An Initial Exploration of Transition Metal Nitroprussides as Electrode Materials for Sodium-ion Batteries

Detta är en Uppsats för yrkesexamina på avancerad nivå från Uppsala universitet/Strukturkemi

Sammanfattning: Na-ion batteries (NIBs) are expected to revolutionise the battery sector by promising an affordable technology while capitalising on sustainable development. To compete with Li-ion batteries, however, electrode materials with higher capacities need to be developed. Transition metal nitroprussides (TM-NPs), NaxM[Fe(CN)5NO]1-y ·zH2O, is a material class derived from one of the most popular positive electrode materials for NIBs, Prussian blue analogues (PBAs), where one of the cyano ligands have been replaced by an electroactive nitrosyl (NO) ligand. Thus, in theory TM-NPs should be able to reach higher capacities than PBAs and therefore be attractive candidates for high-capacity electrodes. However, if the nitrosyl is redox active in NIBs and how the cycling behaviour may be affected by the M cation is unknown. The focus in this thesis is therefore to explore the charge-discharge behaviour of four different TM-NPs (M=Fe, Ni, Mn, and Cu) in Na-ion half-cell batteries to gain an initial understanding of their electrochemical behaviour and to set up research questions to be pursued in the future. Based on our observations and previous studies, we propose that the nitrosyl is electrochemically active in all four TM-NPs, and that it contributes with a considerable amount of capacity, although with a large voltage hysteresis. It is further concluded that all M cations apart from Ni were redox active, but to varying degrees on charging and discharging. We argue that both the redox and the voltage hysteresis is caused by anisotropic charge transfer within the materials, and that it needs to be understood before commercialisation of TM-NPs can be realised. Though there are challenges to overcome, the many interesting attributes of TM-NPs, including anionic redox, anisotropic charge transfer and structural diversity, makes them promising as a new type of cheap and sustainable electrode material for NIBs. 

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