FLEXIBLE AND SHAPE-CONFORMAL ROPE-SHAPE ALKALI METAL-SULFUR BATTERIES

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FLEXIBLE AND SHAPE-CONFORMAL ROPE-SHAPE ALKALI METAL-SULFUR BATTERIES ( flexible-and-shape-conformal-rope-shape-alkali-metal-sulfur- )

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separator which leads to loss of ion transport and large increasesininternalresistanceinthecel. Inresponsetothesechalenges,new electrolytes,protec-15we US 9,905,856 B1 organosulfurandcarbon-sulfurmaterialsrelatestothe materialmassloadingsoftheelectrodesaretolow.Inmost disolutionandexcesiveout-difusionofsolublesul cases,theactivematerialmassloadingsoftheanode(areal fides,polysulfides,organo-sulfides,carbon-sulfidesand density)issignificantlylowerthan15mg/cm2andmostly<8 orcarbon-polysulfides(hereinafterreferedtoasanionic mg/cm2(arealdensity=theamountofactivematerialsper reductionproducts)from thecathodeintotherestofthe 5 electrodecros-sectionalareaalongtheelectrodethicknes cel.Thisphenomenoniscommonlyreferedtoasthe direction).Thecathodeactivematerialamountistypicaly ShutleEfect.Thisprocesleadstoseveralproblems: 1.5-2.5timeshigherthantheanodeactivematerialamount highself-dischargerates,losofcathodecapacity,coro inacel.Asaresult,theweightproportionoftheanode sionofcurentcolectorsandelectricalleadsleadingto activematerial(e.g.carbon)inaNaion-sulfurorLiion losofelectricalcontacttoactivecelcomponents,foul-10sulfurbaterycelistypicalyfrom15%to20%,andthatof ingoftheanodesurfacegivingrisetomalfunctionofthe thecathodeactivematerialfrom20%to35%(mostly anode,andcloggingoftheporesinthecelmembrane <30%).Theweightfractionofthecathodeandanodeactive Thelowactivematerialmassloadingisprimarilydueto beendeveloped.Someinterestingcathodedevelopments theinabilitytoobtainthickerelectrodes(thickerthan100 tivefilmsforthelithiumanode,andsolidelectrolyteshave havebeenreportedrecentlytocontainlithiumpolysulfides; 20um)usingtheconventionalslurycoatingprocedure. but,theirperformancestilfalshortofwhatisrequiredfor Thisisnotatrivialtaskasonemightthink,andinrealitythe practicalapplications. 20electrodethicknesisnotadesignparameterthatcanbe Despitethevariousaproachesproposedforthefabrica- arbitrarilyandfrelyvariedforthepurposeofoptimizing tionofhighenergydensityLiScels,thereremainsaneed thecelperformance.Contrarily,thickersamplestendto forcathodematerialsandproductionprocessesthatimprove becomeextremelybritleorofpoorstructuralintegrityand theutilizationofelectro-activecathodematerials(Sutiliza- wouldalsorequiretheuseoflargeamountsofbinderresin. tioneficiency),andproviderechargeableLi-Scelswith 25Duetothelow-meltingandsoftcharacteristicsofsulfur,it highcapacitiesoveralargenumberofcycles.Mostsignifi- hasbeenpracticallyimpossibletoproduceasulfurcathode cantly,lithiummetal(includingpurelithium,lithiumaloys thickerthan10um.Furthermore,inarealbaterymanu ofhighlithiumcontentwithothermetalelements,or facturingfacility,acoatedelectrodethickerthan150um lithium-containingcompoundswithahighlithiumcontent; wouldrequireaheatingzoneaslongas10metersto e.g.>80% orpreferably >90%byweightLi)stilprovides 30 thoroughly drythecoatedslury.Thiswould significantly thehighestanodespecificcapacityascomparedtoesen- increasetheequipmentcostandreducetheproduction tialyalotheranodeactivematerials(exceptpuresilicon, throughput.Thelowarealdensitiesandlowvolumedensi butsiliconhaspulverizationisues).Lithiummetalwould ties(relatedtothinelectrodesandpoorpackingdensity) beanidealanodematerialinalithium-sulfursecondary resultinarelativelylowvolumetriccapacityandlow batteryifdendriterelatedisuescouldbeaddressed. 