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Confining Electrodeposition of Metals in Structured Electrolytes

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Rational Design of Nanostructured Polymer Electrolytes and Solid–Liquid Interphases for Lithium Batteries

Part of the book series: Springer Theses ((Springer Theses))

Abstract

Electrochemical cells based on alkali metal (Li, Na) anodes have attracted significant recent attention because of their promise for producing large increases in gravimetric energy density for energy storage in batteries. To facilitate stable, long-term operation of such cells, a variety of structured electrolytes have been designed in different physical forms, ranging from soft polymer gels to hard ceramics, including porous ceramics that host a liquid or molten polymer in their pores. In almost every case, the electrolytes are reported to be substantially more effective than anticipated by early theories in improving uniformity of deposition and lifetime of the metal anode. These observations have been speculated to reflect the effect of electrolyte structure in regulating ion transport to the metal-electrolyte interface, thereby stabilizing metal electrodeposition processes at the anode. Here, we create and study model structured electrolytes composed of covalently linked polymer-grafted nanoparticles that host a liquid electrolyte in the pores. The electrolytes exist as freestanding membranes with effective pore size that can be systematically manipulated through straightforward control of the volume fraction of the nanoparticles. By means of physical analysis and direct visualization experiments, we report that at current densities approaching the diffusion limit, there is a clear transition from unstable to stable electrodeposition at Li metal electrodes in membranes with average pore sizes below 500 nm. We show that this transition is consistent with expectations from a recent theoretical analysis that takes into account local coupling between stress and ion transport at metal-electrolyte interfaces.

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Acknowledgments

This work was supported by the National Science Foundation, Division of Materials Research, through Award No. DMR–1609125.

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Authors and Affiliations

  1. Department of Chemical Engineering, Stanford University, Stanford, CA, USA

    Snehashis Choudhury

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  1. Snehashis Choudhury
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Appendix: Supplementary Information

Appendix: Supplementary Information

Supplementary Fig. 4.1
figure 6

Dielectric relaxation of cross-linked hairy nanoparticles: (a, b) Dielectric permittivity at various temperatures fitted with the H-N model for Neat PPO and cross-linked hairy nanoparticles, respectively; (c) polymer relaxation time as a function of temperatures fitted with a VFT model; (d) comparison between the dielectric strength between the neat PPO and cross-linked PPO; the symbols are the same as in part c

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Supplementary Fig. 4.2
figure 7

Characterization of pore architecture in the cross-linked structure: (a) TEM micrographs of cross-linked nanoparticles. The scale bar represents 200 nm. From left to right, the samples are r.c.p. pore sizes 20 nm, 100 nm, and 500 nm. (b) Storage modulus and (c) loss modulus obtained through frequency sweep measurements at strain of 5% for different cross-linked samples and neat PPO at 60 °C

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Supplementary Fig. 4.3
figure 8

Normal distribution of interparticle distances obtained by analysis of TEM images for cross-linked hairy nanoparticles with different random closed packing pore sizes

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Supplementary Fig. 4.4
figure 9

Polarization of a symmetric lithium cell using the cross-linked hairy nanoparticle electrolyte (r.c.p. = 20 nm) soaked with the electrolyte 1 M EC/DMC LiPF6 at 20 mV. The inset shows the impedance results before and after polarization

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Supplementary Fig. 4.5
figure 10

Room temperature conductivity and limiting current density variation with different pore-sized membranes. The arrows show the corresponding values for a neat electrolyte of 1 M EC/MC LiPF6

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Supplementary Fig. 4.6
figure 11

Schematic representing the idea that the pore size of the electrolyte/separator is important and related to the stability of electrodeposition. In this figure, the cross-linked nanoparticles have random closed packing pore size of 20 nm

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Supplementary Fig. 4.7
figure 12

Charge and discharge cycles in a symmetric lithium coin cell using the cross-linked hairy nanoparticles electrolyte with pore size of 20 nm. The battery was operated at a current density of 0.1 mA/cm2 with each half cycle being 3-h long

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Supplementary Fig. 4.8
figure 13

(a, b) SEM images of lithium electrode surface before and after cycling in a symmetric lithium cell for 100 h at 0.1 mA/cm2

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Supplementary Fig. 4.9
figure 14

Electrodeposition with different pore sizes of the cross-linked nanoparticles: Snapshots of the electrode and cross-linked electrolyte with pore sizes of 1000, 500, and 100 nm in every 15 min during charging at the rate of 8 mA cm−2

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Supplementary Fig. 4.10
figure 15

Height of dendrite at various points of the electrode for the initial 1500 s. The inset compares the growth rate by assuming a linear growth for the visualization experiment in Figure S9 at a current density of 8 mA cm−2

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Supplementary Fig. 4.11
figure 16

(a) Snapshots of electrodeposition with different cross-linked membrane pore sizes at variable current density such that the J/J∗ is maintained at 0.9 for each case; (b) height of dendrite as a function of time for different samples. The absolute values of current densities are reported in the label that correspond to J/J = 0.9. The inset shows the comparison of the dendrite growth rates for the respective pore sizes reported in the main figure

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Supplementary Fig. 4.12
figure 17

Pore size dependence of dendrite growth at a current density of 8 mA/cm2, where the pore size is obtained from the TEM analysis. The inset shows the growth rate as a function of pore volume obtained from the plateau modulus using the equation (kT/G’)

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Supplementary Fig. 4.13
figure 18

Critical pore size, representative of crossover from positive to zero growth rate, at various normalized current density. The inset shows the same graph in semilogarithmic scale

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Supplementary Table 4.1 VFT parameters for fitting the dielectric relaxation times at different temperatures for the cross-linked and neat PPO
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Supplementary Table 4.2 Weight fraction of silica nanoparticles corresponding to the effective pore size obtained by the random packing fraction spherical particles
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Choudhury, S. (2019). Confining Electrodeposition of Metals in Structured Electrolytes. In: Rational Design of Nanostructured Polymer Electrolytes and Solid–Liquid Interphases for Lithium Batteries. Springer Theses. Springer, Cham. https://doi.org/10.1007/978-3-030-28943-0_4

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