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Synthesis and Characterization Studies of Li-Fe-In-(PO4) Phases: Chemical Relatives of Battery Cathode Material Lithium Iron Phosphate

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dc.contributor.advisor Khalifah, Peter G en_US
dc.contributor.author Saccomanno, Michael Richard en_US
dc.contributor.other Department of Chemistry. en_US
dc.date.accessioned 2017-09-20T16:52:05Z
dc.date.available 2017-09-20T16:52:05Z
dc.date.issued 2014-12-01 en_US
dc.identifier.uri http://hdl.handle.net/11401/77149 en_US
dc.description 75 pg. en_US
dc.description.abstract Lithium iron(II) phosphate, also known as lithium ferrophosphate (LiFePO<sub>4</sub>, LFP), has been the subject of many recent energy storage studies. As a battery cathode material, LFP has many advantages for commercial applications. Compared to its competitors like LiMn<sub>2</sub>O<sub>4</sub> and the ubiquitous but carcinogenic LiCoO<sub>2</sub>, LFP (specific energy = 600 Wh/kg) exhibits low toxicity, low cost, good thermal stability, and excellent electrochemical performance at high charge/discharge rates. As part of the efforts to understand and improve LFP, a great amount of research has been committed towards developing, characterizing, and electrochemically testing chemical relatives of this phase. In this work, chemical relatives of LFP belonging to the Li<sub>3</sub>PO<sub>4</sub>-Fe<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>-InPO<sub>4</sub> phase system were investigated. This has lead to the discovery of lithium iron(II) indium phosphate [LiFeIn(PO<sub>4</sub>)<sub>2</sub>, LFIP]. Structural studies on LFIP using laboratory and synchrotron X-ray, neutron, and electron diffraction techniques have demonstrated this phase to crystallize in the orthorhombic space group <italic>Pbca</italic> with lattice parameters <italic>a</italic> = 9.276(1) Å, <italic>b</italic> = 13.757(2) Å, and <italic>c</italic> = 9.476(1) Å. Unlike LFP, this new material does not perform well as a battery cathode as found by chemical delithiation tests, electrochemical cycling, and bond-valence sum difference maps of Li<super>+</super> diffusion pathways. LFIP has also been characterized by magnetic and optical measurements. The material does not order magnetically above 2 K, is paramagnetic with weak antiferromagnetic interactions, and has an effective magnetic moment of 5.39 <italic>µ</italic><sub>B</sub>/Fe. LFIP has a band-gap energy of 2.94 eV and d orbital ligand field splitting energies of 0.75 eV and 0.99 eV. Based on our synthesis results, a preliminary assessment of the Li<sub>3</sub>PO<sub>4</sub>-Fe<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>-InPO<sub>4</sub> phase system is presented. en_US
dc.description.sponsorship This work is sponsored by the Stony Brook University Graduate School in compliance with the requirements for completion of degree. en_US
dc.format Monograph en_US
dc.format.medium Electronic Resource en_US
dc.language.iso en_US en_US
dc.publisher The Graduate School, Stony Brook University: Stony Brook, NY. en_US
dc.subject.lcsh Chemistry en_US
dc.subject.other Electrochemistry, Lithium iron(II) indium phosphate, Phase discovery, Solid-state synthesis en_US
dc.title Synthesis and Characterization Studies of Li-Fe-In-(PO4) Phases: Chemical Relatives of Battery Cathode Material Lithium Iron Phosphate en_US
dc.type Thesis en_US
dc.mimetype Application/PDF en_US
dc.contributor.committeemember Marschilok, Amy en_US
dc.contributor.committeemember Parise, John. en_US

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