Abstract
The development of commercial solid-state batteries has to date been hindered by the individual limitations of inorganic and organic solid electrolytes, motivating hybrid concepts. However, the room-temperature conductivity of hybrid solid electrolytes is still insufficient to support the required battery performance. A key challenge is to assess the Li-ion transport over the inorganic and organic interfaces and relate this to surface chemistry. Here we study the interphase structure and the Li-ion transport across the interface of hybrid solid electrolytes using solid-state nuclear magnetic resonance spectroscopy. In a hybrid solid polyethylene oxide polymer–inorganic electrolyte, we introduce two representative types of ionic liquid that have different miscibilities with the polymer. The poorly miscible ionic liquid wets the polymer–inorganic interface and increases the local polarizability. This lowers the diffusional barrier, resulting in an overall room-temperature conductivity of 2.47 × 10−4 S cm−1. A critical current density of 0.25 mA cm−2 versus a Li-metal anode shows improved stability, allowing cycling of a LiFePO4–Li-metal solid-state cell at room temperature with a Coulombic efficiency of 99.9%. Tailoring the local interface environment between the inorganic and organic solid electrolyte components in hybrid solid electrolytes seems to be a viable route towards designing highly conducting hybrid solid electrolytes.
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Data availability
The data that support the findings of this study are available at the online depository Zenodo (https://doi.org/10.5281/zenodo.6334099).
References
Armand, M. & Tarascon, J.-M. Building better batteries. Nature 451, 652–657 (2008).
Dunn, B., Kamath, H. & Tarascon, J.-M. Electrical energy storage for the grid: a battery of choices. Science 334, 928–935 (2011).
Cheng, X. B., Zhao, C. Z., Yao, Y. X., Liu, H. & Zhang, Q. Recent advances in energy chemistry between solid-state electrolyte and safe lithium-metal anodes. Chem 5, 74–96 (2019).
Zaman, W., Hortance, N., Dixit, M. B., De Andrade, V. & Hatzell, K. B. Visualizing percolation and ion transport in hybrid solid electrolytes for Li-metal batteries. J. Mater. Chem. A 7, 23914–23921 (2019).
Armand, M. The history of polymer electrolytes. Solid State Ion. 69, 309–319 (1994).
Bouchet, R. et al. Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries. Nat. Mater. 12, 452–457 (2013).
Ma, Q. et al. Single lithium‐ion conducting polymer electrolytes based on a super‐delocalized polyanion. Angew. Chem. Int. Ed. 55, 2521–2525 (2016).
Dixit, M. B. et al. Scalable manufacturing of hybrid solid electrolytes with interface control. ACS Appl. Mater. Interfaces 11, 45087–45097 (2019).
Osada, I., de Vries, H., Scrosati, B. & Passerini, S. Ionic‐liquid‐based polymer electrolytes for battery applications. Angew. Chem. Int. Ed. 55, 500–513 (2016).
Liu, M. et al. Tandem interface and bulk Li-ion transport in a hybrid solid electrolyte with microsized active filler. ACS Energy Lett. 4, 2336–2342 (2019).
Yang, K. et al. Stable interface chemistry and multiple ion transport of composite electrolyte contribute to ultra-long cycling solid-state LiNi0.8Co0.1Mn0.1O2/lithium metal batteries. Angew. Chem. Int. Ed. 60, 24668–24675 (2021).
Croce, F., Sacchetti, S. & Scrosati, B. Advanced lithium batteries based on high-performance composite polymer electrolytes. J. Power Sources 162, 685–689 (2006).
Syzdek, J. et al. Ceramic-in-polymer versus polymer-in-ceramic polymeric electrolytes—A novel approach. J. Power Sources 194, 66–72 (2009).
Hassoun, J. & Scrosati, B. A high‐performance polymer tin sulfur lithium ion battery. Angew. Chem. Int. Ed. 49, 2371–2374 (2010).
Płcharski, J. & Weiczorek, W. PEO based composite solid electrolyte containing nasicon. Solid State Ion. 28, 979–982 (1988).
Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem. Rev. 114, 11503–11618 (2014).
Lei, D. et al. Cross-linked beta alumina nanowires with compact gel polymer electrolyte coating for ultra-stable sodium metal battery. Nat. Commun. 10, 4244 (2019).
Zheng, J., Tang, M. X. & Hu, Y. Y. Lithium ion pathway within Li7La3Zr2O12-polyethylene oxide composite electrolytes. Angew. Chem. Int. Ed. 55, 12538–12542 (2016).
Wang, S. et al. A dendrite-suppressed flexible polymer-in-ceramic electrolyte membrane for advanced lithium batteries. Electrochim. Acta 353, 136604 (2020).
Fergus, J. W. Ceramic and polymeric solid electrolytes for lithium-ion batteries. J. Power Sources 195, 4554–4569 (2010).
Blanga, R., Burstein, L., Berman, M., Greenbaum, S. & Golodnitsky, D. Solid polymer-in-ceramic electrolyte formed by electrophoretic deposition. J. Electrochem. Soc. 162, D3084–D3089 (2015).
