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US 9,905,856 B1 16 rial-freandelectrolyte-freendsectionthatcanserveasa UsingSchematic Casanotherexample,twospraying terminaltabforconectingtoanexternalload.Thesecond devices324a,324bwereusedtodispensethewetactive electrodemaybeoptionalybutdesirablyencasedor material/electrolytemixture(325a,325b)tothetwo wrappedaroundbyaporousseparatorlayer18. opposedporoussurfacesoftheconductiveporousrod32. Thissecondelectrode,withorwithoutanencasingporous 5 Thewetactivematerialmixtureisforcedtoimpregnateinto separatorlayeristhencombinedwiththefirstelectrode theporousrodfrombothsidesusingoneortwopairsof usingabraidingoryarn-makingproceduretomakea2-ply rolerstoformanimpregnatedactiveelectrode326(an twistyarnorbraid.Ifthefirstelectrodeisananode,thenthe anodeorcathode).Similarly,inSchematicD,twospraying secondelectrodeisacathode;orviceversa.Ayarnorbraid devices 332a,332b were used to dispense thewetactive cancontainmultipleanodes(i.e.multiplefilamentsorrods 10materialmixture(333a,333b)tothetwoopposedporous eachcontainingananodeactivematerialandanelectrolyte) foamrodsurfacesoftheconductiveporousrod330.Thewet combinedwithonesinglecathodeormultiplecathodes.A activematerial-electrolytemixtureisforcedtoimpregnate yarn or braid can contain multiple cathodes (i.e.multiple into the porous rod from both sides using one or two pairs filamentsorrodseachcontainingacathodeactivematerial ofrolerstoformanimpregnatedactiveelectrode338(an and an electrolyte) combined with one single anode or 15 anode or cathode). multipleanodefilaments.Asthefinalstep,thisbraidoryarn Asanotherexample,asilustratedinSchematicEofFIG. structureisencasedorprotectedbyaprotectivecasingor 1(E),theelectrodeproductionprocesbeginsbycontinu sheath19thatiselectricalyinsulating(e.g.aplasticsheath ouslyfeedingaconductiveporousfoamrodorfilament356 orrubershel). ofanycros-sectionalshapefrom afederroler340.The Itmaybenotedthatsomeaditionalelectrolytemaybe20porouslayer356isdirectedbyaroler342togetimersed incorporatedbetween then-plybraid/yarn (n=2)andthe intoawetactivematerialmixturemass346(slury,suspen protectivesheath.However,thisisnotarequirementsince sion,gel,etc.)inacontainer34.Theactivematerial altheelectroderodsorfilamentsalreadycontainanactive mixturebeginstoimpregnateintoporesoftheporousrodor materialand an electrolyteintheirpores. filament356 asittravelstowardroler342b andemerges Insomeembodiments,oneoftheelectrodescomprisesa25 fromthecontainertofeedintothegapbetweentworolers porousrodhavingporestoaccommodateanactivematerial- 348a,348b.Twoprotectivefilms350a,350bareconcur electrolytemixtureandatleastoneoftheelectrodesisa rentlyfedfromtworespectiverolers352a,352btocover non-porousrod(filament,fiber,wire,etc.)havinganactive theimpregnatedporouslayer354,whichmaybecontinu material-electrolytemixturecoatedonitssurface. ouslycolectedonarotatingdrum (awindingroler355). Thereareseveralmeansofmakingthefirstelectrodeor 30 Theprocesisaplicabletoboththeanodeandthecathode thesecondelectrode.AsschematicallyilustratedinFIG. electrodes. 