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Making zinc-air batteries rechargeable using developed cobalt(II) oxide as a catalyst

Zinc-air batteries are a promising alternative to expensive lithium-ion batteries. Compared with lithium-ion technology, zinc-air batteries have a greater energy density, very low production cost, and superior safety. However, their fundamental inability to recharge has lowered their wide-scale adoption.

Zinc-air batteries use charged zinc particles to store large amounts of electricity at a time. When electricity is required, the charged zinc is combined with oxygen from the air (and water), releasing the stored electricity and producing zincate. This process is known as oxygen reduction reaction (ORR).

Theoretically, this zincate can again be broken down into oxygen and zinc ions by passing electricity through it. This process, in turn, is called oxygen evolution reaction (OER). Using these reactions, zinc-air batteries can be made rechargeable, competing with lithium-ion batteries.

The major challenge of the recharging process is the sluggish kinetics of the reactions which lead to poor cycle life. These batteries require a catalyst that could potentially enhance the ORR and the OER reactions, making their kinetics fast. Hence, the development of highly efficient catalysts is of paramount importance for rechargeable zinc-air batteries.

Previous studies have suggested transition-metal oxides as great bifunctional ORR / OER catalysts because of their ability to provide sites for the reversible adsorption of oxygen. But the methods involved in creating well-defined defects for reversible adsorption of oxygen in such oxides are challenging.

To investigate the use of cobalt(II) oxide nanosheets deposited on stainless steel or carbon cloth as a bifunctional catalyst, a group of researchers from different universities of China and Canada collaborated and conducted several experiments. Their research findings were published in the journal Nano Energy .

Research approach

Preparation of catalyst

Different nano-structures were prepared using simple heat treatment and electrodeposition to test them as bifunctional electrocatalysts. The type of nano-structures prepared were:

      • Cobalt hydroxide  nanosheets on steel and carbon cloth
      • Layered cobalt (II) oxide nanosheet on steel and carbon cloth
      • Cobalt (II) oxide on steel
      • Layered cobalt tetroxide nanosheet on steel

Material Characterization

To understand the characteristics of the prepared samples, various analyticaland tests were carried out:

Charging and discharging tests

Later discharge and charge cycling tests of single cells were operated by the battery testing system.

Results

The simple heat treatment strategy created oxygen vacancy sites. According to the authors, layered cobalt-oxide nano-sheets exhibited excellent bifunctional ORR / OER performance. Investigations suggested abundant oxygen vacancies and cobalt sites be the reason for enhanced ORR / OER performance. Later, the developed layered cobalt-oxide nanosheets on steel were used as an electrode in a rechargeable zinc-air flow battery and a record-breaking cycle life of over 1,000 hours with nearly unchanged voltage was observed. Galvanostatic discharging-charging cycles also demonstrated long life and high energy efficiency.

This research carried out provides a new method to design highly efficient bifunctional ORR / OER catalysts that could be used to enhance the cycle life of rechargeable zinc-air flow batteries. At Frontis Energy we are looking forward to industrial applications.

(Photo: Engineersforum)

Reference: https://doi.org/10.1016/j.nanoen.2020.105409 Wu et al., Cobalt (II) oxide nanosheets with rich oxygen vacancies as highly efficient bifunctional catalysts for ultra-stable rechargeable Zn-air flow battery, 2021

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Production of Green Hydrogen through exposure of nano particles to sunlight

The demand for energy is increasing and raw material for the fossil fuel economy is diminishing. Moreover, the emission of gases from fossil fuel usage significantly degrades air quality. The carbon by-products produced from these fossil fuels severely affect the climate.

Hence, there is a need to find a renewable energy resource, that can be produced, stored, and used easily as per requirement. Hydrogen can be a promising energy resource as it is an abundantly available, non-toxic resource, and can be readily used to store excess electrical energy.

