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Solid Polymer Interphases for Lithium Metal Batteries

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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))

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Abstract

Metal-based batteries that comprise of a reactive metal anode like lithium, sodium, or potassium are the future of energy storage devices because of their high volumetric and gravimetric energy density. However, these batteries fail by three distinct modes – chemical instability due to internal reactions, morphological instability due to uneven electrodeposition, and hydrodynamic instability due to convective flows at the vicinity of electrode-electrolyte interface. Both liquid-based and solid-state electrolytes have their individual advantages and disadvantages in mitigating these issues. Here, we show that solid polymer interphases based on cross-linked polymer networks can essentially possess qualities from both of these worlds. We find that by tuning the thermodynamic interactions between the polymer network and oligomer diluents, one can control the bulk properties like ion transport and mass transfer rate. Thus, it is possible to design solid-like electrolyte phases where the electroconvective flows can be inhibited while maintaining high ionic conductivity. We further show that these polymer networks act as excellent interfacial layer for lithium metal electrode to inhibit dendrite growth and side reactions. On pairing with high voltage cathodes, the lithium metal battery at ambient conditions exhibit over 250 cycles of stable operation even at a high rate of 1 mA/cm2.

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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. 10.1
figure 5

Photograph of the flexible cross-linked membrane

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Supplementary Fig. 10.2
figure 6

FTIR analysis of the cross-linked membrane at various PEGDMA content that shows C=O bond at (1700 cm−1) shifting to lower intensity values as the volume percent PEGDMA is increased in solution

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Supplementary Fig. 10.3
figure 7

Schematic demonstrating the concept of stabilization using a solid polymer interphase

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Supplementary Fig. 10.4
figure 8

Thermograms obtained from differential scanning calorimetry for pure diglyme (Φ = 0%) and pure PEGDMA network (Φ = 100%). The dotted lines mark the step-change in the heat flow

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Supplementary Fig. 10.5
figure 9

d.c. conductivity as a function of inverse absolute temperature. Measured values are shown as markers, and the data is fitted to Vogel-Fulcher-Tamman function

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Supplementary Fig. 10.6
figure 10

Current as a function of voltage. Divergence in current was seen for Φ = 0% and Φ = 20%, signaling the presence of electroconvection. For Φ = 40% and beyond, the current reached a limiting value at higher voltages

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Supplementary Fig. 10.7
figure 11

Coulombic efficiency measurement in Li||stainless steel coin cell with and without the solid polymer interphase at a current density of 1 mA cm−2 and capacity of 1 mAh cm−2, using the 1 M LiPF6 in EC/DMC electrolyte

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Supplementary Fig. 10.8
figure 12

Cycling performances for Li||NMC cell operated at a C-rate of (a) C/5 and (b) C/2. Here the lithium metal electrode was coated with the solid polymer interphase that comprises of the polymer network and diglyme, with PEGDMA content of 40%. The thickness of the polymer coating was ~100 μm. The capacity of cathode is 2 mAh/cm2, and the electrolyte used here is 0.6 M LiTFSI, 0.4 M LiBOB, and 0.05 LiPF6 in EC/DMC (1:1 by wt.)

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Supplementary Fig. 10.9
figure 13

Cycling performances for Li||NMC cell operated at a C-rate of C/5. Here the electrolyte utilized was an all-solid-state polymer electrolyte that comprises of the polymer network and diglyme, with PEGDMA content of 40% and with the salt LiNO3 (Li:EO = 0.10) and 0.4 M LiBOB as additive. The thickness of the solid polymer electrolyte was ~400 μm. The capacity of cathode is 2 mAh/cm2. The cathode surface was wetted by liquid electrolyte of diglyme-LiNO3 (Li:EO = 0.1) and 0.4 M LiBOB

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Choudhury, S. (2019). Solid Polymer Interphases for 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_10

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