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Effect of Multiple Cation Electrolyte Mixtures on Rechargeable Zn-MnO2 Alkaline Battery
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
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Number of Authors: 112016 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 28, no 13, p. 4536-4545Article in journal (Refereed) Published
Abstract [en]

A Bi2O3 in beta-MnO2 composite cathode material has been synthesized using a simple hydrothermal method and cycled in a mixed KOH-LiOH electrolyte with a range of concentrations. We show that, at a KOH:LiOH molar ratio of 1:3, both proton insertion and lithium insertion occur, allowing access to a higher fraction of the theoretical capacity of the MnO2 while preventing the formation of ZnMn2O4. This enables a capacity of 360 mAh/g for over 60 cycles, with cycling limited more by anode properties than traditional cathodic failure mechanisms. The structural changes occurring during cycling are characterized using electron microscopy and in situ synchrotron energy-dispersive X-ray diffraction (EDXRD) techniques. This mixed electrolyte shows exceptional cyclability and capacity and can be used as a drop-in replacement for current alkaline batteries, potentially drastically improving their cycle life and creating a wide range of new applications for this energy storage technology.

Place, publisher, year, edition, pages
2016. Vol. 28, no 13, p. 4536-4545
National Category
Chemical Sciences Materials Engineering
Research subject
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-132950DOI: 10.1021/acs.chemmater.6b00232ISI: 000379704100004OAI: oai:DiVA.org:su-132950DiVA, id: diva2:956491
Available from: 2016-08-30 Created: 2016-08-26 Last updated: 2018-12-17Bibliographically approved
In thesis
1. Rechargeable Aqueous Batteries Based on Available Resources: Investigation and Development towards Efficient Battery Performance
Open this publication in new window or tab >>Rechargeable Aqueous Batteries Based on Available Resources: Investigation and Development towards Efficient Battery Performance
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Batteries employing water based electrolytes enable extremely low manufacturing costs and are inherently safer than Li-ion batteries. Batteries based on zinc, manganese dioxide, iron, and air have high energy relevancy, are not resource restricted, and can contribute to large scale energy storage solutions. Zinc has a rich history as electrode material for primary alkaline Zn–MnO2 batteries. Historically, its use in secondary batteries has been limited because of morphological uncertainties and passivation effects that may lead to cell failure. Manganese dioxide electrodes are ineffective as rechargeable electrodes because of failure mechanisms associated with phase transformations during cycling. The irreversibility of manganese dioxide is strongly correlated to the formation of the electrochemically inactive spinel, Mn3O4/ZnMn2O4. The development of the iron electrode for Fe–air batteries was initiated in late the 1960s and these batteries still suffer from charging inefficiency, due to the unwanted hydrogen evolution reaction. Meanwhile, the air electrode is limited in long-term operation because of the sluggish oxygen evolution and reduction kinetics. These limitations of the Fe–air battery yield poor overall efficiencies, which bring vast energy losses upon cycling.

Herein, the limitations described above were countered for rechargeable Zn–MnO2 and Fe–air batteries by synthesizing electrode materials and modifying electrolyte compositions. The electrolyte mixture of 1 M KOH + 3 M LiOH for rechargeable alkaline Zn–MnO2 batteries limited the formation of the inactive spinels and improved their cycle life significantly. Further, the formation of the inactive spinels was overcome in mildly acidic electrolytes containing 2 M ZnSO4, enabling the cells to cycle reversibly at lower pH via a distinctive reaction mechanism. The iron electrodes were improved with the addition of stannate, which suppressed hydrogen evolution. Furthermore, optimal charge protocols of the iron electrodes were identified to minimize the hydrogen evolution rate. On the air electrode, the synthesized NiCo2O4 showed excellent bifunctional catalytic activity for oxygen evolution and reduction, and was incorporated to a flow assisted rechargeable Fe–air battery, in order to prove the practicability of this technology. Studies of the electrode materials on the micro, macro, nano, and atomic scales were carried out to increase the understanding of the nature of and interactions between of these materials. This included both in operando and ex situ characterization. X-ray and neutron radiation, and analytical- and electrochemical methods provided insight to improve the performance and cycle life of the batteries.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm University, 2019. p. 66
Keywords
rechargeable aqueous batteries, alkaline electrolytes, aqueous sulfate electrolytes, zinc electrodes, manganese dioxide electrodes, iron electrodes, air electrodes, oxygen electrocatalysts
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-163154 (URN)978-91-7797-552-6 (ISBN)978-91-7797-553-3 (ISBN)
Public defence
2019-02-15, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
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Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Manuscript. Paper 5: Manuscript.

Available from: 2019-01-23 Created: 2018-12-17 Last updated: 2019-01-22Bibliographically approved

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