The use of interfacial layers to stabilize the lithium surface is a popular research direction for improving the morphology of deposited lithium and suppressing lithium dendrite formation. This work considers a different approach to controlling dendrite formation where lithium is plated underneath an interfacial coating. In the present research, a Li–Sn intermetallic was chosen as a model system due to its lithium-rich intermetallic phases and high Li diffusivity. These coatings also exhibit a significantly higher Li exchange current than bare Li thus leading to better charge transfer kinetics. The exchange current is instrumental in determining whether lithium deposition occurs above or below the Li–Sn coating. High-resolution transmission electron microscopy and cryogenic focused ion beam scanning electron microscopy were used to identify the features associated with Li deposition. Atomic scale simulations provide insight as to the adsorption energies determining the deposition of lithium below the Li–Sn coating.
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C. Fang, J. Li, M. Zhang, Y. Zhang, F. Yang, J.Z. Lee, M.H. Lee, J. Alvarado, M.A. Schroeder, Y. Yang, B. Lu, N. Williams, M. Ceja, L. Yang, M. Cai, J. Gu, K. Xu, X. Wang, Y.S. Meng, Quantifying inactive lithium in lithium metal batteries. Nature 572(7770), 511 (2019)
C. Fang, X. Wang, and Y. S. Meng: Key Issues hindering a practical lithium-metal anode. Trends Chem. 0(0), 1 (2019).
X.B. Cheng, R. Zhang, C.Z. Zhao, Q. Zhang, Toward safe lithium metal anode in rechargeable batteries: a review. Chem. Rev. 117(15), 10403 (2017)
E. Peled, The electrochemical behavior of alkali and alkaline earth metals in nonaqueous battery systems—the solid electrolyte interphase model. J. Electrochem. Soc. 126(12), 2047 (1979)
J. Qian, W. A. Henderson, W. Xu, P. Bhattacharya, M. Engelhard, O. Borodin, and J. G. Zhang: High rate and stable cycling of lithium metal anode. Nat. Commun. 6 (2015).
J.B. Goodenough, Y. Kim, Challenges for rechargeable Li batteries. Chem. Mater. 22(3), 587 (2010)
M.S. Whittingham, Electrical energy storage and intercalation chemistry. Science 192(4244), 1126 (1976)
B.D. Adams, J. Zheng, X. Ren, W. Xu, J.G. Zhang, Accurate determination of coulombic efficiency for lithium metal anodes and lithium metal batteries. Adv. Energy Mater. 8(7), 1 (2018)
D. Aurbach, Review of selected electrode-solution interactions which determine the performance of Li and Li ion batteries. J. Power Sources 89(2), 206 (2000)
X.B. Cheng, R. Zhang, C.Z. Zhao, F. Wei, J.G. Zhang, Q. Zhang, A review of solid electrolyte interphases on lithium metal anode. Adv. Sci. 3(3), 1 (2015)
M.D. Tikekar, S. Choudhury, Z. Tu, L.A. Archer, Design principles for electrolytes and interfaces for stable lithium-metal batteries. Nat. Energy 1(9), 1 (2016)
X.Q. Zhang, X.B. Cheng, X. Chen, C. Yan, Q. Zhang, Fluoroethylene carbonate additives to render uniform li deposits in lithium metal batteries. Adv. Funct. Mater. 27(10), 1 (2017)
D. Aurbach, K. Gamolsky, B. Markovsky, Y. Gofer, M. Schmidt, U. Heider, On the use of vinylene carbonate (VC) as an additive to electrolyte solutions for Li-ion batteries. Electrochim. Acta 47(9), 1423 (2002)
C. P. Yang, Y. X. Yin, S. F. Zhang, N. W. Li, and Y. G. Guo: Accommodating lithium into 3D current collectors with a submicron skeleton towards long-life lithium metal anodes. Nat. Commun. 6(5) (2015).