35volumetric energydensityofthebaterycels. Sodiummetal(Na)andpotasiummetal(K)havesimilar Withthegrowingdemandformorecompactandportable chemicalcharacteristicstoLiandthesulfurcathodeinroom energystoragesystems,thereiskeeninteresttoincreasethe temperaturesodium-sulfurcels(RTNa-Sbateries)or utilizationofthevolumeofthebateries.Novelelectrode potasium-sulfurcels(K—S)facethesameisuesobserved materialsanddesignsthatenablehighvolumetriccapacities inLi-Sbateries,suchas:(i)lowactivematerialutilization 40 andhighmassloadingsareesentialtoachievingimproved rate,(i)poorcyclelife,and(i)lowCoulombiceficiency. celvolumetriccapacitiesandenergydensities. Again,thesedrawbacksarisemainlyfrom insulatingnature Thus,anobjectofthepresentinventionistoprovidea ofS,dissolutionofSandNaorKpolysulfideintermediates rechargeablealkalimetal-sulfurcelbasedonrationalmate inliquidelectrolytes(andrelatedShutleefect),andlarge rialsandbaterydesignsthatovercomeorsignificantly volume change during charge discharge. 45 reduce the following issues commonly associated with con Itmaybenotedthatinmostoftheopenliteraturereports ventionalLi-SandNa—Scels:(a)dendriteformation (scientificpapers)andpatentdocuments,scientistsorinven (internalshorting);(b)extremelylowelectricandionic torschoosetoexpressthecathodespecificcapacitybasedon conductivitiesofsulfur,requiringlargeproportion(typically thesulfurorlithiumpolysulfideweightalone(notthetotal 30-55%)ofnon-activeconductivefilersandhavingsignifi cathodecompositeweight),butunfortunatelyalargepro-50 cantproportionofnon-accessibleornon-reachablesulfuror portionofnon-activematerials(thosenotcapableofstoring alkalimetalpolysulfides);(c)disolutionofSandalkali lithium,suchasconductiveaditiveandbinder)istypicaly metalpolysulfideinelectrolyteandmigrationofpolysul usedintheirLi–Scels.Forpracticalusepurposes,itis fidesfromthecathodetotheanode(whichirreversiblyreact moremeaningfultousethecathodecompositeweight-based withLiorNametalattheanode),resultinginactivematerial capacityvalue. 5 losandcapacitydecay(theshutleefect);(d)shortcycle Low-capacityanodeorcathodeactivematerialsarenot life;and(e)lowactivemassloadinginboththeanodeand theonlyproblemasociatedwiththelithium-sulfuror thecathode. sodium -sulfurbattery. There are serious design and manu - A specific object of the present invention is to provide a facturingisuesthatthebateryindustrydoesnotsemtobe rechargeablealkalimetal-sulfurbatery(e.g.mainlyLi-S awareof,orhaslargelyignored.Forinstance,despitethe60androom temperatureNa Sbattery)thatexhibitsan seeminglyhighgravimetriccapacitiesattheelectrodelevel exceptionalyhighspecificenergyorhighenergydensity. (basedontheanodeorcathodeactivematerialweightalone) Oneparticulartechnicalgoalofthepresentinventionisto asfrequentlyclaimedinopenliteratureandpatentdocu- provideanalkalimetal-sulfuroralkaliion-sulfurcelwitha ments,theseelectrodesunfortunatelyfailtoprovidebatter- celspecificenergygreaterthan400Wh/Kg,preferably ieswithhighcapacitiesatthebaterycelorpacklevel65greaterthan50Wh/Kg,morepreferablygreaterthan60 (basedonthetotalbaterycelweightorpackweight).This Wh/Kg,andmostpreferablygreaterthan700Wh/kg(al isduetothenotionthat,inthesereports,theactualactive basedonthetotalcelweight).Preferably,thevolumetric materialscombinedistypicalyfrom35%to50%ofthecel

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