1(D)andusingasquareorrectangularfoamrodcros- Theresultingelectroderodorfilament(anodeorcathode sectionasan example,onepreferredmethod comprises electrode)canhaveathicknessordiameterfrom 100nm to continuouslyfedingoneorapluralofelectricalyconduc- severalcentimeters(orthicker,ifsodesired).Foramicro tiveporousfoam rod(e.g.304,310,322,or330;onlyone 35cable(e.g.asaflexiblepowersourceforamicro-electronic foamrodbeingshown,buttherecanbemultiplerodsineach device)theelectrodethicknesordiameterisfrom10nm case),fromafeederroler(notshown),intoanactive to10um,moretypicalyfrom1umto50um,andmost material/electrolyteimpregnationzonewhereawetactive typicalyfrom10umto30um.Foramacroscopic,flexible materialmixture(e.g.slury,suspension,orgel-likemass, andconformalcablebatery(e.g.foruseinconfinedspaces such as 306a,306b,312a,312b)ofan electrodeactive 40 in an electric vehicle, EV),the electrode typicaly and material,anelectrolyteandanoptionalconductiveaditive desirablyhasathicknesnolesthan10um(preferably isdeliveredtoatleastaporoussurfaceoftheporousrod >20um,furtherpreferably>300um,morepreferably>400 (e.g.304or310inSchematicAandschematicB,respec- um;furthermorepreferably>50um,600um,oreven tively,ofFIG.1(D).UsingSchematicAasanexample,the >1,000um;notheoreticallimitationontheelectrodethick wet active material/electrolyte mixture (306a, 306b) is 45 ness. forcedtoimpregnate intotheporousrod from bothsides Theabovearebutseveralexamplestoilustratehow the usingoneortwopairsofrolers(302a,302b,302c,and presentlyinventedflexibleandshape-conformablerope-like 302d)toformanimpregnatedactiveelectrode308(an alkalimetalbateriescanbemade.Theseexamplesshould anodeorcathode).Theconductiveporousfoamrodcontains notbeusedtolimitthescopeoftheinstantinvention. interconnectednetworkofelectron-conductingpathways50 Theelectricalyconductiveporousrodsorfilamentsmay andatleast50%byvolumeofpores(preferably>70%,more beselectedfrommetalfoam,metalweborscreen,perfo preferably>80%,furtherpreferably>90%,andmostpref- ratedmetalshet-basedstructure,metalfibermat,metal erably>95%). nanowiremat,conductivepolymernano-fibermat,conduc InSchematicB,twofederrolers316a,316bareusedto tivepolymerfoam,conductivepolymer-coatedfiberfoam, continuouslypayouttwoprotectivefilms314a,314bthat5 carbonfoam,graphitefoam,carbonaerogel,carbonxerogel, supportwetactivematerial/electrolytemixturelayers312a, grapheneaerogel,graphenefoam,grapheneoxidefoam, 312b.Thesewetactivematerial/electrolytemixturelayers reducedgrapheneoxidefoam,carbonfiberfoam,graphite 312a,312bcanbedeliveredtotheprotective(suporting) fiberfoam,exfoliatedgraphitefoam,oracombination films314a,314busingabroadarayofprocedures(e.g. thereof.Theporousrodsorfikamentsmustbemadeofan printing,spraying,casting,coating,etc.,which arewell60electricalyconductivematerial,suchasacarbon,graphite, knownintheart).Astheconductiveporousfoamrod10 metal,metal-coatedfiber,conductivepolymer,orconduc movesthoughthegapsbetweentwosetsofrolers(318a, tivepolymer-coatedfiber,whichisinaformofhighly 3186,318c,318d),thewetactivemixturematerial/electro- porousmat,scren/grid,non-woven,foam,etc.Examplesof lyteisimpregnatedintotheporesoftheporousrod310to conductiveporouslayersarepresentedinFIG.3(A),FIG. formanactivematerialelectrode320(ananodeorcathode 65 3(B),FIG.3(C),andFIG.3(D).Theporositylevelmustbe electrodelayer)coveredbytwoprotectivefilms314a,314b. atleast50%byvolume,preferablygreaterthan70%,further 15 Theseprotectivefilmscanbelaterremoved. preferablygreaterthan90%,andmostpreferablygreaterPDF Image | FLEXIBLE AND SHAPE-CONFORMAL ROPE-SHAPE ALKALI METAL-SULFUR BATTERIES
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