Secondary Zinc-air Batteries Research Articles

Development of Zinc-Air Batteries with Advanced Aqueous Electrolytes: A Model-Based Approach

Zinc-air batteries (ZABs) are promising candidates for next-generation electrochemical energy storage. They offer a high theoretical specific energy (1086 Wh∙kg-1) and energy density (6093 Wh∙l-1), are based on cheap and non-hazardous materials, and have superior operational safety characteristics. In fact, primary alkaline ZABs already have a long history in low-current industrial applications like hearing aids (1). But over time, the alkaline electrolyte reacts with CO2 to form carbonates, which reduces the ionic conductivity of the electrolyte and degrades the performance of the battery (2). Furthermore, metallic zinc can irreversibly passivate when discharged and may build dendrites when charged. We have developed continuum models based on principles of electrochemical thermodynamics and kinetics to simulate the performance of metal-air batteries (3, 4). Our models for ZABs introduce a new method for considering the thermodynamic stability of aqueous species in continuum simulations. By combining this approach with the basic aspects of electrochemical cell modeling (like mass transport in concentrated electrolytes, multi-phase flow in porous media, and concentration-dependent electrochemical reaction kinetics), we are able to investigate transient and spatially resolved changes in cell potential, electrolyte concentrations, and multi-phase volume fractions. Our investigation specifically considers ZABs with two different types of aqueous electrolytes: alkaline KOH and neutral ZnCl2-NH4Cl. For ZABs with alkaline KOH electrolytes, our simulations show that inhomogeneous Zn dissolution and ZnO precipitation cause the zinc electrode to change shape when cycled and lead to the local depletion of KOH, which induces type II (irreversible) ZnO passivation. Furthermore, the dissolution of CO2 in the electrolyte leads to a steady drop in cell potential over months of operation (2). In the neutral ZnCl2-NH4Cl electrolyte, the low OH- concentration limits the formation of carbonates, potentially extending the lifetime of the battery (5-7). However, in the near-neutral pH regime the stability of the aqueous zinc-ligand complexes shifts significantly with even small changes in concentration. This affects the ionic conductivity of the electrolyte, the composition of the final discharge product, and the pH stability. Our simulations show that under conditions reported in the literature, the pH may become strongly acidic, which affects the performance and stability of the bifunctional air catalyst (6-8). We investigate how the composition of the electrolyte and the architecture of the cell can be adjusted to maintain a stable, neutral pH over cycling. In this contribution, we highlight the physical and electrochemical processes which govern ZAB performance, and discuss how these processes can be managed to develop a rechargeable battery. This work is supported by the European Union Horizon 2020 project ZAS! (Zinc Air Secondary Batteries Based on Innovative Nanotechnology for Efficient Energy Storage).

Selective Ion Transporting Polymerized Ionic Liquid Membrane Separator for Enhancing Cycle Stability and Durability in Secondary Zinc-Air Battery Systems.

Rechargeable secondary zinc-air batteries with superior cyclic stability were developed using commercial polypropylene (PP) membrane coated with polymerized ionic liquid as separators. The anionic exchange polymer was synthesized copolymerizing 1-[(4-ethenylphenyl)methyl]-3-butylimidazolium hydroxide (EBIH) and butyl methacrylate (BMA) monomers by free radical polymerization for both functionality and structural integrity. The ionic liquid induced copolymer was coated on a commercially available PP membrane (Celguard 5550). The coat allows anionic transfer through the separator and minimizes the migration of zincate ions to the cathode compartment, which reduces electrolyte conductivity and may deteriorate catalytic activity by the formation of zinc oxide on the surface of the catalyst layer. Energy dispersive X-ray spectroscopy (EDS) data revealed the copolymer-coated separator showed less zinc element in the cathode, indicating lower zinc crossover through the membrane. Ion coupled plasma optical emission spectroscopy (ICP-OES) analysis confirmed over 96% of zincate ion crossover was reduced. In our charge/discharge setup, the constructed cell with the ionic liquid induced copolymer casted separator exhibited drastically improved durability as the battery life increased more than 281% compared to the pure commercial PP membrane. Electrochemical impedance spectroscopy (EIS) during the cycle process elucidated the premature failure of cells due to the zinc crossover for the untreated cell and revealed a substantial importance must be placed in zincate control.

