{"@context":"http://iiif.io/api/presentation/2/context.json","@id":"https://repo.library.stonybrook.edu/cantaloupe/iiif/2/manifest.json","@type":"sc:Manifest","label":"Investigating Electrochemical Processes in Secondary Batteries","metadata":[{"label":"dc.description.sponsorship","value":"This work is sponsored by the Stony Brook University Graduate School in compliance with the requirements for completion of degree"},{"label":"dc.format","value":"Monograph"},{"label":"dc.format.medium","value":"Electronic Resource"},{"label":"dc.identifier.uri","value":"http://hdl.handle.net/11401/78194"},{"label":"dc.language.iso","value":"en_US"},{"label":"dcterms.abstract","value":"For the past twenty-six years, the lithium-ion battery has been the most popular recharge- able battery for portable devices and electric vehicles. Despite its success, the energy storage capability of lithium-ion batteries (LIBs) is significantly limited by both the electrodes and electrolytes employed. Typical LIBs rely on intercalation-type electrodes, that are not capable of storing more than 1 Li+ per formula unit. The energy storage capability of LIBs can be improved through the application of conversion-type materials and beyond lithium chemistries. This research involves multiple projects which explore the electrochemistry of conversion electrodes, magnesium-ion chemistry, and lithium-sulfur chemistry. Application of conversion-electrodes like copper ferrite, CuFe2O4, and magnetite, Fe3O4, are capable of lithium storage over five times greater than that achieved by electrodes used in commercial LIBs. The drawback to utilizing the conversion mechanism is that significant energy storage capability is lost during charge. In this research, X- ray characterization methods, including X-ray Diffraction (XRD) and X-ray Absorption Spectroscopy (XAS) are used to elucidate the lithiation and delithiation mechanism for CuFe2O4 and to understand the source of the irreversibility. These experiments provide significant insight into the reduction processes and cation migration within the structure. During lithiation, CuFe2O4 undergoes a three-step reduction mechanism involving (1) lithiation of CuFe2O4, (2) extrusion of copper metal nanoparticles and formation of rock- salt LiFeO2, followed by the (3) formation of iron metal nanoparticles. Upon delithiation, XAS spectra clearly demonstrate the feasibility of Fe0 oxidation to a rock-salt iron oxide; however, Cu0 oxidation is not observed. Additional experiments explored the kinetic limitations of lithiating Fe3O4 nanoparticles, with different crystallite sizes. The experiments demonstrate that the kinetics of the lithiation mechanism are influenced by the electroactive material\u2019s agglomerate and crystallite size. The rate of lithiation involving small crystallites is dependent on diffusion within the agglomerates; however, as the crystallite size increases, the lithiation rate is inhibited by diffusion within both the agglomerate and the crystallite. Battery chemistries beyond lithium can also lead to energy storage capabilities an order of magnitude higher than LIBs. Both magnesium-ion and lithium-sulfur battery chemistries are investigated in this dissertation. The properties of ionic liquid electrolytes are explored as safer alternatives to harmful Grignard-reagent electrolytes commonly used for magnesium chemistries. Electrochemical evaluation of the ionic liquid electrolytes found that although better conductivity can be achieved with unsaturated electrolytes like imidizolium based electrolytes, greater oxidative voltages are possible with saturated electrolytes like the piperidinium and pyridinium based electrolytes. The higher oxidative voltage is a promising attribute for high voltage applications. Cathode additives, including FeS2 and microporous carbon, are studied to inhibit polysulfide dissolution within the electrolyte of Li|S batteries. Although FeS2 exhibited promising electrochemistry as its own cathode, it was found to be an ineffective additive within sulfur cathodes. Instead, the properties of microporous carbons are explored to identify an appropriate carbon additive to both increase conductivity and impede polysulfide dissolution. A wood based carbon exhibited high capacity and long cycle life at low rate compared to conventional microporous carbons. As a whole, this research has provided valuable insight into the electrochemical processes taking place within a battery, as well as the factors which affect these processes. Electrochemical, spectroscopic, and various scattering methods are used to probe processes which span from the reactions occurring within the electrode to the redox reactions which define the voltage limitations of the electrolyte. These studies demonstrate the impact of each battery component on the overall electrochemical performance and provide fundamental insight into battery operation."},{"label":"dcterms.available","value":"2018-03-22T22:39:17Z"},{"label":"dcterms.contributor","value":"Takeuchi, Kenneth J."},{"label":"dcterms.creator","value":"Cama, Christina A."},{"label":"dcterms.dateAccepted","value":"2018-03-22T22:39:17Z"},{"label":"dcterms.dateSubmitted","value":"2018-03-22T22:39:17Z"},{"label":"dcterms.description","value":"Department of Chemistry."},{"label":"dcterms.extent","value":"159 pg."},{"label":"dcterms.format","value":"Application/PDF"},{"label":"dcterms.identifier","value":"http://hdl.handle.net/11401/78194"},{"label":"dcterms.issued","value":"2017-08-01"},{"label":"dcterms.language","value":"en_US"},{"label":"dcterms.provenance","value":"Made available in DSpace on 2018-03-22T22:39:17Z (GMT). No. of bitstreams: 1\nCama_grad.sunysb_0771E_13379.pdf: 9291836 bytes, checksum: 603b24996d0a42dafb224a7e77b04ead (MD5)\n  Previous issue date: 2017-08-01"},{"label":"dcterms.subject","value":"X-ray Absorption Spectroscopy"},{"label":"dcterms.title","value":"Investigating Electrochemical Processes in Secondary Batteries"},{"label":"dcterms.type","value":"Dissertation"},{"label":"dc.type","value":"Dissertation"}],"description":"This manifest was generated dynamically","viewingDirection":"left-to-right","sequences":[{"@type":"sc:Sequence","canvases":[{"@id":"https://repo.library.stonybrook.edu/cantaloupe/iiif/2/canvas/page-1.json","@type":"sc:Canvas","label":"Page 1","height":1650,"width":1275,"images":[{"@type":"oa:Annotation","motivation":"sc:painting","resource":{"@id":"https://repo.library.stonybrook.edu/cantaloupe/iiif/2/12%2F37%2F09%2F123709556219225978038953130347340994794/full/full/0/default.jpg","@type":"dctypes:Image","format":"image/jpeg","height":1650,"width":1275,"service":{"@context":"http://iiif.io/api/image/2/context.json","@id":"https://repo.library.stonybrook.edu/cantaloupe/iiif/2/12%2F37%2F09%2F123709556219225978038953130347340994794","profile":"http://iiif.io/api/image/2/level2.json"}},"on":"https://repo.library.stonybrook.edu/cantaloupe/iiif/2/canvas/page-1.json"}]}]}]}