Q. Yun, Y.B. He, W. Lv, Y. Zhao, B. Li, F. Kang, Q.H. Yang, Chemical dealloying derived 3D porous current collector for Li metal anodes. Adv. Mater. 28(32), 6932 (2016)
K. Liu, D. Zhuo, H.W. Lee, W. Liu, D. Lin, Y. Lu, Y. Cui, Extending the life of lithium-based rechargeable batteries by reaction of lithium dendrites with a novel silica nanoparticle sandwiched separator. Adv. Mater. 29(4), 1 (2017)
G. Zheng, S.W. Lee, Z. Liang, H.W. Lee, K. Yan, H. Yao, H. Wang, W. Li, S. Chu, Y. Cui, Interconnected hollow carbon nanospheres for stable lithium metal anodes. Nat. Nanotechnol. 9(8), 618 (2014)
Y. Chen, Z. Wang, X. Li, X. Yao, C. Wang, Y. Li, W. Xue, D. Yu, S.Y. Kim, F. Yang, A. Kushima, G. Zhang, H. Huang, N. Wu, Y.W. Mai, J.B. Goodenough, J. Li, Li metal deposition and stripping in a solid-state battery via Coble creep. Nature 578(7794), 251 (2020)
G.A. Umeda, E. Menke, M. Richard, K.L. Stamm, F. Wudl, B. Dunn, Protection of lithium metal surfaces using tetraethoxysilane. J. Mater. Chem. 21(5), 1593 (2011)
D. Lin, Y. Liu, W. Chen, G. Zhou, K. Liu, B. Dunn, Y. Cui, Conformal lithium fluoride protection layer on three-dimensional lithium by nonhazardous gaseous reagent freon. Nano Lett. 17(6), 3731 (2017)
X. Liang, Q. Pang, I.R. Kochetkov, M.S. Sempere, H. Huang, X. Sun, L.F. Nazar, A facile surface chemistry route to a stabilized lithium metal anode. Nat. Energy 6, 17119 (2017)
Q. Yan, G. Whang, Z. Wei, S. T. Ko, P. Sautet, S. H. Tolbert, B. S. Dunn, and J. Luo: Appl. Phys. Lett. 117, (2020).
F. Guo, C. Wu, H. Chen, F. Zhong, X. Ai, H. Yang, J. Qian, Dendrite-free lithium deposition by coating a lithiophilic heterogeneous metal layer on lithium metal anode. Energy Storage Mater. 24(4), 635 (2020)
L. Luo, A. Manthiram, An artificial protective coating toward dendrite-free lithium-metal anodes for lithium-sulfur batteries. Energy Technol. 8(7), 1 (2020)
R. Pathak, K. Chen, A. Gurung, K.M. Reza, B. Bahrami, J. Pokharel, A. Baniya, W. He, F. Wu, Y. Zhou, K. Xu, Q. Qiao, Fluorinated hybrid solid-electrolyte-interphase for dendrite-free lithium deposition. Nat. Commun. 11(1), 1 (2020)
A. Anani, R.A. Huggins, Technical notes kinetic and thermodynamic parameters of several binary lithium. J. Electrochem. Soc. 134(12), 3098 (1987)
J. Wen, R.A. Huggins, Chemical diffusion in intermediate phases in the lithium-tin system. J. Solid State Chem. 35(3), 376 (1980)
M. Wan, S. Kang, L. Wang, H.W. Lee, G.W. Zheng, Y. Cui, Y. Sun, Mechanical rolling formation of interpenetrated lithium metal/lithium tin alloy foil for ultrahigh-rate battery anode. Nat. Commun. 11(1), 1 (2020)
H. Xu, S. Li, C. Zhang, X. Chen, W. Liu, Y. Zheng, Y. Xie, Y. Huang, J. Li, Roll-to-roll prelithiation of Sn foil anode suppresses gassing and enables stable full-cell cycling of lithium ion batteries. Energy Environ. Sci. 12(10), 2991 (2019)
Z. Tu, S. Choudhury, M.J. Zachman, S. Wei, K. Zhang, L.F. Kourkoutis, L.A. Archer, Fast ion transport at solid-solid interfaces in hybrid battery anodes. Nat. Energy 3(4), 310 (2018)
Z. Du, Z. Jiang, C. Guo, Thermodynamic optimizing of the Li-Sn system. Int. J. Mater. Res. 97(1), 10 (2006)
L. Lin, F. Liang, K. Zhang, H. Mao, J. Yang, Y. Qian, Lithium phosphide/lithium chloride coating on lithium for advanced lithium metal anode. J. Mater. Chem. A 6(32), 15859 (2018)
K. Liao, S. Wu, X. Mu, Q. Lu, M. Han, P. He, Z. Shao, H. Zhou, Developing a “Water-Defendable” and “Dendrite-Free” lithium-metal anode using a simple and promising GeCl4 pretreatment method. Adv. Mater. 30(36), 1 (2018)
J.F. Moulder, W.F. Stickle, P.E. Sobol, Handbook of X-Ray Photoelectron Spectroscopy : A Reference Book of Standard Spectra for Identification and Interpretation of XPS Data (Physical Electronics Inc, Eden Prairie, 1995).
