Redox reactions in deep eutectic solvents: characterisation and application

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dc.contributor Aalto-yliopisto fi
dc.contributor Aalto University en
dc.contributor.advisor Lasse Murtomäki, Dr., Aalto University, Department of Chemistry, Finland Lloyd, David 2013-12-13T10:01:08Z 2013-12-13T10:01:08Z 2013
dc.identifier.isbn 978-952-60-5404-9 (electronic)
dc.identifier.isbn 978-952-60-5403-2 (printed)
dc.identifier.issn 1799-4942 (electronic)
dc.identifier.issn 1799-4934 (printed)
dc.identifier.issn 1799-4934 (ISSN-L)
dc.description.abstract Ionic liquids are a field of intense chemical research activity due to their potential to facilitate a wide range of chemical innovations. Due to the cost of ionic liquids alternative materials which exhibit similar properties, but are less expensive, are also the subject of interest and deep eutectic solvents are a prime example. Deep eutectic solvents are commonly based on quaternary ammonium chloride salts and therefore allow the ready dissolution of a range of metal chloride salts to form transition metal complexes. The electrolytes formed in this manner have been proposed as the basis for a range of novel processes to electrodeposit metals. This thesis presents the first application of a range of electroanalytical techniques to quantitatively characterize the properties of electrochemical reactions involving copper and iron chloro complexes in deep eutectic solvents. The methods used are based on cyclic voltammetry, electrochemical impedance spectroscopy and potential steps. Methods based on both static and hydrodynamic electrodes are considered. The reactions are found to be equally kinetically facile as in aqueous solvents, however the relatively viscous nature of the solvent is reflected in the transport properties of the complexes formed. The successful application of these techniques required the development of a suitably responsive reference electrode system. A system employing a quasireference electrode and reference probe in parallel was found to provide both a well-defined reference potential and suitably low impedance. The application of deep eutectic solvents in redox flow batteries is also reported for the first time and shown to allow the simple application of transition metal chlorocomplexes. However, the inferior transport properties of the electrolyte is shown to currently be a limiting factor within the temperature range studied. This requires the application of current densities at least an order of magnitude lower than those typically used in redox flow batteries. Application of deep eutectic solvents as the media for redox flow batteries required the development of a novel separator material based on jellification of the electrolyte using polyethylene glycol, this material was found to possess comparable conductivity to the pure electrolyte. en
dc.format.extent 97 + app. 43
dc.format.mimetype application/pdf
dc.language.iso en en
dc.publisher Aalto University en
dc.publisher Aalto-yliopisto fi
dc.relation.ispartofseries Aalto University publication series DOCTORAL DISSERTATIONS en
dc.relation.ispartofseries 174/2013
dc.relation.haspart [Publication 1]: David Lloyd, Tuomas Vainikka, Lasse Murtomaki, Kyosti Kontturi, Elisabet Ahlberg. The kinetics of the Cu2+/Cu+ redox couple in deep eutectic solvents. Electrochimica Acta, 56(2011)4942 − 4948, April 2011.
dc.relation.haspart [Publication 2]: David Lloyd, Tuomas Vainikka, Sonke Schmachtel, Lasse Murtomaki, Kyosti Kontturi. Simultaneous characterisation of electrode kinetics and electrolyte properties in ionic liquids using a rotating disc electrode. Electrochimica Acta, 69(2012)139 − 145, March 2012.
dc.relation.haspart [Publication 3]: David Lloyd, Tuomas Vainikka, Kyosti Kontturi. The development of an all copper hybrid redox flow battery using deep eutectic solvents. Electrochimica Acta, 100(2013)18 − 23, March 2013.
dc.relation.haspart [Publication 4]: David Lloyd, Tuomas Vainikka, Markus Ronkainen, Kyosti Kontturi. Characterisation and application of the Fe(II)/Fe(III) redox reaction in an ionic liquid analogue. Electrochimica Acta, 109(2013)843 − 851, October 2013.
dc.subject.other Chemistry en
dc.title Redox reactions in deep eutectic solvents: characterisation and application en
dc.type G5 Artikkeliväitöskirja fi Kemian tekniikan korkeakoulu fi School of Chemical Technology en
dc.contributor.department Kemian laitos fi
dc.contributor.department Department of Chemistry en
dc.subject.keyword ionic liquids en
dc.subject.keyword deep eutectic solvents en
dc.subject.keyword transition metal chloro complexes en
dc.subject.keyword electrochemistry en
dc.subject.keyword electrochemical impedance spectroscopy en
dc.subject.keyword rotating disc electrode en
dc.subject.keyword redox flow battery en
dc.identifier.urn URN:ISBN:978-952-60-5404-9
dc.type.dcmitype text en
dc.type.ontasot Doctoral dissertation (article-based) en
dc.type.ontasot Väitöskirja (artikkeli) fi
dc.contributor.supervisor Kontturi, Kyösti, Prof., Aalto University, Department of Chemistry, Finland
dc.opn Abbott, Andrew, Prof., University of Leicester, United Kingdom
dc.contributor.lab Laboratory for Physical Chemistry and Electrochemistry en
dc.rev Berlouis, Len, University of Strathclyde, United Kingdom
dc.rev Mafé, Salvatore, University of Valencia, Spain 2013-12-05

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