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Research Article | Open Access

An all-in-one polymer electrolyte enabled by acrylate-grafted separator copolymerization for high-performance lithium metal batteries

Jie Liu1,3, Jinping Zhang1,3, Yansong Liu1,3, Ruiqi Zhao1,3, Nuo Xu1,3, Xingchen Song1,3, Yuhu Li1,3, Guolin Sun1,3, Yanfeng Ma1,3, Chenxi Li1,3, Hongtao Zhang1,3, Yongsheng Chen1,2,3 ()
The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials, Institute of Polymer Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China
State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China
Renewable Energy Conversion and Storage Center (RECAST), Nankai University, Tianjin 300071, China
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An all-in-one free-standing acrylate-grafted cellulose separator polymer electrolyte (ACSPE) was designed and synthesized via the copolymerization of acrylate-grafted cellulose separator under ultraviolet (UV) irradiation. The Li|ACSPE|LiNi0.8Co0.1Mn0.1O2 (NCM811) cell demonstrated excellent electrochemical performance, delivering a high discharge specific capacity of 189.6 mAh·g−1 at 0.5 C while maintaining excellent cycling stability with a remarkable capacity retention of 86.0% over 500 cycles.

Abstract

Polymer electrolytes featuring flexibility, processability, and compatibility with large-scale roll-to-roll fabrication processes have emerged as promising candidates for solid-state lithium metal batteries. Herein, we have designed and synthesized an all-in-one free-standing acrylate-grafted cellulose separator polymer electrolyte (ACSPE) through the copolymerization of acrylate-grafted cellulose separator (ACS). This synthetic strategy leverages the abundant hydroxyl groups in the cellulose separator, which are substituted with acryloyl chloride to form an acrylate-grafted separator. The resulting ACSPE exhibits a high ionic conductivity of 1.78 × 10−3 S·cm−1 at room temperature, improved oxidation stability (5.57 V), and enhanced mechanical strength (10.0 MPa), indicating its high compatibility with high-voltage cathode, Li metal anode, and scalable roll-to-roll production processes. Li|ACSPE|LiNi0.8Co0.1Mn0.1O2 (NCM811) cells exhibit a long stable cycle life of 1000 cycles at 0.5 C/1 C with capacity retention of 75.6%, achieving stable performance across a wide temperature range from 0 to 60 °C. Furthermore, when paired with a 50 μm thin Li foil, full cells using NCM811 cathode with a mass loading of 6 mg·cm−2 exhibit a high discharge capacity of 191.0 mAh·g−1 at 0.1 C and maintain excellent cycling stability with a retention rate of 93.3% after 100 cycles. This study provides valuable insights into the chemical modification and design strategies for improving the processability and performance of polymer-based solid-state batteries.

Keywords

polymer electrolyteslithium metal batterieshigh-voltagelong cycling

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References

[1]

Deng, J.; Bae, C.; Denlinger, A.; Miller, T. Electric vehicles batteries: Requirements and challenges. Joule 2020, 4, 511–515.

Crossref Google Scholar
[2]

Ni, M. H.; Zhao, Y.; Xu, N.; Kong, M. X.; Ma, Y. F.; Li, C. X.; Zhang, H. T.; Chen, Y. S. Improving the cycling stability of lithium-ion batteries with a dry-processed cathode via the synergistic effect of carboxymethyl cellulose and siloxane. Sci. China Mater. 2024, 67, 76–84.

Crossref Google Scholar
[3]

Ayyaswamy, A.; Vishnugopi, B. S.; Mukherjee, P. P. Revealing hidden predicaments to lithium-ion battery dynamics for electric vertical take-off and landing aircraft. Joule 2023, 7, 2016–2034.

Crossref Google Scholar
[4]

Wang, C. Y.; Liu, T.; Yang, X. G.; Ge, S. H.; Stanley, N. V.; Rountree, E. S.; Leng, Y. J.; McCarthy, B. D. Fast charging of energy-dense lithium-ion batteries. Nature 2022, 611, 485–490.

Crossref Google Scholar
[5]

Choi, J. W.; Aurbach, D. Promise and reality of post-lithium-ion batteries with high energy densities. Nat. Rev. Mater. 2016, 1, 16013.

Crossref Google Scholar
[6]

Liu, J.; Bao, Z. N.; Cui, Y.; Dufek, E. J.; Goodenough, J. B.; Khalifah, P.; Li, Q. Y.; Liaw, B. Y.; Liu, P.; Manthiram, A. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat. Energy 2019, 4, 180–186.

Crossref Google Scholar
[7]

Janek, J.; Zeier, W. G. Challenges in speeding up solid-state battery development. Nat. Energy 2023, 8, 230–240.

Crossref Google Scholar
[8]

Feng, X. N.; Ouyang, M. G.; Liu, X.; Lu, L. G.; Xia, Y.; He, X. M. Thermal runaway mechanism of lithium ion battery for electric vehicles: A review. Energy Storage Mater. 2018, 10, 246–267.

