{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/125578"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/125578","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Characterizing the influence of layered transition metal oxide morphology on cathode performance","abstract":"Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2025-02-04 without embargo terms","abstract_html":"Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2025-02-04 without embargo terms","abstract_has_math":false,"creators":["Caple Jr., Michael Anthony"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Materials Science & Engr","degree_department":null,"school":null,"contributors":["Braun, Paul V","Miljkovic, Nenad","Perry, Nicola H","Krogstad, Jessica A"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2024,"date_issued":"2024-07-12","date_published":"2024-07-12","updated_at":"2026-07-22T22:25:02Z","subjects":["Lithium-ion Batteries","Layered Transition Metal Oxide Cathodes","Molten Salt Synthesis","Electrochemistry"],"languages":["en","eng"],"rights":["Copyright 2024 Michael Caple Jr."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/2142/125578","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Braun, Paul V","Miljkovic, Nenad","Perry, Nicola H","Krogstad, Jessica A"]},{"key":"dc:creator","label":"Author","values":["Caple Jr., Michael Anthony"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2024-07-12","2024-08"]},{"key":"dc:type","label":"Dc Type","values":["text","Thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Materials Science & Engr"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Lithium-ion Batteries","Layered Transition Metal Oxide Cathodes","Molten Salt Synthesis","Electrochemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en","eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2024 Michael Caple Jr."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://hdl.handle.net/2142/125578"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2025-02-04 without embargo terms","The student, Michael Caple Jr., accepted the attached license on 2024-07-08 at 13:11.","The student, Michael Caple Jr., submitted this Dissertation for approval on 2024-07-08 at 13:17.","This Dissertation was approved for publication on 2024-07-12 at 06:18.","DSpace SAF Submission Ingestion Package generated from Vireo submission #20981 on 2025-02-04 at 21:04:22","Layered transition metal oxides are an important class of high energy density lithium-ion battery cathode materials. Because of their widespread use, it is important to elucidate factors that influence their stability in secondary battery applications. Using thick (>10 m), textured lithium cobalt oxide (LCO) cathodes, we reveal the impact of crystallographic orientation on the cycling stability of these layered transition metal oxide materials. We observe that (003) textured (LCO), (104) textured LCO, and composite LCO experience 48.5%, 65.9%, and 67.9% capacity fade after 100 cycles, respectively. Using electrochemical impedance spectroscopy, we measured the half-cell resistance to charge transfer and cathode electrolyte interphase resistance in 20 cycle increments. We detect that the charge transfer resistance grows 2280% for (003) LCO and 755% for (104) LCO, indicating that large regions of the textured cathodes crack during cycling. Conversely, we see that the growth of the cathode electrolyte interphase resistance of composite LCO cathode (95.3%) is much larger than what is observed for the textured LCO cathodes. The subsequent postmortem confocal Raman images confirm that state of charge heterogeneity is present in each cathode; interestingly, the extent of heterogeneity is correlated to the growth of the resistance to charge transfer. We continued to explore the impact of cathode morphology when studying single crystalline LiNi0.8Mn0.1Co0.1O2, a popular next generation cathode material. Fabrication of single crystals with a low initial cation mixing required optimization of the precursor flux. Using electrochemical impedance spectroscopy, we observed the interfacial changes for single crystals with predominately (012), (001), and (104) surface areas. From the obtained results it is calculated that the charge transfer resistance for (001), (012), and (104) dominant crystals grow 69.4%, 87.1%, and 14.5% in 65 cycles, respectively. Furthermore, we find that the cathode electrolyte interphase resistance for the (104) dominant single crystals only grows 3.82% in 65 cycles while this value grows 31.9% for (012) dominant single crystals in the same cycle range. Overall, the electrochemical results from this study support our assertion that cathodes with a predominately (104) surface area have stable interfacial properties, which make them attractive for long-term cycling. Moreover, our findings indicate that tailoring cathode microstructure is crucial to extending lithium-ion battery cycle life."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Characterizing the influence of layered transition metal oxide morphology on cathode performance"]}]}],"canonical_facts":{"dc:contributor":["Braun, Paul V","Miljkovic, Nenad","Perry, Nicola H","Krogstad, Jessica A"],"dc:creator":["Caple Jr., Michael Anthony"],"dc:date":["2024-07-12","2024-08"],"dc:description":["Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2025-02-04 without embargo terms","The student, Michael Caple Jr., accepted the attached license on 2024-07-08 at 13:11.","The student, Michael Caple Jr., submitted this Dissertation for approval on 2024-07-08 at 13:17.","This Dissertation was approved for publication on 2024-07-12 at 06:18.","DSpace SAF Submission Ingestion Package generated from Vireo submission #20981 on 2025-02-04 at 21:04:22","Layered transition metal oxides are an important class of high energy density lithium-ion battery cathode materials. Because of their widespread use, it is important to elucidate factors that influence their stability in secondary battery applications. Using thick (>10 m), textured lithium cobalt oxide (LCO) cathodes, we reveal the impact of crystallographic orientation on the cycling stability of these layered transition metal oxide materials. We observe that (003) textured (LCO), (104) textured LCO, and composite LCO experience 48.5%, 65.9%, and 67.9% capacity fade after 100 cycles, respectively. Using electrochemical impedance spectroscopy, we measured the half-cell resistance to charge transfer and cathode electrolyte interphase resistance in 20 cycle increments. We detect that the charge transfer resistance grows 2280% for (003) LCO and 755% for (104) LCO, indicating that large regions of the textured cathodes crack during cycling. Conversely, we see that the growth of the cathode electrolyte interphase resistance of composite LCO cathode (95.3%) is much larger than what is observed for the textured LCO cathodes. The subsequent postmortem confocal Raman images confirm that state of charge heterogeneity is present in each cathode; interestingly, the extent of heterogeneity is correlated to the growth of the resistance to charge transfer. We continued to explore the impact of cathode morphology when studying single crystalline LiNi0.8Mn0.1Co0.1O2, a popular next generation cathode material. Fabrication of single crystals with a low initial cation mixing required optimization of the precursor flux. Using electrochemical impedance spectroscopy, we observed the interfacial changes for single crystals with predominately (012), (001), and (104) surface areas. From the obtained results it is calculated that the charge transfer resistance for (001), (012), and (104) dominant crystals grow 69.4%, 87.1%, and 14.5% in 65 cycles, respectively. Furthermore, we find that the cathode electrolyte interphase resistance for the (104) dominant single crystals only grows 3.82% in 65 cycles while this value grows 31.9% for (012) dominant single crystals in the same cycle range. Overall, the electrochemical results from this study support our assertion that cathodes with a predominately (104) surface area have stable interfacial properties, which make them attractive for long-term cycling. Moreover, our findings indicate that tailoring cathode microstructure is crucial to extending lithium-ion battery cycle life."],"dc:format":["application/pdf"],"dc:identifier":["https://hdl.handle.net/2142/125578"],"dc:language":["en","eng"],"dc:rights":["Copyright 2024 Michael Caple Jr."],"dc:subject":["Lithium-ion Batteries","Layered Transition Metal Oxide Cathodes","Molten Salt Synthesis","Electrochemistry"],"dc:title":["Characterizing the influence of layered transition metal oxide morphology on cathode performance"],"dc:type":["text","Thesis"],"thesis:degree_discipline":["Materials Science & Engr"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:02Z"}