Manganese oxide catalysts for secondary zinc air batteries: from electrocatalytic activity to bifunctional air electrode performance

An efficient, durable and low cost air cathode with low polarization between the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is essential for a high performance and durable secondary zinc-air battery. Different valence states and morphologies of MnxOy catalysts were synthetized via thermal treatment of EMD (generating Mn2O3 and Mn3O4) and acid digestion of synthetized Mn2O3 (producing α-MnO2) in order to develop an efficient Bifunctional Air Electrode (BAE). Change in the ratio H+ to Mn2O3 during the acid digestion affects the sample microporosity, the crystallographic plane distribution, as well as the physical and chemical adsorbed water which was related to defects, i.e. cation vacancies (Mn4+) and Mn3+. These characteristics were discussed and linked to the electrocatalytic activity. The best ORR performing catalyst was that with the higher surface water content (associated to material BET surface area) and a (310) surface as the 2nd more contributing plane (after 211). On the other hand, the catalyst with the higher structural water and with (110) and (200) crystallographic planes being the most intensity contributors (after 211) was the most OER active material. In this work, it was able to find a relationship between catalyst structure and air-efficiency through a volcano-like relationship between air-efficiency and surface water content. Air-efficiency (also take as round-efficiency discharge/charge in battery context) can be taken as a good descriptor of potentially good materials for Zn-Air secondary batteries technology. In this term, we were able to prepare a Bifunctional Air Electrode based on the selected α-MnO2 sample which demonstrated a round-efficiency of 53%, a ΔV around 1V and a neglected loss of the charge potential (about 2.1V) over the entire lifecycle test (more 200 cycles over 30hours) with a capacity retention superior to 95%.

Enhancement of Cycle Stability and Durability in Secondary Zinc-Air Batteries By Optional Ion-Transporting Separator

Highly durable secondary zinc air batteries were developed using polypropylene (PP) membrane (Celguard 5550) coated with polymerized ionic liquid as separators. The anionic exchange polymer was synthesized copolymerizing 1-[(4-ethenylphenyl)methyl]-3-butyl-imidazolium hydroxide (EBIH) and butyl methacrylate (BMA) monomers by free radical polymerization for both functionality and structural integrity. The ionic liquid induced copolymer was coated on a commercially available PP membrane. The coat allows anionic transfer through the separator and minimizes the migration of zincate ions, which causes the loss of active sites by the formation of zinc oxide on the surface of the catalyst layer. Electrochemical Impedance Spectroscopy (EIS) during the cycle process elucidated the premature failure of cells due to the zinc cross over for the untreated cell and revealed a substantial importance must be placed in zincate control. Scanning electron microscopy (SEM) revealed significant decrease in the porosity of the coated film without large cell performance sacrifice. Energy dispersive x-ray spectroscopy (EDS) data revealed the copolymer coated separator showed less zinc element in the cathode electrolyte, indicating lower zinc permeation through the membrane. Ion Coupled Plasma Optical Emission Spectroscopy (ICP-OES) analysis confirmed over 96% of zinc ion cross over was reduced. In our charge/discharge setup, the constructed cell with the ionic liquid induced copolymer casted separator exhibited drastically improved durability as the battery life increased more than 281% compared to the pure commercial PP membrane.

Alkaline aqueous electrolytes for secondary zinc-air batteries: an overview

Summary New applications and emerging markets in electromobility and large-scale stationary energy storage require the development of new electrochemical systems with higher energy density than current batteries. Rechargeable metal–air batteries, mainly lithium–air and zinc–air systems, are considered one of the most promising candidates. In contrast to lithium, zinc is abundant, inexpensive and its electrodeposition in aqueous electrolytes is relatively easy. Unfortunately, achieving a rechargeable zinc–air battery is still hindered by various technical problems related to the reversibility and lifetime of the electrodes. The most widely used electrolyte in zinc–air batteries has been the classical aqueous alkaline. In this context and with the main objective of providing a complete overview, we studied a wide number of articles starting from the beginning of the development of secondary zinc–air batteries (1970–1980s) to more recent works, with the aim of compiling all available information. It is essential to revise older papers to find relevant information that may get otherwise forgotten and not taken into account to develop new solutions. This information could also be applied in other storage systems based on zinc as nickel–zinc, zinc hybrid or zinc-ion. Copyright © 2016 John Wiley & Sons, Ltd.

