Wan, H., Xu, J. & Wang, C. Designing electrolytes and interphases for high-energy lithium batteries. Nat. Rev. Chem. 8, 30–44 (2024).
Xu, K. Interfaces and interphases in batteries. J. Power Sources 559, 232652 (2023).
Popovic, J. The importance of electrode interfaces and interphases for rechargeable metal batteries. Nat. Commun. 12, 6240 (2021).
Wang, C., Meng, Y. S. & Xu, K. Perspective—fluorinating interphases. J. Electrochem. Soc. 166, A5184–A5186 (2018).
Tan, J., Matz, J., Dong, P., Shen, J. & Ye, M. A growing appreciation for the role of LiF in the solid electrolyte interphase. Adv. Energy Mater. 11, 2100046 (2021).
Chen, J. et al. Electrolyte design for LiF-rich solid–electrolyte interfaces to enable high-performance microsized alloy anodes for batteries. Nat. Energy 5, 386–397 (2020).
Li, T., Zhang, X.-Q., Shi, P. & Zhang, Q. Fluorinated solid-electrolyte interphase in high-voltage lithium metal batteries. Joule 3, 2647–2661 (2019).
Peled, E. & Menkin, S. Review—SEI: past, present and future. J. Electrochem. Soc. 164, A1703–A1719 (2017).
Zhu, Y., He, X. & Mo, Y. Origin of outstanding stability in the lithium solid electrolyte materials: insights from thermodynamic analyses based on first-principles calculations. ACS Appl. Mater. Interfaces 7, 23685–23693 (2015).
Shen, X. et al. The failure of solid electrolyte interphase on Li metal anode: structural uniformity or mechanical strength? Adv. Energy Mater. 10, 1903645 (2020).
Xie, J. et al. Stitching h-BN by atomic layer deposition of LiF as a stable interface for lithium metal anode. Sci. Adv. 3, eaao3170 (2017).
Lin, D. et al. Conformal lithium fluoride protection layer on three-dimensional lithium by nonhazardous gaseous reagent freon. Nano Lett. 17, 3731–3737 (2017).
Fan, X. et al. Highly fluorinated interphases enable high-voltage Li-metal batteries. Chem 4, 174–185 (2018).
Yu, Z. et al. Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries. Nat. Energy 5, 526–533 (2020).
Oyakhire, S. T., Gong, H., Cui, Y., Bao, Z. & Bent, S. F. An X-ray photoelectron spectroscopy primer for solid electrolyte interphase characterization in lithium metal anodes. ACS Energy Lett. 7, 2540–2546 (2022).
Wang, X. et al. New insights on the structure of electrochemically deposited lithium metal and its solid electrolyte interphases via cryogenic TEM. Nano Lett. 17, 7606–7612 (2017).
Ma, C., Xu, F. & Song, T. Dual-layered interfacial evolution of lithium metal anode: SEI analysis via TOF-SIMS technology. ACS Appl. Mater. Interfaces 14, 20197–20207 (2022).
Hope, M. A. et al. Selective NMR observation of the SEI–metal interface by dynamic nuclear polarisation from lithium metal. Nat. Commun. 11, 2224 (2020).
May, R., Fritzsching, K. J., Livitz, D., Denny, S. R. & Marbella, L. E. Rapid interfacial exchange of Li ions dictates high Coulombic efficiency in Li metal anodes. ACS Energy Lett. 6, 1162–1169 (2021).
Menkin, S. et al. Toward an understanding of SEI formation and lithium plating on copper in anode-free batteries. J. Phys. Chem. C 30, 16719–16732 (2021).
Shadike, Z. et al. Identification of LiH and nanocrystalline LiF in the solid–electrolyte interphase of lithium metal anodes. Nat. Nanotechnol. 16, 549–554 (2021).
Yildirim, H., Kinaci, A., Chan, M. K. Y. & Greeley, J. P. First-principles analysis of defect thermodynamics and ion transport in inorganic SEI compounds: LiF and NaF. ACS Appl. Mater. Interfaces 7, 18985–18996 (2015).
