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Designing Solid-Liquid Interphases for Sodium Batteries

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

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Abstract

Secondary batteries based on earth-abundant sodium metal anodes are desirable for both grid-level, stationary storage and for portable electrical energy storage. Room-temperature sodium metal batteries are impractical today because morphological instability during battery recharge leads to dendritic electrodeposition. Chemical instability of liquid electrolytes in contact with metallic sodium also leads to premature cell failure by depleting the electrolyte and electrode via parasitic reactions. Here we show by means of joint density-functional theoretical analysis that the surface diffusion barrier for ion transport across a metal/liquid interface is a sensitive function of the chemistry of solid electrolyte interphase. In particular, we find that a sodium bromide interphase presents an exceptionally low energy barrier to ion transport, comparable to that of metallic magnesium, which can be recharged in liquid electrolytes without forming dendrites. We evaluate this prediction by means of electrochemical measurements and direct visualization studies. These experiments reveal an approximately threefold reduction in activation energy for ion transport across the sodium bromide interphase. By means of direct visualization of sodium electrodeposition at planar interfaces and by electrochemical analysis, we further show that the reduction in transport barrier at a sodium-bromine-liquid electrolyte interphase yields large improvements in stability of sodium deposition in liquid electrolytes.

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Acknowledgments

This work was supported by the Department of Energy, Advanced Research Projects Agency – Energy (ARPA-E) through award #DE-AR0000750. The work made use of electrochemical characterization facilities in the KAUST-CU Center for Energy and Sustainability, supported by the King Abdullah University of Science and Technology (KAUST) through Award # KUS-C1-018-02. Electron microscopy facilities at the Cornell Center for Materials Research (CCMR), an NSF-supported MRSEC through Grant DMR-1120296, were also used for the study. M.J.Z. and L.F.K. acknowledge support by the NSF (DMR-1654596).

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

    Snehashis Choudhury

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Appendix: Supplementary Information

Appendix: Supplementary Information

Supplementary Fig. 6.1
figure 7

Cross-sectional images of NaBr-coated sodium and pristine sodium. (a) EDX mapping of cross sections of sodium anodes with NaBr surface layers after reacting for 1 min (left) and 5 min (right). The cross sections were obtained by cryo-focused ion beam milling; scale bar, 3 μm. (b) Room-temperature FIB-SEM cross-sectional imaging of pristine sodium shows a 5 μm thick oxidation layer on the surface; scale bar, 5 μm

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Supplementary Fig. 6.2
figure 8

Surface composition of cycled sodium metal with NaBr coating obtained by two separate methods of EDX and XPS

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Supplementary Fig. 6.3
figure 9

Equivalent circuit model for fitting Nyquist plots of impedance measurements. Here, R-bulk represents the ion transport in bulk electrolyte. R-interface1 represents interfacial resistance associated with the passivation layer between electrode and electrolyte. R-interface2 denotes the electronic transport in the interface. CPE1 and CPE2 represent the constant phase elements. Warburg element stands for solid-state diffusion contribution

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Supplementary Fig. 6.4
figure 10

Impedance spectroscopy for different anode Nyquist plots at various temperatures for (a) Mg, (c) Na with NaCl, and (e) Na with NaI. Figures (b), (d), and (f) represent the temperature dependence of the reciprocal impedances (both bulk and interface) which is plotted as a function of Arrhenius temperature; the lines represent corresponding VFT fits. The labels represent the type of electrode interface used for the experiment

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Supplementary Fig. 6.5
figure 11

Activation energy obtained by Arrhenius analysis. (a) Reciprocal of interfacial resistance plotted as a function of inverse temperature. The fits represent prediction from Arrhenius equation; (b) the activation energy is plotted for different interface or metal electrodes, obtained by Arrhenius fitting. Mg and Na represent cells with magnesium and sodium electrodes, respectively, without any modification, while NaCl, NaBr, and NaI represent data for respective halide-coated sodium metal

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Supplementary Fig. 6.6
figure 12

Electrochemical setup for in situ visualization of sodium electrodeposition consisting of an airtight cuvette and two rods serving as current collectors for attaching the sodium electrodes. The cap is well sealed with a black tape to ensure that there is no leakage of electrolyte or air contamination

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Supplementary Fig. 6.7
figure 13

Performance and characterization of Na||SPAN cell. (a) Charge and discharge capacity as a function of cycle no. for pristine sodium-based half-cell and NaBr-coated sodium-based half-cell comprising of the SPAN cathode. (b) SEM image of sodium metal after cycling in Na||SPAN cell with NaBr coating anode; scale bar, 100 μm. The adjacent image shows the EDX mapping of the elements of Na anode

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Supplementary Table 6.1 Parameters of VFT analysis bulk impedance represents the ion transport in the electrolyte media, while interfacial impedance indicates the ion transport across electrode-electrolyte interface. The temperature-dependent data is fitted to VFT model
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Choudhury, S. (2019). Designing Solid-Liquid Interphases for Sodium Batteries. 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_6

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