Enhancing performance and longevity of solid-state zinc-iodine batteries with fluorine-rich solid electrolyte interphase

doi: 10.1088/2752-5724/ad50f1

1.
Australian Institute for Bioengineering and Nanotechnology (AIBN), The University of Queensland, Brisbane, QLD, 4072, Australia
2.
School of Chemical Engineering, The University of Queensland, Brisbane, QLD, 4072, Australia
3.
School of Chemistry and Molecular Biosciences, Faculty of Science, The University of Queensland, Brisbane, QLD, 4072, Australia
4.
Department of Chemistry, Faculty of Science, Imam Mohammad Ibn Saud Islamic University (IMSIU), Riyadh 11564, Saudi Arabia

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Corresponding author: E-mail: c.zhang3@uq.edu.au; E-mail: b.luo1@uq.edu.au

摘要

Abstract: AbstractRechargeable zinc-iodine (ZnI₂) batteries have gained popularity within the realm of aqueous batteries due to their inherent advantages, including natural abundance, intrinsic safety, and high theoretical capacity. However, challenges persist in their practical applications, notably battery swelling and vulnerability in aqueous electrolytes, primarily linked to the hydrogen evolution reaction and zinc dendrite growth. To address these challenges, this study presents an innovative approach by designing a solid-state ZnI₂ battery featuring a solid perfluoropolyether based polymer electrolyte. The results demonstrate the formation of a solid electrolyte interphase layer on zinc, promoting horizontal zinc growth, mitigating dendrite penetration, and enhancing battery cycle life. Moreover, the solid electrolyte hinders the iodine ion shuttle effect, reducing zinc foil corrosion. Symmetric batteries employing this electrolyte demonstrate excellent cycle performance, maintaining stability for approximately 5000 h at room temperature, while solid-state ZnI₂ batteries exhibit over 7000 cycles with a capacity retention exceeding 72.2%. This work offers a promising pathway to achieving reliable energy storage in solid-state ZnI₂ batteries and introduces innovative concepts for flexible and wearable zinc batteries.
- zinc-iodine battery /
- solid electrolyte /
- zinc metal anode /
- electrolyte interphase /
- shuttle effect
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Figure 1. Schematic illustration of ZnI₂ batteries with (a) aqueous ZnSO₄ solution and (b) solid PFZ as electrolyte. (c) FTIR spectra of PFZ and PF. (d) Tg comparison of PF polymer and PFZ. (e) LSV curves of the PFZ electrolyte and the liquid electrolyte (2 M aqueous ZnSO₄ solution electrolyte) using a two-electrode configuration (stainless steel foil as working electrode and Zn foil as reference and counter electrodes). (f) CV curves of Zn plating/stripping using two-electrodes configuration in PFZ (stainless steel foil as working electrode and Zn foil as reference and counter electrodes) and 2 M aqueous ZnSO₄ solution. Inset: Digital photos of the battery cycled in 2 M aqueous ZnSO₄ solution electrolyte and PFZ electrolyte. (g) Potentiodynamic polarization curves using two-electrode configuration (zinc foil as working electrode and another zinc foil as reference electrode and counter electrode) showing the corrosion behaviors on zinc metal. (h) EIS spectra of PFZ electrolyte and the fitting curve.

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Figure 2. Symmetric batteries performance. (a) Galvanostatic Zn plating and stripping in Zn//ZnSO₄//Zn and Zn//PFZ//Zn symmetrical batteries at current densities of 0.2 mA cm^-2. The inset is the voltage profile of symmetrical cell at (b)1st hour, (c) 4000th hour. SEM images of cross-section of the zinc foil cycled in (d) 2 M ZnSO₄ aqueous solution and g) PFZ. (e) Coulombic efficiency of Zn deposition at the current density of 0.2 mA cm^-2 and (f) the details of 1000th cycle, 2000th cycle and 3000th cycle.

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Figure 3. Full solid-state Zn//PFZ//I₂ batteries performance. (a) Cycle stability and coulombic efficiency of Zn//PFZ//I₂ battery at 0.5 C. (b) Voltage profiles at different cycles of Zn//PFZ//I₂ battery. (c) Rate performance and charge/discharge profiles of the Zn//PFZ//I₂ battery at current densities varying from 0.5 C to 20 C. (d) Rate performance comparison with other zinc iodine batteries with gel electrolyte. (e) CV curves at different scan rates of 0.5 mV s^-1, 2 mV s^-1, and 5 mV s^-1. (f) First 6 cycles charge/discharge curve of Zn//PFZ//I₂ soft-pack battery.

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Figure 4. Effects on I₃^- shuttling process in ZnI₂ batteries. (a) Photographs of H-shape tanks containing a deep brown triiodide solution (1 M KI + 0.1 M I₂, left tank) and a colorless 0.5 M KI solution (right tank), each separated by either a GF separator or PFZ at various time intervals. (b), (c) UV-vis curve of solution in the H-shape right tanks after different time using different separators (GF separator and PFZ). (d) I 3d XPS spectra of Zn surface cycled 10 times with GF as separator etched by 10 keV Ar⁺ as a function of etching time. (e) I 3d XPS spectra of Zn surface cycled 10 times with PFZ as separator etched by 10 keV Ar⁺ as a function of etching time. (f), (g) Voltage drops in charge-discharge cycling and self-discharge tests of (f) aqueous ZnI₂ battery and (g) solid-state ZnI₂ battery.

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Figure 5. Characterization of metallic Zn electrode. XRD patterns of Zn anodes at various states of charge and discharge cycled in (a) 2 M ZnSO₄ aqueous solution and (b) PFZ. SEM images of Zn anode cycled in (c) 2 M ZnSO₄ aqueous solution and (d) PFZ at 0.5 mA cm^-2 in the Zn//PFZ//Zn symmetric battery. (e) XRD patterns of Zn anode cycled 5, 50 and 500 times in PFZ. (f), (g) XPS results of Zn anode cycled 5 times in Zn//PFZ//Zn symmetric battery. (h) Raman spectroscopy of Zn anode cycled in 2 M ZnSO₄ aqueous solution and PFZ.

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