Crossref Google Scholar
[9]

Shi, X. M.; Jia, Z. Z.; Wang, D. H.; Jiang, B. W.; Liao, Y. Q.; Zhang, G. H.; Wang, Q. S.; He, D. Q.; Huang, Y. H. Phonon engineering in solid polymer electrolyte toward high safety for solid-state lithium batteries. Adv. Mater. 2024, 36, 2405097.

Crossref Google Scholar
[10]

Liu, K.; Liu, Y. Y.; Lin, D. C.; Pei, A.; Cui, Y. Materials for lithium-ion battery safety. Sci. Adv. 2018, 4, eaas9820.

Crossref Google Scholar
[11]

Yuan, S. Y.; Ding, K.; Zeng, X. Y.; Bin, D.; Zhang, Y. J.; Dong, P.; Wang, Y. G. Advanced nonflammable organic electrolyte promises safer Li-metal batteries: From solvation structure perspectives. Adv. Mater. 2023, 35, 2206228.

Crossref Google Scholar
[12]

Manthiram, A.; Yu, X. W.; Wang, S. F. Lithium battery chemistries enabled by solid-state electrolytes. Nat. Rev. Mater. 2017, 2, 16103.

Crossref Google Scholar
[13]

Shi, P. R.; Ma, J. B.; Liu, M.; Guo, S. K.; Huang, Y. F.; Wang, S. W.; Zhang, L. H.; Chen, L. K.; Yang, K.; Liu, X. T. et al. A dielectric electrolyte composite with high lithium-ion conductivity for high-voltage solid-state lithium metal batteries. Nat. Nanotechnol. 2023, 18, 602–610.

Crossref Google Scholar
[14]

He, F.; Tang, W. J.; Zhang, X. Y.; Deng, L. J.; Luo, J. Y. High energy density solid state lithium metal batteries enabled by sub-5 µm solid polymer electrolytes. Adv. Mater. 2021, 33, 2105329.

Crossref Google Scholar
[15]

Tang, L. F.; Chen, B. W.; Zhang, Z. H.; Ma, C. Q.; Chen, J. C.; Huang, Y. G.; Zhang, F. R.; Dong, Q. Y.; Xue, G. Y.; Chen, D. Q. et al. Polyfluorinated crosslinker-based solid polymer electrolytes for long-cycling 4.5 V lithium metal batteries. Nat. Commun. 2023, 14, 2301.

Crossref Google Scholar
[16]

Dai, C.; Stadler, F. J.; Li, Z. M.; Huang, Y. F. E-beam irradiation of poly(vinylidene fluoride-trifluoroethylene) induces high dielectric constant and all- trans conformation for highly ionic conductive solid-state electrolytes. Energy Mater. Devices 2023, 1, 9370016.

Crossref Google Scholar
[17]

Zhang, J. P.; Zhu, J.; Zhao, R. Q.; Liu, J.; Song, X. C.; Xu, N.; Liu, Y. S.; Zhang, H. T.; Wan, X. J.; Ma, Y. F. et al. An all-in-one free-standing single-ion conducting semi-solid polymer electrolyte for high-performance practical Li metal batteries. Energy Environ. Sci. 2024, 17, 7119–7128.

Crossref Google Scholar
[18]

Yuan, Y.; Chen, L. K.; Li, Y. H.; An, X. F.; Lv, J. S.; Guo, S. K.; Cheng, X.; Zhao, Y.; Liu, M.; He, Y. B. et al. Functional LiTaO3 filler with tandem conductivity and ferroelectricity for PVDF-based composite solid-state electrolyte. Energy Mater. Devices 2023, 1, 9370004.

Crossref Google Scholar
[19]

Han, S. T.; Wen, P.; Wang, H. J.; Zhou, Y.; Gu, Y.; Zhang, L.; Shao-Horn, Y.; Lin, X. R.; Chen, M. Sequencing polymers to enable solid-state lithium batteries. Nat. Mater. 2023, 22, 1515–1522.

Crossref Google Scholar
[20]

Zhao, Q. Interphases of polymer electrolytes. Joule 2019, 3, 1569–1571.

Crossref Google Scholar
[21]

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
[22]

Ye, Y. N.; Zhu, X. G.; Meng, N.; Lian, F. Largely promoted mechano-electrochemical coupling properties of solid polymer electrolytes by introducing hydrogen bonds-rich network. Adv. Funct. Mater. 2023, 33, 2307045.

Crossref Google Scholar
[23]

Du, A.; Lu, H. T.; Liu, S. S.; Chen, S. Y.; Chen, Z. H.; Li, W. H.; Song, J. W.; Yang, Q. H.; Yang, C. P. Breaking the trade-off between ionic conductivity and mechanical strength in solid polymer electrolytes for high-performance solid lithium batteries. Adv. Energy Mater. 2024, 14, 2400808.

Crossref Google Scholar
[24]

Xue, Z. G.; He, D.; Xie, X. L. Poly(ethylene oxide)-based electrolytes for lithium-ion batteries. J. Mater. Chem. A 2015, 3, 19218–19253.

