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Title: Borate polyanion-based systems as Li- and Mg-ion cathode materials
Author: Glass, Hugh
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 2017
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The aim of this thesis is to investigate pyroborates, M2B2O5, and orthoborates, M3(BO3)2, where M = Mg, Mn, Co, Ni, as high capacity and high voltage Li- and Mg-ion cathode materials. We explore the layered orthoborates (M3(BO3)2 which, to our knowledge, have not been previously considered as Li- or Mg-ion cathodes, perhaps due to the lack of Li analogues. Structural analysis shows that mixed metal orthoborates form a solid solution, with cation order driven by the presence of directional d orbitals. Electrochemical studies show that Mg can be removed from the structure and replaced with Li in a 1:1 ion ratio. In the compound Mg2Mn(BO3)2 removal of 1 Mg is achieved giving a capacity of 209.9 mAh g 1. The pyroborates (M2B2O5) are an unexplored family of borate polyanions, which offer higher theoretical capacities and voltages than LiMBO3 due to their more condensed frameworks. There are no known Li containing pyroborates, we use electrochemical ion exchange, with the aim of replacing each Mg with 2 Li to form LixMB2O¬5. The stoichiometry can be varied to alter the redox couple utilised and the Mg available for removal. MgxM2-xB2O5 has been synthesised for M = Mn, Co, Fe and Ni and all forms have been shown to form a solid solution with cation ordering over the two M sites. In MgMnB2O5 we have shown that Mg can be fully removed while retaining the pyroborate structure. Subsequently up to 1.1 Li can be inserted giving discharge capacities of 240 mAhg-1 above 1.5 V. After 100’s of cycles 2 Li can be reversibly cycled. The insertion of Li has been confirmed by 7Li NMR and the oxidation state changes in Mn have been investigated by SQUID magnetometry and XANES spectroscopy. Electrochemical studies in materials where M = Fe, Co, and Ni show high voltage plateaus ( > 3.5 V) but limited capacity at room temperature. Increased temperatures improves cycling, with Co and Fe based compounds reaching full theoretical capacities ( > 200 mAhg-1). As Mg can be removed from the structure, the pyroborates could be of interest in Mg-ion batteries, which offer benefits in energy density, cost, and safety. Mg-ion battery research is still in its infancy, therefore here we develop methods to reliably test Mg-ion cathodes and electrolytes. We demonstrate that despite significant side reactions, Mg can be reversibly cycled in the MgMnB2O5 system in a full Mg-ion cell, showing that pyroborates are a promising family of materials for high capacity, high voltage Mg-ion cathodes. This study shows that the pyroborates and orthoborates are a promising family of materials for Li- and Mg-ion cathodes, with the light weight structure leading to high specific capacities. The ability to replace Mg for Li in polyanion materials without disrupting the crystal structure opens a new way to search for novel, high energy density, Li-ion cathodes.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
Keywords: Polyanion ; Magnesium ; Lithium ; batteries ; cathodes ; Mg-ion ; Li-ion ; borate