Thesis (Ph. D.)--University of Texas at Austin, 2007. / Vita. Includes bibliographical references.

Thesis (M. Phil.)--University of Hong Kong, 2007. / Title proper from title frame. Also available in printed format.

Thesis supervisor: Michelle M. Scherer. Includes bibliographic references (p. 168-179).

published_or_final_version / abstract / Biological Sciences / Master / Master of Philosophy

No description available.

Thesis (M.S.)--Oregon State University, 2002. / Typescript (photocopy). Includes bibliographical references (leaves 62-64). Also available on the World Wide Web.

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Lithium ion batteries have been successful in portable electronics market due to their high energy density, adopting the layered LiCoO₂ as the cathode material in commercial lithium ion cells. However, increasing interest in lithium ion batteries for electric vehicle and hybrid electric vehicle applications requires alternative cathode materials due to the high cost, toxicity, and limited power capability of the layered LiCoO₂ cathode. In this regard, spinel LiMn₂O₄ has become appealing as manganese is inexpensive and environmentally benign, but LiMn₂O₄ is plagued by severe capacity fade at elevated temperatures. This dissertation explores the factors that control and limit the electrochemical performance of spinel LiMn₂O₄ cathodes and focuses on improving the performance parameters such as the capacity, cyclability, and rate capability of various spinel cathodes derived from LiMn₂O₄. From a systematic investigation of a number of cationic and anionic (fluorine) substituted spinel oxide compositions, the improvements in electrochemical properties and performances are found to be due to the reduced manganese dissolution and suppressed lattice parameter difference between the two cubic phases formed during the charge-discharge process. Investigations focused on fluorine substitution reveal that spinel LiMn[subscript 2-yz]LiyZnzO[subscript 4-eta]F[subscript eta] oxyfluoride cathodes synthesized by solid-state reactions at 800 °C employing ZnF₂ as a raw material and spinel LiMn[subscript 2-y-z]Li[subscript y]Ni[subscript z]O[subscript 4-eta]F[subscript eta] oxyfluoride cathodes synthesized by firing the cation-substituted LiMn[subscript 2-y-z]LiyNi[subscript z]O₄ oxides with NH₄HF₂ at a moderate temperature of 450 °C show superior cyclability, increased capacity, reduced Mn dissolution, and excellent storage performance compared to the corresponding oxide analogs and the conventional LiMn₂O₄. Spinel-layered composite cathodes are found to exhibit better electrochemical performance with graphite anode when charged to 4.7 V in the first cycle followed by cycling at 4.3-3.5 V compared to the normal cycling at 4.3 - 3.5 V. The improved performance is explained to be due to the trapping of trace amounts of protons that may be present in the electrolyte within the layered oxide lattice during the first charge to 4.7 V and the consequent reduction in Mn dissolution. Electrochemical performances of 3 V spinel Li₄Mn₅O₁₂ cathodes are also improved by fluorine substitution due to the suppression of the disproportionation of Li4Mn5O12 during synthesis and the formation of the Li₂MnO₃ phase.

The crystallographic and magnetic properties of manganese oxides belonging to the Ruddlesden Popper (RP) series, described by the formula A_n+1B_nO_3n+1, are presented. Compounds having n = 2, 3 and ∞ are discussed in Chapters 3, 4 and 5, respectively, their properties being studied by powder X-ray and neutron diffraction, SQUID magnetometry and magnetotransport measurements. In Chapter 3 (A₃B₂O₇) it is shown that Sr_2-xNd_1+xMn₂O₇ (0 ≤ x ≤ 0.5) and Sr₂PrMn₂O₇ exhibit colossal, negative magnetoresistance (CMR) below 150K. The zero field resistivity signal is reduced by 2-3 orders of magnitude in a field of 14T, at ~4.2K. The compounds Sr₂HoMn₂O₇ and Sr₂YMn₂O₇ show no significant magnetoresistance. In contrast to the tetragonal Sr,Nd and Sr,Pr compositions, these compounds show a symmetry lowering to space group P4₂/mnm, and spin glass freezing on the Mn sublattice at ~20K. Chapter 4 (A₄B₃O₁₀) focuses on A- and B-cation substitutions in the parent compound Ca₄Mn₃O_10-δ. Substitution of Ca by Sr yields Sr₄Mn₃O_10-δ, an orthorhombic (Cmca) compound, composed of trimers of face sharing octahedra. The magnetic susceptibility of this sample is interpreted in terms of direct and indirect antiferromagnetic (AFM) Mn-Mn exchange interactions. The orthorhombic (Pbca) RP phase Ca_3.95La_0.05Mn₃O_10-δ has a magnetic transition at ~114K, suggesting that the antiferromagnetic groundstate, with associated weak ferromagnetism arising through the Dzyaloshinsky-Moriya interaction observed in Ca₄Mn₃O_10-δ, is preserved on introduction of a fraction of La³⁺ dopant cations. Ca_3.95La_0.05Mn₃O_10-δ displays CMR at 4K, with the resistivity signal reduced to 18% of the zero field value, in 14T. B-cation substitution yields Ca₄Mn₂TiO_9.93, an orthorhombic (Pbca) RP phase in which the Mn:Ti cation distribution, deduced from the combined results of anomalous dispersion X-ray experiments and neutron diffraction studies, is 59.8%(2.6):40.2%(2.6) and 70.1%(1.3):29.9%(1.3) across the 4b and 8c octahedral sites, respectively. Neutron diffraction studies at 5K show the presence of only short range magnetic interactions in this insulating material, the resistivity of which is reduced by just 10% at 75K in 14T. Chapter 5 (ABO₃ or A₂BB'O₆) describes the mixed B-cation phases, La₂GaMnO₆ and Nd₂GaMnO₆, containing Mn³⁺, 3d⁴ cations. Both are cation disordered, orthorhombic (Pnma) materials, and Nd₂GaMnO₆ exhibits a static, cooperative Jahn-Teller (JT) distortion. La₂GaMnO₆ contains a relatively higher proportion of dynamic, cooperative JT distortions, and as such exhibits isotropic ferromagnetism at 5OK and 5K (2.80(5)μ_B per Mn aligned along y at 5K), predicted by the 'quasistatic hypothesis', which describes the correlation between electron spin configurations of neighbouring JT cations. The magnetic structure of Nd₂GaMnO₆ at 5K and 1.7K is modelled as 'A_X F_Y G_Z' for the Mn sublattice, and 'F_γ' for the Nd sublattice, using Bertaut's notation, resulting in competing ferromagnetic and antiferromagnetic superexchange interactions on the Mn sublattice along the [010] direction of the unit cell. Both materials are highly insulating and neither displays CMR, with resistivity values in each being reduced to just 96% of the zero field value at 200K, in a field of 14T.