Abstract
Electrolyte interface resistance and low ionic conductivity are essential issues for commercializing solid-state lithium metal batteries (SSLMBs). This work details the fabrication of a double-layer solid composite electrolyte (DLSCE) for SSLMBs. The composite comprises poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF–HFP) and poly(methyl methacrylate) (PMMA) combined with 10 wt.% of Li6.4La3Zr1.4Ta0.6O12 (LLZTO), synthesized through an ultraviolet curing process. The ionic conductivity of the DLSCE (2.6 × 10−4 S·cm−1) at room temperature is the high lithium-ion transference number (0.57), and the tensile strength is 17.8 MPa. When this DLSCE was assembled, the resulted LFP/DLSCE/Li battery exhibited excellent rate performance, with the discharge specific capacities of 162.4, 146.9, 93.6, and 64.0 mA·h·g−1 at 0.1, 0.2, 0.5, and 1 C, respectively. Furthermore, the DLSCE demonstrates remarkable stability with lithium metal batteries, facilitating the stable operation of a Li/Li symmetric battery for over 200 h at both 0.1 and 0.2 mA·cm−2. Notably, the formation of lithium dendrites is also effectively inhibited during cycling. This work provides a novel design strategy and preparation method for solid composite electrolytes.
Article PDF
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Avoid common mistakes on your manuscript.
References
Hung I M, Mohanty D. Preparation and characterization of LLZO–LATP composite solid electrolyte for solid-state lithium-ion battery. Solid State Communications, 2023, 364: 115135
Chen Z, Kim G T, Kim J K, et al. Highly stable quasi-solid-state lithium metal batteries: reinforced Li1.3Al0.3Ti1.7(PO4)3/Li interface by a protection interlayer. Advanced Energy Materials, 2021, 11(30): 2101339
Liang X, Ning Y, Lan L, et al. Electrochemical performance of a PVDF–HFP–LiClO4–Li6.4La3Zr1.4Ta0.6O12 composite solid electrolyte at different temperatures. Nanomaterials, 2022, 12(19): 3390
Zhang W J, Li S L, Zhang Y R, et al. A quasi-solid-state electrolyte with high ionic conductivity for stable lithium-ion batteries. Science China: Technological Sciences, 2022, 65(10): 2369–2379
Cho Y H, Wolfenstine J, Rangasamy E, et al. Mechanical properties of the solid Li-ion conducting electrolyte: Li0.33La0.57TiO3. Journal of Materials Science, 2012, 47(16): 5970–5977
Liu S, Zhao Y, Li X, et al. Solid-state lithium metal batteries with extended cycling enabled by dynamic adaptive solid-state interfaces. Advanced Materials, 2021, 33(12): 2008084
Ping X, Zheng Q, Meng B, et al. Influence of sintering atmosphere on the phase, microstructure, and lithium-ion conductivity of the Al-doped Li7La3Zr2O12 solid electrolyte. Ceramics International, 2022, 48(18): 25689–25695
Su J, Huang X, Song Z, et al. Overcoming the abnormal grain growth in Ga-doped Li7La3Zr2O12 to enhance the electrochemical stability against Li metal. Ceramics International, 2019, 45(12): 14991–14996
Ren Y, Shen Y, Lin Y, et al. Direct observation of lithium dendrites inside garnet-type lithium-ion solid electrolyte. Electrochemistry Communications, 2015, 57: 27–30
Han F, Westover A S, Yue J, et al. High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes. Nature Energy, 2019, 4(3): 187–196
Liang Y, Lin Z, Qiu Y, et al. Fabrication and characterization of LATP/PAN composite fiber-based lithium-ion battery separators. Electrochimica Acta, 2011, 56(18): 6474–6480
Lu X, Hai J, Zhang F, et al. Preparation and infiltration of NASICON-type solid electrolytes with microporous channels. Ceramics International, 2022, 48(2): 2203–2211
Nam M G, Moon J, Kim M, et al. p - Phenylenediamine-bridged binder-electrolyte-unified supramolecules for versatile lithium secondary batteries. Advanced Materials, 2024, 36(5): 2304803
Xu L, Xiao X, Tu H, et al. Engineering functionalized 2D metal–organic frameworks nanosheets with fast Li+ conduction for advanced solid li batteries. Advanced Materials, 2023, 35(38): 2303193
Hu J H. Mechanical and optical properties of PMMA prepared by modified microemulsion polymerization. Acta Chimica Sinica, 2009, 6712: 1370
Ooe M, Miyata K, Yoshioka J, et al. Direct observation of mobility of thin polymer layers via asymmetric interdiffusion using neutron reflectivity measurements. The Journal of Chemical Physics, 2019, 151(24): 244905
Han Z, Dong Y, Liu C. Coordination of modified PAN fibers with Fe3+ and catalytic activity of their complexes for dye degradation. Chemical Journal of Chinese Universities, 2010, 315: 986–993
Wu Q Y, Chen X N, Wan L S, et al. Interactions between polyacrylonitrile and solvents: density functional theory study and two-dimensional infrared correlation analysis. The Journal of Physical Chemistry B, 2012, 116(28): 8321–8330
Cui S, Li L, Wang Q. Fabrication of (PPC/NCC)/PVA composites with inner-outer double constrained structure and improved glass transition temperature. Carbohydrate Polymers, 2018, 191: 35–43
Ullrich C K, Lehmann L, London W B, et al. End-of-life care patterns associated with pediatric palliative care among children who underwent hematopoietic stem cell transplant. Biology of Blood and Marrow Transplantation, 2016, 22(6): 1049–1055
