{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/98113"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/98113","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Spatially resolved ionic measurements with scanning electrochemical microscopy","abstract":"Modern electrochemical energy storage systems operate by the concerted shuttling of electrons and cations between a cathode and an anode. Strategies for looking at this process do not have a direct measure of ion movement as it occurs, and thus do not provide essential mechanistic details for optimizing battery performance. This work pioneers the use of Hg-based probes to address this gap in knowledge. First, I show the collection of Li+ over an electrified interface and characterize the linear response of Hg-based signals to changes in ion concentration. To improve the sensing strategy, I then develop a framework and model extracting position and reactivity information from cyclic voltammetry scanning electrochemical microscopy (CV-SECM) and associated methods. This maximizes spatial resolution of substrate ionic reactivity while also minimizing threats to the integrity of the probe. I then improve the sensing platform, delineating a reproducible protocol for generating Hg disc-well probes and providing side-by-side performance comparisons between the new and old probe geometries. Following this, I demonstrate the utility of CV-SECM methods and Hg disc-well probes by separating ionic activity from solid electrolyte interphase (SEI) development processes at an operating model battery anode. Ongoing and future applications for the probes and methods generated by this research include multi-ion measurements, cathode studies, and localized charge–discharge experiments to inform the rational design of the next generation of energy storage materials.","abstract_html":"Modern electrochemical energy storage systems operate by the concerted shuttling of electrons and cations between a cathode and an anode. Strategies for looking at this process do not have a direct measure of ion movement as it occurs, and thus do not provide essential mechanistic details for optimizing battery performance. This work pioneers the use of Hg-based probes to address this gap in knowledge. First, I show the collection of Li+ over an electrified interface and characterize the linear response of Hg-based signals to changes in ion concentration. To improve the sensing strategy, I then develop a framework and model extracting position and reactivity information from cyclic voltammetry scanning electrochemical microscopy (CV-SECM) and associated methods. This maximizes spatial resolution of substrate ionic reactivity while also minimizing threats to the integrity of the probe. I then improve the sensing platform, delineating a reproducible protocol for generating Hg disc-well probes and providing side-by-side performance comparisons between the new and old probe geometries. Following this, I demonstrate the utility of CV-SECM methods and Hg disc-well probes by separating ionic activity from solid electrolyte interphase (SEI) development processes at an operating model battery anode. Ongoing and future applications for the probes and methods generated by this research include multi-ion measurements, cathode studies, and localized charge–discharge experiments to inform the rational design of the next generation of energy storage materials.","abstract_has_math":false,"creators":["Barton, Zachary James"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Rodríguez-López, Joaquín","Gewirth, Andrew A.","Leckband, Deborah E.","Flaherty, David W."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2017,"date_issued":"2017-09-29T16:37:54Z","date_published":"2017-09-29T16:37:54Z","updated_at":"2026-07-22T22:24:34Z","subjects":["Scanning electrochemical microscopy (SECM)","Li-ion battery"],"languages":["en"],"rights":["Copyright 2017 Zachary James Barton"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/98113","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Rodríguez-López, Joaquín","Gewirth, Andrew A.","Leckband, Deborah E.","Flaherty, David W."]},{"key":"dc:creator","label":"Author","values":["Barton, Zachary James"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2017-09-29T16:37:54Z","2017-06-13","2017-08"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"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":["Scanning electrochemical microscopy (SECM)","Li-ion battery"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2017 Zachary James Barton"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/98113"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Modern electrochemical energy storage systems operate by the concerted shuttling of electrons and cations between a cathode and an anode. Strategies for looking at this process do not have a direct measure of ion movement as it occurs, and thus do not provide essential mechanistic details for optimizing battery performance. This work pioneers the use of Hg-based probes to address this gap in knowledge. First, I show the collection of Li+ over an electrified interface and characterize the linear response of Hg-based signals to changes in ion concentration. To improve the sensing strategy, I then develop a framework and model extracting position and reactivity information from cyclic voltammetry scanning electrochemical microscopy (CV-SECM) and associated methods. This maximizes spatial resolution of substrate ionic reactivity while also minimizing threats to the integrity of the probe. I then improve the sensing platform, delineating a reproducible protocol for generating Hg disc-well probes and providing side-by-side performance comparisons between the new and old probe geometries. Following