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. 2023 Jul 20;13(7):680.
doi: 10.3390/membranes13070680.

Electrodeposited Ionomer Protection Layer for Negative Electrodes in Zinc-Air Batteries

Papa K Kwarteng  1 , Suanto Syahputra  1 , Luca Pasquini  1 , Florence Vacandio  1 , Maria Luisa Di Vona  2 , Philippe Knauth  1
Affiliations

Electrodeposited Ionomer Protection Layer for Negative Electrodes in Zinc-Air Batteries

Papa K Kwarteng et al. Membranes (Basel). .

Abstract

The protection of zinc anodes in zinc-air batteries (ZABs) is an efficient way to reduce corrosion and Zn dendrite formation and improve cyclability and battery efficiency. Anion-conducting poly(N-vinylbenzyl N,N,N-trimethylammonium)chloride (PVBTMA) thin films were electrodeposited directly on zinc metal using cyclic voltammetry. This deposition process presents a combination of advantages, including selective anion transport in PVBTMA reducing zinc crossover, high interface quality by electrodeposition improving the corrosion protection of zinc and high ionomer stiffness opposing zinc dendrite perforation. The PVBTMA layer was observed by optical and electron microscopy, and the wettability of the ionomer-coated surface was investigated by contact angle measurements. ZABs with PVBTMA-coated Zn showed an appreciable and stable open-circuit voltage both in alkaline electrolyte (1.55 V with a Pt cathode) and in miniaturized batteries (1.31 V with a carbon paper cathode). Cycling tests at 0.5 mA/cm2 within voltage limits of 2.1 and 0.8 V gave a stable discharge capacity for nearly 100 cycles with a liquid electrolyte and more than 20 cycles in miniaturized batteries. The faster degradation of the latter ZAB was attributed to the clogging of the carbon air cathode and drying or carbonation of the electrolyte sorbed in a Whatman paper.

Keywords: anion exchange membranes; electropolymerization; metal–air batteries; oxygen reduction reaction.

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Conflict of interest statement

There are no conflict to declare.

Figures

Scheme 1
Scheme 1
Chemical formula of PVBTMA.
Figure 1
Figure 1
(a) Cyclovoltammogram of PVBTMA electrodeposition on Zn; (b) micrometric determination of PVBTMA coating thickness.
Figure 2
Figure 2
Spectroscopic characterization of PVBTMA. (a) 1H NMR spectrum; (b) FTIR spectrum.
Figure 3
Figure 3
(a) Typical impedance spectra and fit before and after PVBTMA electropolymerization on Zn (precursor solution: 0.01 M); (b) zoomed-in view of the high-frequency region.
Figure 4
Figure 4
SEM micrograph of Zn disk with PVBTMA layer.
Figure 5
Figure 5
Contact angle measurements: (a) bare Zn disk; (b) Zn with PVBTMA coating.
Figure 6
Figure 6
Open-circuit voltages of ZAB with PVBTMA-coated Zn.
Figure 7
Figure 7
(a) Charge–discharge curves (150 cycles) of ZAB with PVBTMA-coated Zn (0.01 M precursor solution) in alkaline electrolyte with i = 0.5 mA/cm2, (b) zoomed-in view of the first 10 cycles and (c) discharge capacity vs. cycle number.
Figure 8
Figure 8
Galvanostatic charge–discharge profiles of ZAB in alkaline electrolyte (i = 0.5 mA/cm2) with PVBTMA-coated Zn anode as function of the cycle number.
Figure 9
Figure 9
Impedance spectra before and after cycling of ZAB in alkaline solution using bare Zn and Zn with PVBTMA coating (insets: zoomed-in view (top), equivalent circuit (bottom)).
Figure 10
Figure 10
Optical microscope images of a Zn anode with PVBTMA coating: (a) before cycling; (b) after 150 cycles.
Figure 11
Figure 11
Miniaturized zinc–air battery components and assembly. The images show from the left the cathode part with carbon paper, the Whatman paper soaked with electrolyte, the PVBTMA-coated zinc anode and a Teflon piece to provide a robust assembly.
Figure 12
Figure 12
(a) First 22 charge–discharge cycles of miniaturized ZAB with PVBTMA-coated Zn; (b) ZAB charge–discharge cycling (75 cycles).
Figure 13
Figure 13
(a) Discharge capacity vs. cycle number (red dots) and open-circuit voltage (inset) and (b) voltage versus capacity curves at various cycles for a miniaturized ZAB with PVBTMA-coated Zn.
Figure 14
Figure 14
(a) Typical impedance spectra of miniaturized ZAB with PVBTMA-coated Zn and (b) zoomed-in view with Zplot fit.
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