ElectrochemicalImpedanceSpectroscopyanditsApp

Andrzej LasiaElectrochemicalImpedanceSpectroscopyanditsApplicationsElectrochemicalImpedanceSpectroscopyanditsApplicationsAndrzejLasiaElectrochemicalImpedanceSpectroscopyanditsApplicationsAndrzejLasiaDe´partementdechimieUniversite´deSherbrookeSherbrooke,Que´becCanadaAdditionalmaterialtothisbookcanbedownloadedfrom(eBook)DOI10.1007/978-1-4614-8933-7SpringerNewYorkHeidelbergDordrechtLondonLibraryofCongressControlNumber:2013954801©SpringerScience+BusinessMediaNewYork2014Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartofthematerialisconcerned,specificallytherightsoftranslation,reprinting,reuseofillustrations,recitation,broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionorinformationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilarmethodologynowknownorhereafterdeveloped.Exemptedfromthislegalreservationarebriefexcerptsinconnectionwithreviewsorscholarlyanalysisormaterialsuppliedspecificallyforthepurposeofbeingenteredandexecutedonacomputersystem,forexclusiveusebythepurchaserofthework.DuplicationofthispublicationorpartsthereofispermittedonlyundertheprovisionsoftheCopyrightLawofthePublisher’slocation,initscurrentversion,andpermissionforusemustalwaysbeobtainedfromSpringer.PermissionsforusemaybeobtainedthroughRightsLinkattheCopyrightClearanceCenter.ViolationsareliabletoprosecutionundertherespectiveCopyrightLaw.Theuseofgeneraldescriptivenames,registerednames,trademarks,servicemarks,etc.inthispublicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse.Whiletheadviceandinformationinthisbookarebelievedtobetrueandaccurateatthedateofpublication,neithertheauthorsnortheeditorsnorthepublishercanacceptanylegalresponsibilityforanyerrorsoromissionsthatmaybemade.Thepublishermakesnowarranty,expressorimplied,withrespecttothematerialcontainedherein.Printedonacid-freepaperSpringerispartofSpringerScience+BusinessMedia()Allimpedancesarecomplex,butsomearemorecomplexthanothers.MargarethaSluyters-RehbachPrefaceMyfirstpracticalcontactwithelectrochemicalimpedancespectroscopy(EIS)wasduringmypostdoctoraltraininginthelaboratoryofProf.RonW.FawcettattheUniversityofGuelph,Ontario,Canada,in1975.AtthattimeIwasusingacvoltammetryonadroppingmercuryelectrode.Sincethen,thetechniqueandequipmenthaveevolvedsignificantly.IwascontinuallyusingEISinsubsequentyearsinthekineticsofthereductionofmetalcationsinnonaqueoussolventstodeterminethekineticsofhydrogenevolution,adsorptionandabsorptionintometals,impedanceofporouselectrodes,andelectrocatalyticreactions.AfteraseriesofseminarsontheimpedancespectroscopyinthelaboratoryofProf.BrianConwayinOttawain1994,heencouragedmetowriteareviewinModernAspectsofElectrochemistry,whichwaspublishedin1999.Prof.ConwayhasalsoaskedmetowriteasecondchapterinModernAspectsontheimpedanceofhydrogenadsorption,absorption,andevolution(2002).Later,Prof.M.Schlesingeraskedmetowriteyetanotherchapterontheimpedanceofporouselectrodes(2009).Thisbookoriginatedfrommypreviousreviewsandlecturesatvariousuniversities.Thepurposeofthisbookistopresenttheconceptofimpedance,impedanceofelectricalandelectrochemicalsystems,itslimitations,andcertainapplications.TheavailablebooksonEISwerewritteneitherbyphysicistsorengineers,andIwantedtopresentitfromthechemist’spointofview.Someknowledgeofelectro-chemistryisnecessarytounderstandthedevelopmentsofkineticequations.Ihopethatitwillbeusefultostudentswhoarejuststartingtousethistechniqueandtoothersalreadyusingitintheirresearch.Thebookcontainstheoryandapplications,numericalexamplesshowninthetext,andexerciseswithfullsolutionsontheInternet.First,electricalcircuitscontainingresistancesonlyarepresented,followedbycircuitscontainingR,C,andLelementsintransientandacconditions.Tounder-standtheconceptofimpedance,thenotionsofLaplaceandFouriertransformsarepresentedandmustbeunderstoodthoroughly.Inthischapter,impedanceplotsarealsopresented,alongwithseveralexamplesforvariouscircuits.Next,methodsfordeterminingimpedances,includingfastFouriertransform-basedtechniques,arediscussed.viiBasedonthatknowledge,theimpedanceofelectrodeprocessesinthepresenceofdiffusioninvariousgeometriesandadsorptionismathematicallydeveloped.Thisleadstothegeneralmethodofdeterminingtheimpedancesofcomplexmechanisms.Asanillustration,theimpedanceofelectrocatalyticreactionsinvolvinghydrogenadsorption,absorption,andevolutionispresented.Thenexttwochaptersdealwithimpedancedispersionatsolidelectrodesandtheimpedanceofporouselectrodesintheabsenceandpresenceofelectroactivespecies.ItisdifficulttopresentallapplicationsofEIS;someapplications(suchasthosetosolidmaterialsandPEMfuelcells,corrosionandpassivity,batteries;seeSect.1.3)maybefoundinavailablebooks.Asexamples,Mott-Schottkyplotsobtainedforsemiconductors,theimpedanceofcoatingandpaints,andelectro-catalysisofhydrogenadsorption,absorptionandevolutionwerepresentedastheyarewellknown