Y. Ozhabes, D. Gunceler, and T. A. Arias: Stability and surface diffusion at lithium-electrolyte interphases with connections to dendrite suppression. 1 (2015) arXiv:1504.05799.
H. Rawson, Inorganic Glass-Forming Systems (Academic Press, London, 1967).
G. Rack: The binary system SnCl2-LiCl. Centr. Min. Geol. 326–8 (1914).
Phase Equilibria Diagrams Online Database (NIST Standard Reference Database 31). Am. Ceram. Soc. Natl. Inst. Stand. Technol. Figure Number 3090 (2020).
M. Shojiya, M. Takahashi, R. Kanno, Y. Kawamoto, K. Kadono, Optical transitions of Er3+ ions in ZnCl2-based glass. J. Appl. Phys. 82(12), 6259 (1997)
K. Annapurna, R.N. Dwivedi, P. Kundu, S. Buddhudu, Fluorescence properties of Sm3+: ZnCl2-BaCl2-LiCl glass. Mater. Res. Bull. 38(3), 429 (2003)
J. Easteal, E.J. Sare, C.T. Moynihan, C.A. Angell, Glass-transition temperature, electrical conductance, viscosity, molar volume, refractive index, and proton magnetic resonance study of chlorozinc complexation in the system ZnCl2+LiCl+H2O. J. Solution Chem. 3(11), 807 (1974)
J. Bard, L.R. Faulkner, Electrochemical Methods: Fundamental and Applications, 2nd Editio (Wiley, New York, 2001).
T. Boyle, X. Kong, A. Pei, P.E. Rudnicki, F. Shi, W. Huang, Z. Bao, J. Qin, Y. Cui, Transient voltammetry with ultramicroelectrodes reveals the electron transfer kinetics of lithium metal anodes. ACS Energy Lett. 5(3), 701 (2020)
G. Bieker, M. Winter, P. Bieker, Electrochemical in situ investigations of SEI and dendrite formation on the lithium metal anode. Phys. Chem. Chem. Phys. 17(14), 8670 (2015)
S. Kang, Y.-S. Lee, D.-W. Kim, Improved cycling stability of lithium electrodes in rechargeable lithium batteries. J. Electrochem. Soc. 161(1), A53 (2014)
A. Wei, H. Fei, Y. An, Y. Tao, J. Feng, Y. Qian, Uniform Li deposition by regulating the initial nucleation barrier: via a simple liquid-metal coating for a dendrite-free Li-metal anode. J. Mater. Chem. A 7(32), 18861 (2019)
K. Park, J.B. Goodenough, Dendrite-suppressed lithium plating from a liquid electrolyte via wetting of Li3N. Adv. Energy Mater. 7(19), 1 (2017)
H. Jung, B. Lee, M. Lengyel, R. Axelbaum, J. Yoo, Y.S. Kim, Y.S. Jun, Nanoscale: In situ detection of nucleation and growth of Li electrodeposition at various current densities. J. Mater. Chem. A 6(11), 4629 (2018)
F. Sagane, K.I. Ikeda, K. Okita, H. Sano, H. Sakaebe, Y. Iriyama, Effects of current densities on the lithium plating morphology at a lithium phosphorus oxynitride glass electrolyte/copper thin film interface. J. Power Sources 233, 34 (2013)
