Effect of Solvents on the Behavior of Lithium and Superoxide Ions in Lithium-Oxygen Battery Electrolytes
溶剂对锂氧电池电解液中锂和超氧化物离子行为的影响
出版日期:2018
作者单位:VladimirS.Smirnov,JointInstituteforHighTemperaturesofthe,RussianAcademyofSciences,Moscow,RussiaMoscowInstituteofPhysicsandTechnology,Dolgoprudny,MoscowRegion,RussiaDr.SergeyA.KislenkoE-mailaddress:kislenko@ihed.ras.ruORCID:orcid.org/0000-0003-3579-5221JointInstituteforHighTemperaturesofthe,RussianAcademyofSciences,Moscow,RussiaMoscowInstituteofPhysicsandTechnology,Dolgoprudny,MoscowRegion,Russia杂志名称:ChemPhysChem
卷号:19
期数:1
刊号:1439-7641
出版日期:2018
简介:Themolecularlifeofintermediates,namely,O2−andLi+,producedduringthedischargeofaproticLi–O2batterieswasinvestigatedbymoleculardynamicssimulation.ThisworkisofpotentialinterestinthedevelopmentofnewelectrolytesforLi–airbatteries.WepresenttheresultsonthestructureandstabilityoftheLi+andO2−solvationshellsandthethermodynamicsandkineticsoftheion-associationreactioninsolventssuchasdimethylsulfoxide(DMSO),dimethoxyethane(DME),andacetonitrile(ACN).TheresidencetimeofsolventmoleculesintheLi+solvationshellincreaseswiththesolventdonornumberandis100timeslargerinDMSOthaninACN.InDMSOandDME,theLi+iondiffuseswithitssolvationshellasawhole.Onthecontrary,inACNitdiffusesasa“bare”ionbecauseofweaksolvation.TherateconstantfortheassociationofthelithiumionwiththesuperoxideanioninDMSOistwoordersofmagnitudeslowerthanthatinACNduetofactthatthefree-energybarrieris2.5?timeslargerinDMSOthaninACN.Inaddition,weshowthatdespitethestrongdependenceoftheLi+shellstabilityondonornumber,therateofassociationdoesnotnecessarilycorrelatewiththissolventproperty.