Zinc electrode with anion conducting polyvinyl alcohol/poly(diallyldimethylammonium chloride) film coated ZnO for secondary zinc air batteries

Zinc electrode with polyvinyl alcohol(PVA)/poly(diallyldimethylammonium chloride) (PDDA) film coated ZnO was prepared by a chemical cross-linking method. The PVA/PDDA polymer film has an interpenetrating network structure where PVA works as polymer matrix and PDDA as anion charge carriers. Fourier transform infrared spectra (FT-IR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies reveal that a polymer film with well-connected three dimensional network structure is formed around ZnO nanoparticles. Linear sweep voltammetry, cyclic voltammetry (CV) and charge/discharge cycling tests were carried out on the ZnO/PVA/PDDA composite electrode, which exhibits higher electrochemical activity and dramatically superior cycle stability than the bare ZnO electrode without polymer films. The ZnO/PVA/PDDA electrode showed remarkably lower solubility during cycling.

Model based quantification of air-composition impact on secondary zinc air batteries

In this work we present an isothermal mathematical model of a secondary zinc air battery with alkaline liquid electrolyte. The model approach is flexible and allows to analyze the impact of surrounding air composition with its relative humidity, carbon dioxide and oxygen content on battery operation. We thereby apply an idealized approach to explore general limitations which give useful predictions for practical zinc air battery operation. Galvanostatic charge and discharge simulations show that air composition strongly impacts zinc air battery operation. Water level at anode and cathode, species concentrations and cell potential are shown to vary with air-composition impact during operation and may reach critical values which reduce battery lifetime. In detail, we deduce that intermediate relative humidity values of approximately 65%, carbon dioxide concentrations below 10 ppm and pure oxygen are beneficial for high performance and long term stable zinc air battery operation at 298 K with 6M potassium hydroxide as alkaline liquid electrolyte. The presented results will give useful information on operating strategies for zinc air batteries and electrochemical energy storage systems with open air electrode. The model might be adapted for other metal air batteries with aqueous electrolyte.

Gas Diffusion Electrodes and Ionic Liquid Electrolytes for Secondary Zinc-Air Batteries: Electrochemical Characterization

not Available.

Electrochemical, Transport, and Spectroscopic Properties of 1-Ethyl-3-methylimidazolium Ionic Liquid Electrolytes Containing Zinc Dicyanamide

The electrochemical, physical, and transport properties of 1-ethyl-3-methylimidazolium dicyanamide [emim][dca] containing varying levels of Zn2+ and H2O have been investigated to evaluate the suitability of dicyanamide (dca–) ionic liquids (ILs) for applications in secondary zinc–air batteries. Electrochemical experiments indicate that [emim][dca] containing Zn(dca)2 can support high current density Zn0/Zn2+ deposition and stripping, at Zn(dca)2 concentrations up to 40 mol % and H2O concentrations of 10 wt %. Physical property experiments show that good conductivities can be obtained in these IL/Zn2+ systems. The [emim][dca] containing 30 mol % Zn(dca)2 electrolyte displayed higher conductivities (15 mS·cm–1 at 25 °C) than the same IL containing 30 mol % ZnCl2 (12 mS·cm–1 at 25 °C). A significant difference in the solvation environments of the Zn2+ in the two IL/zinc salt mixtures has been suggested to be the cause of the significant improvement in physical and electrochemical properties of [emim][dca] co...

Synthesis and electrochemical performance of La0.7Sr0.3Co1−xFexO3 catalysts for zinc air secondary batteries

We prepared La0.7Sr0.3Co1−xFexO3 (x=0.1–0.4) catalysts for a zinc air battery by using the citrate method under controlled pH. The prepared precursor powder was heat treated at the calcination temperature of 700 °C and examined for the optimum structure of the cathode. The structure and performance of the catalysts were examined by x-ray diffraction and a scanning electron microscope. The air electrode was prepared by blending the catalyst, Vulcan XC-72R (carbon black), and (polytetrafluoroethylene PTFE) suspension. The oxygen reduction reaction and the oxygen evolution reaction were examined by linear sweep voltammetry. The results showed that La0.7Sr0.3Co0.7Fe0.3O3 (LSCF0.7) is an excellent catalyst for the zinc air secondary battery.

