Morphology prediction of lithium plating by finite element modeling and simulations based on non-linear kinetics

LIN Zhenkang1 QIAO Yaoxuan1 WANG Wei1 YUAN Hong2,3 FAN Cheng1 SUN Kening1

(1.School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, China 100081)
(2.Advanced Research Institute for Multidisciplinary Science, Beijing Institute of Technology, Beijing, China 100081)
(3.Department of Chemical Engineering, Tsinghua University, Beijing, China 100084)

【Abstract】Lithium metal has a very high theoretical energy density and is one of the most promising anode materials for a new generation of lithium batteries. It is easy to form dendrites during the deposition of lithium metal, which greatly affects the safety and service life of lithium metal batteries. The mechanism of dendrite propagation in lithium metal batteries (LMB) is still to be fundamentally described. Herein, we studied the effects of electrochemical parameters on the behavior of lithium plating at the electrode/electrolyte interface using a tertiary current model by finite element methods. The results show that dendrite growth is intrinsically influenced by differences in concentration and potential. A higher diffusion coefficient (De) of Li ion in electrolyte is effective to improve the uniformity of local concentration and a smaller exchange current density (i0) is essential for reducing the sensitivity of interface reaction. Activation polarization is beneficial for uniform plating of lithium. Thus, the polarization curve is extremely important to determine whether lithium deposits uniformly or not. This work results in a new understanding of principles for dendrite growth, and is expected to lead to new insights into strategies for dendrite suppression.

【Keywords】 Li metal batteries; electrochemistry; kinetics; numerical simulation; Li dendrite;


Download this article

(Translated by WANG YX)


    [1] Li M, Lu J, Chen Z, et al. 30 years of lithium-ion batteries [J]. Advanced Materials, 2018, 30 (33): 1800561.

    [2] Schmuch R, Wagner R, Hörpel G, et al. Performance and cost of materials for lithium-based rechargeable automotive batteries [J]. Nature Energy, 2018, 3 (4): 267–278.

    [3] Cheng X B, Zhang R, Zhao C Z, et al. Toward safe lithium metal anode in rechargeable batteries: a review [J]. Chemical Reviews, 2017, 117 (15): 10403–10473.

    [4] Xu W, Wang J, Ding F, et al. Lithium metal anodes for rechargeable batteries [J]. Energy & Environmental Science, 2014, 7 (2): 513–537.

    [5] Steiger J, Kramer D, Mönig R. Mechanisms of dendritic growth investigated by in situ light microscopy during electrodeposition and dissolution of lithium [J]. Journal of Power Sources, 2014, 261: 112–119.

    [6] Steiger J, Kramer D, Mönig R. Microscopic observations of the formation, growth and shrinkage of lithium moss during electrodeposition and dissolution [J]. Electrochimica Acta, 2014, 136: 529–536.

    [7] Park M S, Ma S B, Lee D J, et al. A highly reversible lithium metal anode [J]. Scientific Reports, 2014, 4: 3815.

    [8] Aryanfar A, Brooks D J, Colussi A J, et al. Thermal relaxation of lithium dendrites [J]. Physical Chemistry Chemical Physics, 2015, 17 (12): 8000–8005.

    [9] Aryanfar A, Brooks D, Merinov B V, et al. Dynamics of lithium dendrite growth and inhibition: pulse charging experiments and Monte Carlo calculations [J]. The Journal of Physical Chemistry Letters, 2014, 5 (10): 1721–1726.

    [10] Ely D R, Jana A, García R E. Phase field kinetics of lithium electrodeposits [J]. Journal of Power Sources, 2014, 272: 581–594.

    [11] Chen L, Zhang H W, Liang L Y, et al. Modulation of dendritic patterns during electrodeposition: a nonlinear phase-field model [J]. Journal of Power Sources, 2015, 300: 376–385.

    [12] Shen X, Zhang R, Chen X, et al. The failure of solid electrolyte interphase on Li metal anode: structural uniformity or mechanical strength? [J]. Advanced Energy Materials, 2020, 10 (10): 1903645.

    [13]Zhang R, Shen X, Wang J F, et al. Plating of Li ions in 3D structured lithium metal anodes [J]. CIESC Journal, 2020, 71 (6): 2688–2695 (in Chinese).

    [14] Zhang R, Shen X, Cheng X B, et al. The dendrite growth in 3D structured lithium metal anodes: electron or ion transfer limitation? [J]. Energy Storage Materials, 2019, 23: 556–565.

    [15] Yang Q, Li W, Dong C, et al. PIM-1 as an artificial solid electrolyte interphase for stable lithium metal anode in high-performance batteries [J]. Journal of Energy Chemistry, 2020, 42: 83–90.

    [16] Ma Y, Dong C, Yang Q, et al. Investigation of polysulfone film on high-performance anode with stabilized electrolyte/electrode interface for lithium batteries [J]. Journal of Energy Chemistry, 2020, 42: 49–55.

    [17] Tan J, Tartakovsky A M, Ferris K, et al. Investigating the effects of anisotropic mass transport on dendrite growth in high energy density lithium batteries [J]. Journal of the Electrochemical Society, 2016, 163 (2): A318–A327.

    [18] Mayers M Z, Kaminski J W, Miller T F. Suppression of dendrite formation via pulse charging in rechargeable lithium metal batteries [J]. The Journal of Physical Chemistry C, 2012, 116 (50): 26214–26221.