Crossref Google Scholar
[25]

Zhao, L. Y.; Dong, Q. Y.; Wang, Y. Q.; Xue, G. Y.; Wang, X. C.; Li, Z. Y.; Shao, H.; Chen, H. W.; Shen, Y. B.; Chen, L. W. Anion modulation: Enabling highly conductive stable polymer electrolytes for solid-state Li-metal batteries. Angew. Chem., Int. Ed. 2024, 63, e202412280.

Crossref Google Scholar
[26]

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
[27]

Zhang, Q. Q.; Liu, K.; Ding, F.; Liu, X. J. Recent advances in solid polymer electrolytes for lithium batteries. Nano Res. 2017, 10, 4139–4174.

Crossref Google Scholar
[28]

Yang, X. F.; Sun, Q.; Zhao, C. T.; Gao, X. J.; Adair, K. R.; Liu, Y. L.; Luo, J.; Lin, X. T.; Liang, J. N.; Huang, H. et al. High-areal-capacity all-solid-state lithium batteries enabled by rational design of fast ion transport channels in vertically-aligned composite polymer electrodes. Nano Energy 2019, 61, 567–575.

Crossref Google Scholar
[29]

Qi, S. G.; Li, S. L.; Zou, W. W.; Zhang, W. F.; Wang, X. J.; Du, L.; Liu, S. M.; Zhao, J. Q. Enabling scalable polymer electrolyte with synergetic ion conductive channels via a two stage rheology tuning UV polymerization strategy. Small 2022, 18, 2202013.

Crossref Google Scholar
[30]

Sun, Q. F.; Wang, S.; Ma, Y.; Song, D. W.; Zhang, H. Z.; Shi, X. X.; Zhang, N.; Zhang, L. Q. Li-ion transfer mechanism of gel polymer electrolyte with sole fluoroethylene carbonate solvent. Adv. Mater. 2023, 35, 2300998.

Crossref Google Scholar
[31]

Feng, J. W.; Wang, J. Y.; Gu, Q.; Li, P. T.; Xu, H. L.; Deng, Y. H.; Gao, P. 1 µm-thick robust gel polymer electrolyte with excellent interfacial stability for high-performance Li metal batteries. Adv. Funct. Mater. 2024, 35, 2412287.

Crossref Google Scholar
[32]

Goujon, L. J.; Khaldi, A.; Maziz, A.; Plesse, C.; Nguyen, G. T. M.; Aubert, P. H.; Vidal, F.; Chevrot, C.; Teyssié, D. Flexible solid polymer electrolytes based on nitrile butadiene rubber/poly(ethylene oxide) interpenetrating polymer networks containing either LiTFSI or EMITFSI. Macromolecules 2011, 44, 9683–9691.

Crossref Google Scholar
[33]

Oh, S.; Kim, D. W.; Lee, C.; Lee, M. H.; Kang, Y. K. Poly(vinylpyridine-co-styrene) based in situ cross-linked gel polymer electrolyte for lithium-ion polymer batteries. Electrochim. Acta 2011, 57, 46–51.

Crossref Google Scholar
[34]

Lu, Q. W.; He, Y. B.; Yu, Q. P.; Li, B. H.; Kaneti, Y. V.; Yao, Y. W.; Kang, F. Y.; Yang, Q. H. Dendrite-free, high-rate, long-life lithium metal batteries with a 3D cross-linked network polymer electrolyte. Adv. Mater. 2017, 29, 1604460.

Crossref Google Scholar
[35]

Qi, S. G.; Li, M. R.; Gao, Y. Q.; Zhang, W. F.; Liu, S. M.; Zhao, J. Q.; Du, L. Enabling scalable polymer electrolyte with dual-reinforced stable interface for 4.5 V lithium metal batteries. Adv. Mater. 2023, 35, 2304951.

Crossref Google Scholar
[36]

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
[37]

Zhou, K. F.; Zhang, M.; Zhang, X. N.; Wang, T. Y.; Wang, H. L.; Wang, Z. Q.; Tang, X. Y.; Bai, M.; Li, S. W.; Wang, Z. H. et al. A cellulose reinforced polymer composite electrolyte for the wide-temperature-range solid lithium batteries. Chem. Eng. J. 2023, 464, 142537.

Crossref Google Scholar
[38]

Ji, X.; Hou, S.; Wang, P. F.; He, X. Z.; Piao, N.; Chen, J.; Fan, X. L.; Wang, C. S. Solid-state electrolyte design for lithium dendrite suppression. Adv. Mater. 2020, 32, 2002741.

Crossref Google Scholar
[39]

Ni, L. S.; Zhang, S.; Di, A. D.; Deng, W. T.; Zou, G. Q.; Hou, H. S.; Ji, X. B. Challenges and strategies towards single-crystalline Ni-rich layered cathodes. Adv. Energy Mater. 2022, 12, 2201510.

Crossref Google Scholar
Nano Research
Volume 18 Issue 4,
April 2025
Article number: 94907323
DOI: 10.26599/NR.2025.94907323
Cite this article:
Liu J, Zhang J, Liu Y, et al. An all-in-one polymer electrolyte enabled by acrylate-grafted separator copolymerization for high-performance lithium metal batteries. Nano Research, 2025, 18(4): 94907323. https://doi.org/10.26599/NR.2025.94907323
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