아연공기이차전지용 La1-xSrxCoO3양극촉매의 제조 및 이를 적용한 양극의 전기화학적 특성연구

We synthesized nano-sized <TEX>$La_{1-x}Sr_xCoO_3$</TEX> (<TEX>$x=0.1{\sim}0.4$</TEX>) cathode catalyst for the zinc air secondary batteries by citrate method, And we measured the cathode's electrochemical characteristics according to content of strontium compose the cathode catalyst. We controlled the pH of precursor solution by 10 in the process of manufacturing the precursor, We heat treated the prepared precursor at various calcination temperature (<TEX>$500{\sim}900^{\circ}C$</TEX>), and examined the optimum calcinations temperature by XRD analysis and electrochemical evaluation. We examined the ORR (oxygen reduction reaction) and OER (oxygen evolution reaction) performance of the prepared <TEX>$La_{1-x}Sr_xCoO_3$</TEX> catalyst powder. When we consider ORR and OER performance simultaneously, <TEX>$La_{0.7}Sr_{0.3}CoO_3$</TEX> catalyst has shown the best performance because of its lowest voltage deference between charge and discharge.

Electrochemical evaluation of La1 − x Ca x CoO3 cathode material for zinc air batteries application

We synthesized nano-sized La1 − xCaxCoO3 (x = 0.1–0.4) cathode catalysts for zinc air secondary batteries by the citrate method, and measured electrochemical characteristics of the cathodes according to the cathode catalyst’s calcium content. We heat treated the prepared precursor at a calcination temperature of 700°C, and examined it by XRD analysis and electrochemical evaluation. We examined the prepared La1 − xCaxCoO3 catalyst powder’s oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and cycle-stability performance. When we consider ORR, OER and cycle-stability performance simultaneously, La0.9Ca0.1MnO3 catalyst showed the best performance because of its lowest voltage deference between charge and discharge, and its lowest degradation according to cycle.

Preparation and Electrochemical Evaluation of La&lt;sub&gt;1-x&lt;/sub&gt;Sr&lt;sub&gt;x&lt;/sub&gt;MnO&lt;sub&gt;3&lt;/sub&gt; Cathode Material for Zinc Air Secondary Batteries Application

We prepared nano-sized La1-xSrxMnO3 (x=0.2~0.5) cathode catalyst for the zinc air secondary batteries by citrate method and measured cathode’s electrochemical characteristics according to content of strontium compose the cathode catalyst. We heat treated the prepared precursor at various calcination temperature (500~900), and examined the optimum calcinations temperature by XRD analysis and electrochemical evaluation. We examined the ORR (oxygen reduction reaction) and OER (oxygen evolution reaction) performance of the prepared La1-xSrxMnO3 catalyst powder. La0.7Sr0.3MnO3 and La0.8Sr0.2MnO3 catalyst has shown the best performance in the ORR. But in the OER, La0.7Sr0.3MnO3 catalyst has shown better performance. When we consider ORR and OER performance simultaneously, La0.7Sr0.3MnO3 catalyst has shown the best performance because of its lowest voltage difference between charge and discharge.

On the use of third electrodes in a secondary zinc-air battery: J. J. Postula and R. Thacker, Electrochemistry Department, Research Laboratories, General Motors Corporation, Warren, Michigan, U.S.A. Energy Conversion10, 45–49 (1970)

On the use of third electrodes in a secondary zinc-air battery: J. J. Postula and R. Thacker, Electrochemistry Department, Research Laboratories, General Motors Corporation, Warren, Michigan, U.S.A. Energy Conversion10, 45–49 (1970)

On the use of third electrodes in a secondary zinc-air battery

The use of third electrodes for charging a secondary zinc-air battery is described. Performance data for single cells and for the battery are presented. The characteristics of the battery are: open-circuit voltage, 21·1 V; maximum power, 366 W at 38 A and 9·6 V; energy density, 23 W-hr/lb and 1350 W-hr/ft 3; peak density, 15 W/lb and 880 W/ft 3. Some of the problems encountered in the operation of the battery are discussed.

On the use of third electrodes in a secondary zinc-air battery: J. J. Postula and R. Thacker, Electrochemistry Department, Research Laboratories, General Motors Corporation, Warren, Michigan, U.S.A. Energy Conversion10, 45–49 (1970)

On the use of third electrodes in a secondary zinc-air battery: J. J. Postula and R. Thacker, Electrochemistry Department, Research Laboratories, General Motors Corporation, Warren, Michigan, U.S.A. Energy Conversion10, 45–49 (1970)

On the use of third electrodes in a secondary zinc-air battery: J. J. Postula and R. Thacker, Electrochemistry Department, Research Laboratories, General Motors Corporation, Warren, Michigan, U.S.A. Energy Conversion10, 45–49 (1970)

On the use of third electrodes in a secondary zinc-air battery: J. J. Postula and R. Thacker, Electrochemistry Department, Research Laboratories, General Motors Corporation, Warren, Michigan, U.S.A. Energy Conversion10, 45–49 (1970)