Chen, L. et al. PEO/garnet composite electrolytes for solid-state lithium batteries: from “ceramic-in-polymer” to “polymer-in-ceramic”. Nano Energy 46, 176–184 (2018).
Huo, H. Y. et al. Rational design of hierarchical “ceramic-in-polymer” and “polymer-in-ceramic” electrolytes for dendrite-free solid-state batteries. Adv. Energy Mater. 9, 1804004 (2019).
Bonizzoni, S. et al. NASICON-type polymer-in-ceramic composite electrolytes for lithium batteries. Phys. Chem. Chem. Phys. 21, 6142–6149 (2019).
Dixit, M. B. et al. Nanoscale mapping of extrinsic interfaces in hybrid solid electrolytes. Joule 4, 207–221 (2020).
Simon, F. J. et al. Properties of the interphase formed between argyrodite-type Li6PS5Cl and polymer-based PEO10:LiTFSI. ACS Appl. Mater. Interfaces 11, 42186–42196 (2019).
Simon, F. J., Hanauer, M., Richter, F. H. & Janek, J. Interphase formation of PEO20:LiTFSI–Li6PS5Cl composite electrolytes with lithium metal. ACS Appl. Mater. Interfaces 12, 11713–11723 (2020).
Zheng, J., Wang, P., Liu, H. & Hu, Y.-Y. Interface-enabled ion conduction in Li10GeP2S12–poly (ethylene oxide) hybrid electrolytes. ACS Appl. Energy Mater. 2, 1452–1459 (2019).
Yu, C. et al. Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface. Nat. Commun. 8, 1086 (2017).
Ganapathy, S., Yu, C., van Eck, E. R. H. & Wagemaker, M. Peeking across grain boundaries in a solid-state ionic conductor. ACS Energy Lett. 4, 1092–1097 (2019).
Schwietert, T. K. et al. Clarifying the relationship between redox activity and electrochemical stability in solid electrolytes. Nat. Mater. 19, 428–435 (2020).
Hoefling, A. et al. Mechanism for the stable performance of sulfur-copolymer cathode in lithium–sulfur battery studied by solid-state NMR spectroscopy. Chem. Mater. 30, 2915–2923 (2018).
Rataboul, F. et al. Molecular understanding of the formation of surface zirconium hydrides upon thermal treatment under hydrogen of [(⋮SiO)Zr(CH2tBu)3] by using advanced solid-state NMR techniques. J. Am. Chem. Soc. 126, 12541–12550 (2004).
Zhu, C., Cheng, H. & Yang, Y. Electrochemical characterization of two types of PEO-based polymer electrolytes with room-temperature ionic liquids. J. Electrochem. Soc. 155, A569 (2008).
Kodama, K. et al. Structural effects of polyethers and ionic liquids in their binary mixtures on lower critical solution temperature liquid-liquid phase separation. Polym. J. 43, 242–248 (2011).
Cesare Marincola, F. et al. NMR investigation of imidazolium‐based ionic liquids and their aqueous mixtures. ChemPhysChem 13, 1339–1346 (2012).
Wang, B.-H., Xia, T., Chen, Q. & Yao, Y.-F. Probing the dynamics of Li+ ions on the crystal surface: a solid-state NMR study. Polymers 12, 391 (2020).
Zhao, Z. et al. Ionic‐association‐assisted viscoelastic nylon electrolytes enable synchronously coupled interface for solid batteries. Adv. Funct. Mater. 30, 2000347 (2020).
Ganapathy, S., van Eck, E. R., Kentgens, A. P., Mulder, F. M. & Wagemaker, M. Equilibrium lithium‐ion transport between nanocrystalline lithium‐inserted anatase TiO2 and the electrolyte. Chem. Eur. J. 17, 14811–14816 (2011).
Kumar, M. & Sekhon, S. S. Role of plasticizer’s dielectric constant on conductivity modification of PEO–NH4F polymer electrolytes. Eur. Polym. J. 38, 1297–1304 (2002).
Liu, M. et al. Novel gel polymer electrolyte for high-performance lithium–sulfur batteries. Nano Energy 22, 278–289 (2016).
Fung, B., Khitrin, A. & Ermolaev, K. An improved broadband decoupling sequence for liquid crystals and solids. J. Magn. Reson. 142, 97–101 (2000).
Acknowledgements
We thank F. Ooms, F. Zhang and C. Ma for their assistance with experiments. M.L. and M.W. acknowledge the financial support from the Netherlands Organization for Scientific Research (NWO) under the VICI grant nr. 16122. E.R.H.v.E. further acknowledges NWO for their support of the solid-state NMR facility for advanced materials science, which is part of the uNMR-NL grid (NWO grant 184.035.002). M.W. gratefully acknowledges the financial support from the Advanced Dutch Energy Materials (ADEM) programme of the Dutch Ministry of Economic Affairs, Agriculture and Innovation.
