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Rational Design of Nanostructured Polymer Electrolytes and Solid–Liquid Interphases for Lithium Batteries pp 13–33Cite as

Hybrid Hairy Nanoparticle Electrolytes Stabilize Lithium Metal Batteries

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Abstract

Rechargeable batteries comprising an energetic metal (e.g., Li, Na, Al) at the anode provide unparalleled opportunities for increasing the energy stored in batteries either on a per unit mass or volume basis. A major problem that has hindered development of such batteries for the last three decades concerns the electrochemical and mechanical instability of the interface between an energetic metal and an ion conducting organic liquid electrolyte. This study reports that hybrid electrolytes created by blending low volatility liquids with a bi-disperse mixture of hairy nanoparticles provide multiple attractive attributes for engineering electrolytes that are stable in the presence of reactive metals and at high charge potentials. Specifically, we report that such hybrid electrolytes exhibit exceptionally high-voltage stability (>7 V) over extended times; protect the Li metal anode by forming a particle-rich coating on the electrode that allows stable long-term cycling of the anode at high-coulombic efficiency; and manifest low bulk and interfacial resistance at room temperature that enables stable cycling of Li/LiFePO4 half-cells at a C/3 rate. We also investigate connections between particle curvature and ion transport in the bulk and at interfaces in such bi-disperse hybrid electrolytes.

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Authors and Affiliations

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

    Snehashis Choudhury

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Appendix: Supplementary Information

Appendix: Supplementary Information

Supplementary Fig. 2.1
figure 7

Variation of glass transition temperature (open symbols) and diffusivity (close symbols) as a function of fraction of larger particles xL, for core volume fractions (a) ϕ = 0.2 and (b) ϕ = 0.4. The dashed lines are guide to the eye

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Supplementary Fig. 2.2
figure 8

Evolution of structure factor S(q) as a function of the wave vector q at volume fractions Φ = 0.2, 0.3, and 0.4 for (a) xL = 0, (b) xL = 0.25, (c) xL = 0.75, and (d) xL = 1. The open symbols are experimental values, and the dashed lines are fit to experimental S(q) using binary hard sphere model

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Supplementary Fig. 2.3
figure 9

Variation in three components of structure factor, viz., S11, S12, and S22, as estimated from binary hard sphere model predictions. Here, 1 and 2 indicate smaller and larger particles, respectively. The structure factors are shown for xL = 0.5 for different volume fractions (a) Φ = 0.2, (b) Φ = 0.3, and (c) Φ = 0.4

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Supplementary Fig. 2.4
figure 10

Electrical double layer (square symbols) and electrochemical capacitance (triangle symbols) for different values of xL at (a) Φ = 0.2 and (b) Φ = 0.4

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Supplementary Fig. 2.5
figure 11

(a) Electrochemical impedance measurements for a symmetric lithium cell before polarization (open symbols) and after steady state is reached (closed symbols). R0 and Rss were determined by fitting these impedances to the circuit model mentioned in the main text. (b) Current decay for the cell undergoing polarization at 20 mV potential. I0 and ISS were used in the calculations as observed in the plot

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Choudhury, S. (2019). Hybrid Hairy Nanoparticle Electrolytes Stabilize Lithium Metal 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_2

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