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|Title: ||Nanomaterials for energy storage|
|Authors: ||Jiao, Feng|
|Supervisors: ||Bruce, Peter G.|
|Keywords: ||Lithium batteries|
|Issue Date: ||1-Jan-2008|
|Abstract: ||The results presented in this thesis demonstrate the first synthesis of several nanostructured transition metal oxides and lithium containing transition metal oxides. Their uses in lithium-ion batteries and/or as magnetic materials have been investigated.
The first example of two and three dimensional mesoporous Fe₂O₃ has been prepared by using the soft templating (surfactant) method. The materials have amorphous walls and exhibit superparamagnetic behaviour.
By using a hard template route, a mesoporous α-Fe₂O₃ with highly crystalline walls has been synthesized. Its unique magnetic behaviour, distinct from bulk α-Fe₂O₃, nanoparticulate α-Fe₂O₃, and mesoporous Fe₂O₃ with disordered walls, has been demonstrated.
The hard template method was also used to prepare nanowire and mesoporous Co₃O₄, β-MnO₂ and MnO₃ with crystalline walls. Their electrochemical properties as electrodes in Li-ion batteries have been investigated. Mesoporous β-MnO₂ can accommodate 0.9 Li/Mn in stark contrast to bulk β-MnO₂ which cannot accommodate Li.
To prepare mesoporous materials which cannot be obtained directly by the hard template method, a post-templating route has been developed. Mesoporous Fe₃O₄, γ-Fe₂O₃, and Mn3O4 with ordered mesostructures and highly crystalline walls have been obtained by post-synthesis reduction/oxidation treatments. All the materials show unique magnetic properties compared with nanoparticulate and bulk materials.
Also, the first example of lithium containing mesoporous material, LT-LiCoO₂, was synthesized by first preparing mesoporous Co₃O₄, then reacting this with LiOH to form LT-LiCoO₂, with retention of the ordered nanostructure. The nanostructured LT-LiCoO₂ compounds demonstrate superior performance compared with normal or nanoparticulate LT-LiCoO₂, when used as intercalation electrodes in lithium batteries.
Finally, monodispersed Mn₃O₄ nanoparticles (diameter ~ 8 nm) with a core-shell structure (a highly crystalline Mn₃O₄ core encased in a thin MnO₂ shell) have been prepared for the first time. Ordered three-dimensional arrays form by spontaneous self-assembly. Magnetic measurements demonstrated that the self-assembled three-dimensional arrays exhibit spin-glass behaviour, rather than the anticipated superparamagnetic behaviour for isolated nanoparticles. Such behaviour is interpreted as arising from strong interactions between the core (crystallized Mn₃O₄) and shell (MnO₂).|
|Publisher: ||University of St Andrews|
|Appears in Collections:||Chemistry Theses|
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