Chen, Y. et al. Origin of dendrite-free lithium deposition in concentrated electrolytes. Nat. Commun. 14, 2655 (2023).
Qian, J. F. et al. High rate and stable cycling of lithium metal anode. Nat. Commun. 6, 6362 (2015).
May, R., Hestenes, J. C., Munich, N. A. & Marbella, L. E. Fluorinated ether decomposition in localized high concentration electrolytes. J. Power Sources 553, 232299 (2023).
Svirinovsky-Arbeli, A., Juelsholt, M., May, R., Kwon, Y. & Marbella, L. E. Using NMR spectroscopy to link structure to function at the Li solid electrolyte interphase. Joule 8, 1919–1935 (2024).
Hu, J. Z., Kwak, J. H., Yang, Z., Wan, X. & Shaw, L. L. Detailed investigation of ion exchange in ball-milled LiH+MgB2 system using ultra-high field nuclear magnetic resonance spectroscopy. J. Power Sources 195, 3645–3648 (2010).
Zhong, G. et al. Insights into the lithiation mechanism of CFx by a joint high-resolution 19F NMR, in situ TEM and 7Li NMR approach. J. Mater. Chem. A 7, 19793–19799 (2019).
Gombotz, M. et al. Insulator:conductor interfacial regions — Li ion dynamics in the nanocrystalline dispersed ionic conductor LiF:TiO2. Solid State Ion. 369, 115726 (2021).
Saldan, I. et al. Hydrogen sorption in the LiH–LiF–MgB2 system. J. Phys. Chem. C 117, 17360–17366 (2013).
Pinatel, E. R., Corno, M., Ugliengo, P. & Baricco, M. Effects of metastability on hydrogen sorption in fluorine substituted hydrides. J. Alloys Compd. 615, S706–S710 (2014).
Pighin, S. A., Urretavizcaya, G. & Castro, F. J. Reversible hydrogen storage in Mg(HxF1−x)2 solid solutions. J. Alloys Compd. 708, 108–114 (2017).
Pistidda, C. et al. Effect of the partial replacement of CaH2 with CaF2 in the mixed system CaH2 + MgB2. J. Phys. Chem. C 118, 28409–28417 (2014).
Sitthiwet, C. et al. Hydrogen sorption kinetics and suppression of NH3 emission of LiH-sandwiched LiNH2-LiH-TiF4-MWCNTs pellets upon cycling. J. Alloys Compd. 909, 164673 (2022).
Yu, W., Yu, Z., Cui, Y. & Bao, Z. Degradation and speciation of Li salts during XPS analysis for battery research. ACS Energy Lett. 7, 3270–3275 (2022).
Breuer, O., Gofer, Y., Elias, Y., Fayena-Greenstein, M. & Aurbach, D. Misuse of XPS in analyzing solid polymer electrolytes for lithium batteries. J. Electrochem. Soc. 171, 030510 (2024).
Steinberg, K. et al. Imaging of nitrogen fixation at lithium solid electrolyte interphases via cryo-electron microscopy. Nat. Energy 8, 138–148 (2023).
Ilott, A. J. & Jerschow, A. Probing solid-electrolyte interphase (SEI) growth and ion permeability at undriven electrolyte–metal interfaces using 7Li NMR. J. Phys. Chem. C 122, 12598–12604 (2018).
Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994).
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Perdew, J. P. et al. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Perdew, J. P. et al. Restoring the density-gradient expansion for exchange in solids and surfaces. Phys. Rev. Lett. 100, 136406 (2008).
Henkelman, G. et al. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).
Wang, V. et al. VASPKIT: a user-friendly interface facilitating high-throughput computing and analysis using VASP code. Comput. Phys. Commun. 267, 108033 (2021).
Momma, K. & Izumi, F. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272–1276 (2011).
Brivio, F. et al. Thermodynamic origin of photoinstability in the CH3NH3Pb(I1−xBrx)3 hybrid halide perovskite alloy. J. Phys. Chem. Lett. 7, 1083–1087 (2016).