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FLEXIBLE AND SHAPE-CONFORMAL ROPE-SHAPE ALKALIMETAL-SULFUR BATTERIES FIELDOF THEINVENTION Thisinventionisdirectedatasecondary(rechargeable) lithium-sulfurbatery(includingLi—SandLiion-Scels), sodium-sulfurbatery(includingNa—SandNaion-Scels), 120-250Wh/kg,mosttypicaly150-20Wh/kg.Thesespe cificenergyvaluesaretwotothreetimeslowerthanwhat would be required forbattery-powered electric vehicles to bewidelyacepted. With therapiddevelopmentofhybrid (HEV),plug-in hybrid electric vehicles(HEV),and al-batery electric vehicles(EV),thereisanurgentneedforanodeandcathode materialsthatprovidearechargeablebaterywithasignifi cantlyhigherspecificenergy,higherenergydensity,higher US 9,905,856 B1 ortheircombinationorhybridcelthatisflexible,confor-10ratecapability,longcyclelife,andsafety.Oneofthemost mal,andnon-flammable. promising energy storage devices is the lithium -sulfur (Li— S)celsincethe theoreticalcapacity of Liis3,861 BACKGROUNDOF THEINVENTION mAh/gandthatofSis1,675mAh/g.Initssimplestform, aLi—Scelconsistsofelementalsulfurasthepositive Conventionalbateries(e.g.18650-typecylindricalcels, 15 electrodeand lithium asthenegativeelectrode.Thelithium rectangularpouchcels,orprismaticcels)aremechanicaly sulfurceloperateswitharedoxcouple,describedbythe rigidandthisnon-flexibilityfeaturehasseverelyconstrained reactionSa+16LiH8Li,Sthatliesnear2.2Vwithrespectto itsadaptabilityorfeasibilityofbeingimplementedincon- Li+/Li°.Thiselectrochemicalpotentialisaproximately23 finedspacesorforuseinwearabledevices.Flexibleand ofthatexhibitedbyconventionalpositiveelectrodes(e.g. shape-conformable power sources can be used to overcome 20 LiMnO2) in a conventional lithium -ion battery.However, thesedesignlimitations.Thesenewpowersourceswil thisshortcomingisofsetbytheveryhightheoretical enablethedevelopmentofnext-generationelectronic capacitiesofbothLiandS.Thus,comparedwithconven devices,suchassmartmobilegadgets,rol-updisplays, tionalintercalation-basedLi-ionbateries,Li Scelshave wearabledevices,andbiomedicalsensors.Flexibleand theopportunitytoprovideasignificantlyhigherenergy conformable power sources will also save weight and space 25 density (a product of capacity and voltage). Assuming inelectricvehicles. complete reaction to Li,S, energy densities values can Rechargeablelithium-ion(Li-ion)andlithiummetalbat approach 2,500Wh/kgand2,800Wh/L,respectively,based teries(includingLi-sulfurandLimetal-airbateries)are onthecombinedLiandSweightorvolume.Ifbasedonthe consideredpromisingpowersourcesforelectricvehicle totalcelweightorvolume,theenergydensitiescanreach (EV),hybridelectricvehicle(HEV),andportableelectronic 30aproximately 1,0Wh/kgand1,30Wh/L,respectively. devices,suchaslap-topcomputersandmobilephones. However,thecurentLi-sulfurcelsreportedbyindustry Historicaly,rechargeablelithiummetalbaterieswerepro- leadersinsulfurcathodetechnologyhaveamaximumcel ducedusingnon-lithiatedcompoundshavingrelativelyhigh specificenergyof250-400Wh/kgand350-50Wh/L(based specificcapacities,suchasTiS2,MoS2,MnO2,C002,and onthetotalcelweightorvolume),whicharefarbelowwhat V,05,asthecathodeactivematerials,whichwerecoupled 35 isposible. with alithiummetalanode.When thebaterywasdis- Insummary,despiteitsconsiderableadvantages,the charged,lithiumionsweretransferedfromthelithium Li–Scelisplaguedwithseveralmajortechnicalproblems metalanodethroughtheelectrolytetothecathode,andthe thathavethusfarhindereditswidespreadcommercializa cathodebecamelithiated.Unfortunately,uponrepeated tion: charges/discharges,thelithiummetalresultedintheforma-40(1)Conventionallithiummetalcelsstilhavedendrite tionofdendritesattheanodethatultimately grew to formationandrelatedinternalshortingisues. penetratethroughtheseparator,causinginternalshorting (2)Sulfurorsulfur-containingorganiccompoundsare andexplosion.Asaresultofaseriesofacidentsasociated highly insulating,both electricaly and ionicaly.To withthisproblem,theproductionofthesetypesofsecond enableareversibleelectrochemicalreactionathighcur arybatterieswasstoppedintheearly1990's,givingwaysto45 rentdensitiesorcharge/dischargerates,thesulfurmust lithium-ionbateries. maintainintimatecontactwithanelectricalyconductive Inlithium-ionbateries,purelithiummetalshetorfilm aditive.Variouscarbon-sulfurcompositeshavebeen was replaced by carbonaceousmaterials as the anode.The utilized for this purpose,but only with limited success carbonaceousmaterialabsorbslithium (throughintercala owingtothelimitedscaleofthecontactarea.Typical tionoflithiumionsoratomsbetweengrapheneplanes,for50 reportedcapacitiesarebetween300and550mAh/g instance)anddesorbslithiumionsduringthere-chargeand (basedonthecathodecarbon-sulfurcompositeweight)at dischargephases,respectively,ofthelithiumionbatery moderaterates. operation.Thecarbonaceousmaterialmaycompriseprimar- (3)Theceltendstoexhibitarapidandsignificantcapacity ilygraphitethatcanbeintercalatedwithlithium andthe decayduringdischarge-chargecycling.Thisismainlydue resultinggraphiteintercalationcompoundmaybeexpresed5 tothehighsolubilityofthelithiumpolysulfideanions asLiCo,wherexistypicalylesthan1. formedasreactionintermediatesduringbothdischarge Althoughlithium-ion(Li-ion)bateriesarepromising andchargeprocesesinthepolarorganicsolventsusedin energystoragedevicesforelectricdrivevehicles,state-of electrolytes.Duringcycling,thelithium polysulfide the-artLi-ionbaterieshaveyettomeetthecostandper anionscanmigratethroughtheseparatortotheLinega formancetargets.Li-ioncelstypicallyusealithiumtran-60 tiveelectrodewhereupontheyarereducedtosolidpre sition-metaloxideorphosphateasapositiveelectrode cipitates(Li,S,and/orLi,S),causingactivemasslos.In (cathode)thatde/re-intercalatesLi*atahighpotentialwith adition,thesolidproductthatprecipitatesonthesurface respecttothecarbonnegativeelectrode(anode).Thespe ofthepositiveelectrodeduringdischargebecomeselec cificcapacityoflithiumtransition-metaloxideorphosphate trochemicaly ireversible,which also contributesto basedcathodeactivematerialistypicalyintherangeof65 activemasslos. 140-170mAh/g.Asaresult,thespecificenergyofcommer- (4)Moregeneralyspeaking,asignificantdrawbackwith cialyavailableLi-ioncelsistypicalyintherangeof celscontainingcathodescomprisingelementalsulfur,PDF Image | FLEXIBLE AND SHAPE-CONFORMAL ROPE-SHAPE ALKALI METAL-SULFUR BATTERIES
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