Dirican M, Yan C, Zhu P, et al. Composite solid electrolytes for all-solid-state lithium batteries. Materials Science and Engineering R: Reports, 2019, 136: 27–46
Huang Y, Zhang Z, Gao H, et al. Li1.5Al0.5Ti1.5(PO4)3 enhanced polyethylene oxide polymer electrolyte for all-solid-state lithium batteries. Solid State Ionics, 2020, 356: 115437
Barai P, Higa K, Srinivasan V. Lithium dendrite growth mechanisms in polymer electrolytes and prevention strategies. Physical Chemistry Chemical Physics, 2017, 19(31): 20493–20505
Yao Z, Zhu K, Li X, et al. Double-layered multifunctional composite electrolytes for high-voltage solid-state lithium–metal batteries. ACS Applied Materials & Interfaces, 2021, 13(10): 11958–11967
Wang X, Hao X, Xia Y, et al. A polyacrylonitrile (PAN)-based double-layer multifunctional gel polymer electrolyte for lithium–sulfur batteries. Journal of Membrane Science, 2019, 582: 37–47
He T, Zeng G, Feng C, et al. A solid-electrolyte-reinforced separator through single-step electrophoretic assembly for safe high-capacity lithium ion batteries. Journal of Power Sources, 2020, 448: 227469
Xie H X, Fu Q G, Li Z, et al. Ultraviolet-cured semi-interpenetrating network polymer electrolytes for highperformance quasi-solid-state lithium metal batteries. Chemistry, 2021, 27(28): 7773–7780
Liu L, Wang X, Yang C, et al. PVDF–HFP-based gel polymer electrolyte with semi-interpenetrating networks for dendrite-free lithium metal battery. Acta Metallurgica Sinica: English Letters, 2021, 34(3): 417–424
Wang D, Cai D, Zhong Y, et al. A three-dimensional electrospun Li6.4La3Zr1.4Ta0.6O12–poly (vinylidene fluoride-hexafluoropropylene) gel polymer electrolyte for rechargeable solid-state lithium ion batteries. Frontiers in Chemistry, 2021, 9: 751476
Gu Y, Liu H. PVDF–HFP/LLZTO composite electrolytes with UV cure for solid-state lithium rechargeable batteries. Journal of Solid State Electrochemistry, 2023, 27(10): 2671–2679
Li S, Zhang S Q, Shen L, et al. Progress and perspective of ceramic/polymer composite solid electrolytes for lithium batteries. Advanced Science, 2020, 7(5): 1903088
Li S, Lu J, Geng Z, et al. Solid polymer electrolyte reinforced with a Li1.3Al0.3Ti1.7(PO4)3-coated separator for all-solid-state lithium batteries. ACS Applied Materials & Interfaces, 2022, 14(1): 1195–1202
Zheng X, Liu K, Yang T, et al. Sandwich composite PEO@(Er0.5Nb0.5)0.05Ti0.95O2@cellulose electrolyte with high cycling stability for all-solid-state lithium metal batteries. Journal of Alloys and Compounds, 2021, 877: 160307
Fan H, Yang C, Wang X, et al. UV-curable PVDF–HFP-based gel electrolytes with semi-interpenetrating polymer network for dendrite-free lithium metal batteries. Journal of Electroanalytical Chemistry, 2020, 871: 114308
Luo K, Shao D, Yang L, et al. Semi-interpenetrating gel polymer electrolyte based on PVDF–HFP for lithium ion batteries. Journal of Applied Polymer Science, 2021, 138(11): e49993
Xu K, Xu C, Jiang Y, et al. Sandwich structured PVDF–HFP-based composite solid electrolytes for solid-state lithium metal batteries. Ionics, 2022, 28(7): 3243–3253
Yousefi F, Mousavi S B, Heris S Z, et al. UV-shielding properties of a cost-effective hybrid PMMA-based thin film coatings using TiO2 and ZnO nanoparticles: a comprehensive evaluation. Scientific Reports, 2023, 13(1): 7116
Zhang J, Chen S, Xie X, et al. Porous poly(vinylidene fluoride-co-hexafluoropropylene) polymer membrane with sandwich-like architecture for highly safe lithium ion batteries. Journal of Membrane Science, 2014, 472: 133–140
Acknowledgements
This research was supported by the Liuzhou Science and Technology Fund Project (Grant No. 2023PRj0103), the National Natural Science Foundation of China (Grant Nos. 52161033 and 22262005), the Guangxi Key Laboratory of Automobile Components and Vehicle Technology Fund Project (Grant Nos. 2022GKLACVTKF02 and 2023GKLACVTZZ02), and the Fund Project of the Key Lab of Guangdong Science and Technology Innovation Strategy Special Fund Project in 2023 (Grant No. pdjh2023a0819).
Author information
Authors and Affiliations
Contributions
Authors’ contributions Conceptualization, X.L. and P.S.; methodology, J.W.; software, P.S.; validation, X.L., P.S. and G.Y.; formal analysis, M.H. and Y.W.; investigation, P.S. and Q.H; resources, X.L.; data curation, P.S.; writing — original draft preparation, P.S.; writing — review and editing, X.L.; visualization, L.L.; supervision, X.L.; project administration, X.L.; funding acquisition, L.L. All authors have read and agreed to the published version of the manuscript.
Corresponding authors
Ethics declarations
Declaration of competing interests The authors declare that they have no competing interests.
Rights and permissions
About this article
Cite this article
Liang, X., Shen, P., Lan, L. et al. High-stability double-layer polymer–inorganic composite electrolyte fabricated through ultraviolet curing process for solid-state lithium metal batteries. Front. Mater. Sci. 18, 240685 (2024). https://doi.org/10.1007/s11706-024-0685-9
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11706-024-0685-9