Hydrogen when combined with oxygen in a fuel cell produces electricity and the by-products obtained are water and heat. Based on the method of production of hydrogen it is categorized as blue hydrogen and green hydrogen. Blue hydrogen is produced from fossil fuels such as methane, gasoline, coal while green hydrogen is produced from non-fossil fuels / water. The cleanest way to produce eco-friendly hydrogen is via electrolysis of water where water is electrolyzed to separate hydrogen and oxygen. Renewable energy can be used as a power electrolyzer to produce hydrogen from water. Solar driven photo electrochemical (PEC) water splitting is one of the common method used these days. In photo electrochemical (PEC) water splitting, hydrogen is produced from water using sunlight.

PEC cells comprise of a working photoelectrode and a counter electrode. The photoelectrode consists of semiconductor material with a band gap to absorb solar light and generate an electron-hole pair. The photo-generated charges are responsible for the oxidation of water and its reduction into hydrogen. The PEC suffer devices from low stability and efficiency.

The research team from the  Institut national de la recherche scientifique (INRS) along with researchers from the Institute of Chemistry and Processes for Energy, Environment and Health (ICPEES) , a CNRS-University of Strasbourg joint research lab published a way to significantly improve the efficiency of water dissociation to produce hydrogen by the development of sunlight photosensitive-nanostructured electrodes.

A comparative study between cobalt and nickel oxide nanoparticles deposited onto TiO 2 nanotubes prepared through anodization was carried out. The TiO 2 nanotubes were decorated with CoO (cobalt oxide) and NiO (nickel oxide) nanoparticles using the reactive pulsed laser deposition method. The surface loadings of CoO or NiO nanoparticles were controlled by the number of laser ablation pulses. The efficiency of CoO and NiO nanoparticles as co-catalysts for photo-electrochemical water splitting was studied by cyclic voltammetry, under both simulated sunlight and visible light illuminations and by external quantum efficiency measurements

The entire research work was carried out in the following steps:

Catalyzed Green Hydrogen synthesis
Steps followed to improve the efficiency of hydrogen production

(Source: Favet et al ., Solar Energy Materials and Solar Cells , 2020)

In this study Cobalt (CoO) and Nickel (NiO) oxides were considered as effective co-catalysts for splitting water molecules. Both co-catalysts improved photo-electrochemical conversion of ultra violet as well visible light photons.

However, CoO nanoparticles were found to be the best co-catalyst under visible light illumination, with a Photo Conversion Efficiency almost 10 times higher than for TiO 2 . The performance of CoO nanoparticles got enhanced in the visible spectral region (λ> 400 nm). The possible reason can be a consequence of their visible bandgap which enables them to harvest more photon in the 400-500 nm range and transferring effectively the photo-generated electrons to TiO 2 nanotubes.

At Frontis Energy we are exited about these new discovery to improve hydrogen production from sunlight and hope to see an industrial application soon.

(Image: Engineersforum)

Reference: Favet et al ., Solar Energy Materials and Solar Cells , 2020

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Cobalt Nanocrystals Make Lithium-Ion Batteries Age More Slowly

In todays Li-ion batteries, cobalt oxide cathodes improve performance and durability. While, such cobalt cathodes show the same performance as nickel oxide cathodes, they come at a higher price. Nickel cathodes, in turn, crack and dissolve quickly, which reduces their lifespan. Nevertheless, nickel cathodes are very popular because they are so cheap.

Now, the research team led by Jaephil Cho of the Ulsan National Institute of Science and Technology in South Korea has developed a cathode made of more than 80% nickel. The researchers reported in the journal Energy & Environmental Science that a cathode coated with nanocrystals of cobalt aged more slowly than conventional nickel cathodes. After recharging 400 times at room temperature, the battery was able to retain 86% of its original capacity.

The novel nickel cathodes could help meet the growing demand for rechargeable batteries in electric vehicles if cobalt prices rise in the future.

(Photo: Wikipedia)