this, I demonstrate the utility of CV-SECM methods and Hg disc-well probes by separating ionic activity from solid electrolyte interphase (SEI) development processes at an operating model battery anode. Ongoing and future applications for the probes and methods generated by this research include multi-ion measurements, cathode studies, and localized charge–discharge experiments to inform the rational design of the next generation of energy storage materials.","Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2017-09-29 without embargo terms","The student, Zachary Barton, accepted the attached license on 2017-06-09 at 23:36.","The student, Zachary Barton, submitted this Dissertation for approval on 2017-06-09 at 23:56.","This Dissertation was approved for publication on 2017-06-13 at 13:55.","DSpace SAF Submission Ingestion Package generated from Vireo submission #11206 on 2017-09-29 at 11:26:04","Made available in DSpace on 2017-09-29T16:37:54Z (GMT). No. of bitstreams: 11 BARTON-DISSERTATION-2017.pdf: 73290954 bytes, checksum: a1107f65ac888afd370fae636d4ac366 (MD5) Dissertation, Zachary J. Barton.docx: 89289872 bytes, checksum: eaafd9230aa06ea4f19c58260c9fb364 (MD5) LICENSE.txt: 4211 bytes, checksum: 1882cac818ed2681c2bf51b66612c50a (MD5) ch2f03permission.pdf: 202395 bytes, checksum: cf8a42bb89216ec0997d920d18ce9d01 (MD5) ch2f04permission.pdf: 175063 bytes, checksum: 8ca5c1ec442a7dafcd77a7e59642a07e (MD5) ch2f05permission.pdf: 126917 bytes, checksum: 597187faac56a5fc5b9b76280f564e91 (MD5) ch2permission.pdf: 181043 bytes, checksum: f8d492f356cc86c91807cb059db82238 (MD5) ch3permission.pdf: 126696 bytes, checksum: d1fc67d685d8aa796e3b19bb815b073c (MD5) ch4permission.pdf: 126006 bytes, checksum: 4a402e6e44d63cbeec8326637f33fe07 (MD5) ch5permission.pdf: 126129 bytes, checksum: c46348e808b83d6e8f1e5cb888585093 (MD5) ch6permission.pdf: 182179 bytes, checksum: e9234f012e1f4df60363a45688702c04 (MD5) Previous issue date: 2017-06-13"]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Spatially resolved ionic measurements with scanning electrochemical microscopy"]}]}],"canonical_facts":{"dc:contributor":["Rodríguez-López, Joaquín","Gewirth, Andrew A.","Leckband, Deborah E.","Flaherty, David W."],"dc:creator":["Barton, Zachary James"],"dc:date":["2017-09-29T16:37:54Z","2017-06-13","2017-08"],"dc:description":["Modern electrochemical energy storage systems operate by the concerted shuttling of electrons and cations between a cathode and an anode. Strategies for looking at this process do not have a direct measure of ion movement as it occurs, and thus do not provide essential mechanistic details for optimizing battery performance. This work pioneers the use of Hg-based probes to address this gap in knowledge. First, I show the collection of Li+ over an electrified interface and characterize the linear response of Hg-based signals to changes in ion concentration. To improve the sensing strategy, I then develop a framework and model extracting position and reactivity information from cyclic voltammetry scanning electrochemical microscopy (CV-SECM) and associated methods. This maximizes spatial resolution of substrate ionic reactivity while also minimizing threats to the integrity of the probe. I then improve the sensing platform, delineating a reproducible protocol for generating Hg disc-well probes and providing side-by-side performance comparisons between the new and old probe geometries. Following this, I demonstrate the utility of CV-SECM methods and Hg disc-well probes by separating ionic activity from solid electrolyte interphase (SEI) development processes at an operating model battery anode. Ongoing and future applications for the probes and methods generated by this research include multi-ion measurements, cathode studies, and localized charge–discharge experiments to inform the rational design of the next generation of energy storage materials.","Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2017-09-29 without embargo terms","The student, Zachary Barton, accepted the attached license on 2017-06-09 at 23:36.","The student, Zachary Barton, submitted this Dissertation for approval on 2017-06-09 at 23:56.","This Dissertation was approved for publication on 2017-06-13 at 13:55.","DSpace SAF Submission Ingestion Package generated from Vireo submission #11206 on 2017-09-29 at 11:26:04","Made available in DSpace on 2017-09-29T16:37:54Z (GMT). No. of bitstreams: 11 BARTON-DISSERTATION-2017.pdf: 73290954 bytes, checksum: a1107f65ac888afd370fae636d4ac366 (MD5) Dissertation, Zachary J. Barton.docx: 89289872 bytes, checksum: eaafd9230aa06ea4f19c58260c9fb364 (MD5) LICENSE.txt: 4211 bytes, checksum: 1882cac818ed2681c2bf51b66612c50a (MD5) ch2f03permission.pdf: 202395 bytes, checksum: cf8a42bb89216ec0997d920d18ce9d01 (MD5) ch2f04permission.pdf: 175063 bytes, checksum: 8ca5c1ec442a7dafcd77a7e59642a07e (MD5) ch2f05permission.pdf: 126917 bytes, checksum: 597187faac56a5fc5b9b76280f564e91 (MD5) ch2permission.pdf: 181043 bytes, checksum: f8d492f356cc86c91807cb059db82238 (MD5) ch3permission.pdf: 126696 bytes, checksum: d1fc67d685d8aa796e3b19bb815b073c (MD5) ch4permission.pdf: 126006 bytes, checksum: 4a402e6e44d63cbeec8326637f33fe07 (MD5) ch5permission.pdf: 126129 bytes, checksum: c46348e808b83d6e8f1e5cb888585093 (MD5) ch6permission.pdf: 182179 bytes, checksum: e9234f012e1f4df60363a45688702c04 (MD5) Previous issue date: 2017-06-13"],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/2142/98113"],"dc:language":["en"],"dc:rights":["Copyright 2017 Zachary James Barton"],"dc:subject":["Scanning electrochemical microscopy (SECM)","Li-ion battery"],"dc:title":["Spatially resolved ionic measurements with scanning electrochemical microscopy"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:24:34Z"}