wu, F. Biomimetic ant-nest ionogel electrolyte boosts the performance of dendrite-free lithium batteries. Energy Environ. Sci. 2017, 10, 1660–1667.
Suo, L. M.; Oh, D.; Lin, Y. X.; Zhuo, Z. Q.; Borodin, O.; Gao, T.; Wang, F.; Kushima, A.; Wang, Z. Q.; Kim, H. C. et al. How solid-electrolyte interphase forms in aqueous electrolytes. J. Am. Chem. Soc. 2017, 139, 18670–18680.
Liang, Y.; Liu, Y.; Chen, D.; Dong, L.; Guang, Z.; Liu, J.; Yuan, B.; Yang, M.; Dong, Y.; Li, Q. et al. Hydroxyapatite functionalization of solid polymer electrolytes for high-conductivity solid-state lithium-ion batteries. Mater. Today Energy 2021, 20, 100694.
Wu, H.; Yao, Z. G.; Wu, Q. P.; Fan, S. S.; Yin, C. L.; Li, C. L. Confinement effect and air tolerance of Li plating by lithiophilic poly(vinyl alcohol) coating for dendrite-free Li metal batteries. J. Mater. Chem. A 2019, 7, 22257–22264.
Li, C. L.; Chen, K. Y.; Zhou, X. J.; Maier, J. Electrochemically driven conversion reaction in fluoride electrodes for energy storage devices. npj Comput. Mater. 2018, 4, 22.
Chen, K. Y.; Lei, M.; Yao, Z. G.; Zheng, Y. J.; Hu, J. L.; Lai, C. Z.; Li, C. L. Construction of solid-liquid fluorine transport channel to enable highly reversible conversion cathodes. Sci. Adv. 2021, 7, eabj1491.
Wang, L. P.; Wu, Z. R.; Zou, J.; Gao, P.; Niu, X. B.; Li, H.; Chen, L. Q. Li-free cathode materials for high energy density lithium batteries. Joule 2019, 3, 2086–2102.
Zhang, Y.; Meng, J. W.; Chen, K. Y.; Wu, Q. P.; Wu, X. X.; Li, C. L. Behind the candelabra: A facile flame vapor deposition method for interfacial engineering of garnet electrolyte to enable ultralong cycling solid-state Li-FeF3 conversion batteries. ACS Appl. Mater. Interfaces 2020, 12, 33729–33739.
Zhang, D. C.; Xu, X. J.; Huang, X. Y.; Shi, Z. C.; Wang, Z. S.; Liu, Z. B.; Hu, R. Z.; Liu, J.; Zhu, M. A flexible composite solid electrolyte with a highly stable interphase for dendrite-free and durable all-solid-state lithium metal batteries. J. Mater. Chem. A 2020, 8, 18043–18054.
Zhang, D. C.; Liu, Z. B.; Wu, Y. W.; Ji, S. M.; Yuan, Z. X.; Liu, J.; Zhu, M. In situ construction a stable protective layer in polymer electrolyte for ultralong lifespan solid-state lithium metal batteries. Adv. Sci. 2022, 9, 2104277.
Li, C. C.; Zhang, X. S.; Zhu, Y. H.; Zhang, Y.; Xin, S.; Wan, L. J.; Guo, Y. G. Modulating the lithiophilicity at electrode/electrolyte interface for high-energy Li-metal batteries. Energy Mater. 2022, 1, 100017.