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S.G. and M.W. designed and supervised the research. M.L., S.Z. and C.W. synthesized and characterized the hybrid solid electrolytes. M.L. and S.Z. carried out the electrochemical measurements. M.L., S.G. and E.R.H.v.E. measured and analysed the NMR data. M.L., S.G. and M.W. wrote the manuscript.
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Nature Nanotechnology thanks Ye-Feng Yao and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Extended data
Extended Data Fig. 1 SEM image of the pristine micron-sized Li6PS5Cl and LiTFSI-PEO-Li6PS5Cl HSE.
(a) SEM image of the pristine micron-sized Li6PS5Cl. (b) SEM image showing the morphology of the HSE where the Li6PS5Cl particles are marked with circles.
Extended Data Fig. 2 1H-6Li CPMAS spectra of the LiTFSI-PEO-Li6PS5Cl HSE.
1H-6Li CPMAS spectra of the LiTFSI-PEO-Li6PS5Cl HSE measured at contact times ranging from 0.2 ms (lightest grey) to 6 ms (black).
Extended Data Fig. 3 1D 6Li magic angle spinning (MAS) spectrum corresponding to the Li6PS5Cl -LiTFSI-PEO HSE.
1D 6Li magic angle spinning (MAS) spectrum corresponding to the Li6PS5Cl -LiTFSI-PEO HSE.
Extended Data Fig. 4 DSC measurements showing the heat flow of the HSE, HSE-EMIM, HSE-PP13.
DSC measurements showing the heat flow of the HSE, HSE-EMIM, HSE-PP13 under heating up from 0 to 65 °C.
Extended Data Fig. 5 1H-1H cross peak intensity buildup of protons in EMIM-TFSI and PP13-TFSI correlated to PEO from the 2D 1H-1H NOESY spectra of HSE-PP13 and HSE-EMIM.
1H-1H cross peak intensity buildup of protons in EMIM-TFSI (a) and PP13-TFSI (b) correlated to PEO from the 2D 1H-1H NOESY spectra of HSE-PP13 and HSE-EMIM given in Fig. 4. All the cross peaks between EMIM-TFSI and LiTFSI-PEO appear at nearly at the same mixing time which means that there is no preferred orientation of the EMIM-TFSI species with respect to PEO. While a sequence of cross peak evolution with mixing time is observed in HSE-PP13. At the shortest mixing times, 1H-1H correlations are first observed between 1H resonances at positions 1.0 ppm and 1.6 ppm on the piperidine ring of PP13-TFSI and the –OCH2- protons from PEO. These ring protons are the furthest away from the bulky propyl and methyl groups attached to the N atom on the piperidine ring.
Extended Data Fig. 6 1D 7Li CPMAS spectra and intensity plots measured of the HSE-EMIM and HSE-PP13, and the full build-up of the peak intensity of the broad component.
1D 7Li CPMAS spectra and intensity plots measured of the (a,c) HSE-EMIM and (b,d) HSE-PP13 at contact times between 200 µs and 12 ms (e) Full build-up of peak intensity at 0.2–0.7 ppm as function of contact time of the spectra given in (a) and (b).
Extended Data Fig. 7 Li+ transport characterization in HSE-EMIM and HSE-PP13 using 6,7Li-6,7Li 2D EXSY NMR.
Li+ transport characterization in HSE with PP13-TFSI and EMIM-TFSI IL additives. 7Li–7Li, 6Li-6Li 2D-EXSY corresponding to the HSE-EMIM (a, b) and HSE-PP13 (c, d) ILs measured under MAS at a spinning speed of 5 kHz mixing time of 1.5 s and 2 s at 328 K.
Extended Data Fig. 8 Plating and stripping curves of a Li metal symmetrical cell with HSE-EMIM and HSE-PP13.
Plating and stripping curves of a Li metal symmetrical cell with LiTFSI-PEO-Li6PS5Cl HSEs with PP13 TFSI and EMIM TFSI ionic liquids. The cell with HSE-EMIM shows quick polarization after 300 h of cycling at a current density of 0.05 mA/cm2. In comparison the cell with HSE-PP13 shows a very stable over-potential (lower than 200 mV) during 800 hours of cycling, indicating a higher ionic conductivity and better interfacial stability against Li-metal.
Extended Data Fig. 9 Electrochemical impedance spectroscopy measurements (EIS) of the cell with LiTFSI-PEO-Li6PS5Cl HSE with both PP13-TFSI and EMIM-TFSI ionic liquids.
Electrochemical impedance spectroscopy measurements (EIS) of cell with LiTFSI-PEO-Li6PS5Cl HSE with both PP13-TFSI and EMIM-TFSI (PP13-TFSI and EMIM-TFSI, 0.25:1 molar ratio IL:Li-ion, HSE—EMIM-PP13) ionic liquids.
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Supplementary Figs. 1 and 2, discussion and Tables 1 and 2.
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Liu, M., Zhang, S., van Eck, E.R.H. et al. Improving Li-ion interfacial transport in hybrid solid electrolytes. Nat. Nanotechnol. 17, 959–967 (2022). https://doi.org/10.1038/s41565-022-01162-9
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DOI: https://doi.org/10.1038/s41565-022-01162-9
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