Synthesis and characterization ofmanganese dioxide cathodes for Zn-ionbatteries
Başlık çevirisi mevcut değil.
- Tez No: 720418
- Danışmanlar: PROF. BENEDETTO BOZZİNİ, PROF. FRANCESCA ROSSİ
- Tez Türü: Yüksek Lisans
- Konular: Enerji, Mühendislik Bilimleri, Energy, Engineering Sciences
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 2021
- Dil: İngilizce
- Üniversite: Politecnico di Milano
- Enstitü: Yurtdışı Enstitü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 114
Özet
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Özet (Çeviri)
The chemistry of rechargeable aqueous Zn/MnO2 batteries in a neutral or mildly acidic electrolyte has drawn great attention recently due to the fact that all of the components of a Zn/MnO2 battery are safe, abundant, and sustainable. MnO2-based cathodes are promising for zin ion battery (ZIB) applications due to their high theoretical capacity and voltage. However, they suffer from severe capacity fading after prolonged charge-discharge cycles, and the reaction mechanism of the MnO2 cathode remains a topic of discussion. This thesis concerns two important subject matters: synthesis of manganese dioxide catalyst with the micro-wave-assisted hydrothermal method and electrodeposition methods, followed by electrochemical characterization of the synthesized active manganese-based material by various electrochemical and structural analysis. The first section of this thesis examined the basic electrodeposition mechanism of MnO2 films on different electrodes using the cyclic voltammetry technique, beginning by reproducing previously published experiments and then varying the chemical composition of aqueous electrodeposition solutions to provide meaning for the potential role of cations in the intercalation mechanisms. In the following section, we conducted a systematic exploration of a subset of the electrodeposition parameter space in order to lay the groundwork for our next work on the effect of Zn2+ in neutral electrolytes. Due to the scarcity of electroanalytic work in neutral electrolytes, work in an acidic environment at a Pt electrode was chosen as a benchmark case. Finally, we conducted cycling tests in the operating potential range to determine the effect of Zn2+ on the electrochemical behavior of MnOx-based ZIB cathodes. We specifically carried out battery-like tests in electrolytes without and with added Zn2+, for MnOx films electrodeposited potentiostaticaly from the electrolytes. To confirm the importance of MnSO4 and ZnSO4 co-presence in the electrolyte, we performed split-cell experiments in 0.1 M Na2SO4 and 1 M ZnSO4 neutral solutions. Finally, birnessite-type MnO2 films appear to be a viable cathode material for ZIB applications, as they exhibit reversible Zn2+ intercalation and good stability in a moderate ZnSO4 aqueous electrolyte containing a MnSO4 additive that inhibits irreversible cathode deactivation. In the second part of this work, we examine the electrochemical performance of drop-cast α-MnO2 electrodes, prepared by the hydrothermal method. We explored the structural and morphological evolution of α-MnO2 electrodes in detail using XRD, Raman spectroscopy, and SEM-EDS mapping. This material is commonly used for ZAB cathodes, thus we investigated cyclic voltammetry tests in KOH solution, which is typically used for electrocatalytic ORR tests, but here in the absence of O2, as is the case in ZIBs. Then, we also conducted cycle voltammetry measurements in the operating potential range in various near neutral solutions, as in the previous section, to examine electrochemical behavior of α-MnO2 for ZIB applications. In the end, cycling behavior of hydrothermally produced cryptomelane-type α-MnO2 is better in Zn solutions as compared to Zn-alone solutions, but rapid capacity loss is still observed in both cases.
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