    [19] Zhang X Q, Chen X, Cheng X B, et al. Highly stable lithium metal batteries enabled by regulating the solvation of lithium ions in nonaqueous electrolytes [J]. Angewandte Chemie International Edition, 2018, 57 (19): 5301–5305.

    [20]Chen Y, Mu T C. Application of deep eutectic solvents in battery and electrocatalysis [J]. CIESC Journal, 2020, 71 (1): 106–121 (in Chinese).

    [21] Xu K, von Cresce A, Lee U. Differentiating contributions to “ion transfer” barrier from interphasial resistance and Li+ desolvation at electrolyte/graphite interface [J]. Langmuir, 2010, 26 (13): 11538–11543.

    [22] Barai P, Higa K, Srinivasan V. Effect of initial state of lithium on the propensity for dendrite formation: a theoretical study [J].Journal of the Electrochemical Society, 2017, 164 (2): A180–A189.

    [23] Mogi R, Inaba M, Iriyama Y, et al. In situ atomic force microscopy study on lithium deposition on nickel substrates at elevated temperatures [J]. Journal of the Electrochemical Society, 2002, 149 (4): A385–A390.

    [24] Byrne P, Fontes E, Parhammar O, et al. A simulation of the tertiary current density distribution from a chlorate cell (I): Mathematical model [J]. Journal of the Electrochemical Society, 2001, 148 (10): D125–D132.

    [25] Pérez T, Nava J L. Numerical simulation of the primary, secondary and tertiary current distributions on the cathode of a rotating cylinder electrode cell: influence of using plates and a concentric cylinder as counter electrodes [J]. Journal of Electroanalytical Chemistry, 2014, 719: 106–112.

    [26] Kim G S, Merchant T, D'Urso J, et al. Systematic study of surface chemistry and comprehensive two-dimensional tertiary current distribution model for copper electrochemical deposition [J].Journal of the Electrochemical Society, 2006, 153 (11): C761–C772.

    [27] Suresh R, Rengaswamy R. Modeling and control of battery systems (I): Revisiting Butler-Volmer equations to model non-linear coupling of various capacity fade mechanisms [J]. Computers & Chemical Engineering, 2018, 119: 336–351.

    [28] Sokirko A V, Bark F H. Diffusion–migration transport in a system with Butler-Volmer kinetics, an exact solution [J]. Electrochimica Acta, 1995, 40 (12): 1983–1996.

    [29] Pei A, Zheng G, Shi F, et al. Nanoscale nucleation and growth of electrodeposited lithium metal [J]. Nano Letters, 2017, 17 (2): 1132–1139.

    [30] Dreyer W, Guhlke C, Müller R. A new perspective on the electron transfer: recovering the Butler-Volmer equation in nonequilibrium thermodynamics [J]. Physical Chemistry Chemical Physics, 2016, 18 (36): 24966–24983.

    [31] Liu W, Lin D, Pei A, et al. Stabilizing lithium metal anodes by uniform Li-ion flux distribution in nanochannel confinement [J].Journal of the American Chemical Society, 2016, 138 (47): 15443–15450.

    [32] Liu C, Liu L. Optimal design of Li-ion batteries through multiphysics modeling and multi-objective optimization [J]. Journal of the Electrochemical Society, 2017, 164 (11): E3254–E3264.

    [33] Lin X, Park J, Liu L, et al. A comprehensive capacity fade model and analysis for Li-ion batteries [J]. Journal of the Electrochemical Society, 2013, 160 (10): A1701–A1710.

    [34] Bonino F, Scrosati B, Selvaggi A, et al. Electrode processes at the lithium–polymer electrolyte interface [J]. Journal of Power Sources, 1986, 18 (1): 75–81.

    [35] Hughes M, Karunathilaka S, Hampson N A, et al. The faradaic impedance of the lithium–sulphur dioxide system. A kinetic interpretation [J]. Journal of Applied Electrochemistry, 1982, 12 (5): 537–543.

    [36] Kim S P, van Duin A C T, Shenoy V B. Effect of electrolytes on the structure and evolution of the solid electrolyte interphase (SEI) in Li-ion batteries: a molecular dynamics study [J]. Journal of Power Sources, 2011, 196 (20): 8590–8597.

    [37] Yan J, Xia B J, Su Y C, et al. Phenomenologically modeling the formation and evolution of the solid electrolyte interface on the graphite electrode for lithium-ion batteries [J]. Electrochimica Acta, 2008, 53 (24): 7069–7078.

    [38] Borodin O, Smith G D, Fan P. Molecular dynamics simulations of lithium alkyl carbonates [J]. The Journal of Physical Chemistry B, 2006, 110 (45): 22773–22779.

    [39] Chen X R, Yao Y X, Yan C, et al. A diffusion–reaction competition mechanism to tailor lithium deposition for lithium–metal batteries [J]. Angewandte Chemie, 2020, 132 (20): 7817–7821.

    [40] Nishikawa K, Mori T, Nishida T, et al. Li dendrite growth and Li+ ionic mass transfer phenomenon [J]. Journal of Electroanalytical Chemistry, 2011, 661 (1): 84–89.

This Article


CN: 11-1946/TQ

Vol 71, No. 09, Pages 4228-4237

September 2020


Article Outline


  • Introduction
  • 1 Simulation and calculation
  • 2 Results and discussion
  • 3 Conclusions
  • References