I. Popov, S. S. Djokić, and B. N. Grgur: in Fundam. Asp. Electrometall. (Springer US, Boston, MA, 2002), pp. 29–100.
J.Z. Lee, T.A. Wynn, M.A. Schroeder, J. Alvarado, X. Wang, K. Xu, Y.S. Meng, Cryogenic focused ion beam characterization of lithium metal anodes. ACS Energy Lett. 4(2), 489 (2019)
A.R. Ely, R.E. García, Heterogeneous nucleation and growth of lithium electrodeposits on negative electrodes. J. Electrochem. Soc. 160(4), A662 (2013)
Y. Lu, Z. Tu, L.A. Archer, Stable lithium electrodeposition in liquid and nanoporous solid electrolytes. Nat. Mater. 13(10), 961 (2014)
Q. Pang, X. Liang, I.R. Kochetkov, P. Hartmann, L.F. Nazar, Stabilizing lithium plating by a biphasic surface layer formed in situ. Angew. Chemie - Int. Ed. 57(31), 9795 (2018)
C. Kozen, C.F. Lin, A.J. Pearse, M.A. Schroeder, X. Han, L. Hu, S.B. Lee, G.W. Rubloff, M. Noked, Next-generation lithium metal anode engineering via atomic layer deposition. ACS Nano 9(6), 5884 (2015)
A.C. Kazyak, K.N. Wood, N.P. Dasgupta, Improved cycle life and stability of lithium metal anodes through ultrathin atomic layer deposition surface treatments. Chem. Mater. 27(18), 6457 (2015)
W. Kohn, L.J. Sham, Self-consistent equations including exchange and correlation effects. Phys. Rev. 140(4A), A1133 (1965)
G. Kresse, J. Hafner, Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47(1), 558 (1993)
G. Kresse, J. Furthmüller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54(16), 11169 (1996)
J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple. Phys. Rev. Lett. 77(18), 3865 (1996)
P.E. Blöchl, Projector augmented-wave method. Phys. Rev. B 50(24), 17953 (1994)
G. Kresse, D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59(3), 1758 (1999)
K. Mathew, R. Sundararaman, K. Letchworth-Weaver, T. A. Arias, and R. G. Hennig: Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. J. Chem. Phys. 140(8) (2014)
J.K. Nørskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J.R. Kitchin, T. Bligaard, H. Jónsson, Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108(46), 17886 (2004)
J.S. Filhol, M.L. Doublet, An ab initio study of surface electrochemical disproportionation: the case of a water monolayer adsorbed on a Pd(1 1 1) surface. Catal. Today 202(1), 87 (2013)
J.S. Filhol, M.L. Doublet, Conceptual surface electrochemistry and new redox descriptors. J. Phys. Chem. C 118(33), 19023 (2014)
J. Towns, T. Cockerill, M. Dahan, I. Foster, K. Gaither, A. Grimshaw, V. Hazlewood, S. Lathrop, D. Lifka, G.D. Peterson, R. Roskies, J.R. Scott, and N. Wilkins-Diehr, XSEDE: accelerating scientific discovery. Comput. Sci. Eng. 16(5), 62 (2014)
G.W. and Q.Y. contributed equally to this work. This work was supported by the Center for Synthetic Control Across Length-scales for Advancing Rechargeables (SCALAR), an Energy Frontier Research Center funded by the United States Department of Energy, Office of Science, Basic Energy Sciences under Award No. DESC0019381. D.L. is grateful for her one-year support through the Joint PhD Training Fellowship Program from the University of Chinese Academy of Sciences. The authors also would like to thank Dr. Lele Peng for his helpful discussions throughout the course of the project. This work used the shared user facilities at the San Diego Nanotechnology Infrastructure (SDNI) of UCSD, a member of the National Nanotechnology Coordinated Infrastructure supported by the National Science Foundation (Grant ECCS-1542148). The calculations were performed on the Hoffman2 cluster at the UCLA Institute for Digital Research and Education (IDRE), and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant number ACI- 1548562, through allocation TG-CHE170060.
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Whang, G., Yan, Q., Li, D. et al. Avoiding dendrite formation by confining lithium deposition underneath Li–Sn coatings. Journal of Materials Research (2021). https://doi.org/10.1557/s43578-020-00047-8