Patent Lithium Extraction with coated ion exchange particles

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Patent Lithium Extraction with coated ion exchange particles ( patent-lithium-extraction-with-coated-ion-exchange-particles )

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LITHIUM EXTRACTION WITH COATED ION EXCHANGE PARTICLES CROSS-REFERENCE LiTiz0123 LiTiO3, LizMn03, Li2Sn03, LiMn204 Li1.6Mn1.604, LiA102, LiCuO2, LiTiO2, LiTi04, Li,Ti,024, LizV04, LiSiz07, LiFePO4, LiMnPO4, Li-CUP-07, Al(OH)3, LiCl.xAl(OH)3.yH,O, US 10,695,694B2 12 5 SnO2.xSb205.yH2O,TiO2.xSb2O3.yH20,solidsolutions ThisaplicationisacontinuationofU.S.aplicationSer. thereof,andcombinationsthereof.Insomeembodiment,x BACKGROUND OF THE INVENTION ablebateriesandothertechnologies.Lithium canbefound 15LizMnOz,LiTiO3,LiTi,012,LiMn3012,Li1.6Mn1.604, No.15/811,415,filedNov.13,2017,whichclaimsthe isselectedfrom0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1, benefitofU.S.ProvisionalAplicationNo.62/421,934,filed 2,3,4,5,6,7,8,9,and10.Insomeembodiments,yis Nov.14,2016,bothofwhichareincorporatedhereinby selectedfrom0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,2, referenceintheirentireties. inavarietyofliquidsolutions,includingnaturalandsyn andcombinationsthereof. 10 3,4,5,6,7,8,9,and10.Insomeembodiments,xandyis independentlyselectedfrom0.1,0.2,0.3,0.4,0.5,0.6,0.7, 0.8,0.9,1,2,3,4,5,6,7,8,9,and10.Insomeembodi Lithiumisanesentialelementforhigh-energyrecharge ments,theionexchangematerialisselectedfromLiSnoz, theticbrines,leachatesolutionsfromminerals,andrecycled Insomeembodiments,thecoatedionexchangeparticle products. has an averagediameteroflesthan 10um.In some embodiments,thecoatedionexchangeparticlehasanaver SUMMARY OF THE INVENTION 20agediameteroflesthan10um.Insomeembodiments,the coatedionexchangeparticlehasanaveragediameterofles Lithiumcanbeextractedfromliquidresourcesusingan than1,0nm.Insomeembodiments,thecoatedion ionexchangeprocesbasedoninorganicionexchange exchangeparticlehasanaveragediameteroflesthan10 materials.Inorganicionexchangematerialsabsorblithium nm . ionsfromaliquidresourcewhilereleasinghydrogenions,25 Anaspectdescribedhereinisaporousstructureforion andthenelutelithiumionsinacidwhileabsorbinghydrogen exchangecomprising:a)astructuralsuport;andb)a ions.Theionexchangeprocescanberepeatedtoextract pluralityofparticlesselectedfromcoatedionexchange lithiumionsfromaliquidresourceandyieldaconcentrated particles,uncoatedionexchangeparticles,andacombina lithiumionsolution.Theconcentratedlithiumionsolution tionthereof. canbefurtherprocesedintochemicalsforthebatery30 Insomeembodiments,thestructuralsuportcomprisesa industryorotherindustries. polymer,anoxide,aphosphate,orcombinationsthereof.In Amajorchalengeforlithiumextractionusinginorganic someembodiments,thestructuralsuportcomprisesapoly ionexchangematerialsisthedisolutionanddegradationof mer.Insomeembodiments,thepolymerispolyvinylidene materials.Thisisespecialysoduringlithiumelutioninacid fluoride,polyvinylfluoride,polyvinylchloride,polyvi butalsoduringlithiumuptakeinliquidresources.Toyield35 nylidenechloride,achloro-polymer,afluoro-polymer,a proces,itisdesirabletouseaconcentratedacidsolutionto fluoro-chloro-polymer,polyethylene,polypropylene,poly a concentrated lithium solution from the ion exchange elute the lithium . However, concentrated acid solutions disolveanddegradeinorganicionexchangematerials, whichdecreasetheperformanceandlifespanofthemate-40polybutadiene,asulfonatedpolymer,acarboxylatedpoly rials.Thereisanedthereforeforamethodofextracting mer,polyacrylonitrile,tetrafluoroethylene,perfluoro-3,6-di lithiumionsinwhichinorganicionexchangematerialsare oxa-4-methyl-7-octene-sulfonicacid(NAFION®(copoly protectedfromdisolutionanddegradation. merofperfluoro-3,6-dioxa-4-methyl-7octene-sulfonicacid Anaspectdescribedhereinisacoatedionexchange andtetrafluoroethylene),copolymersthereof,orcombina particlecomprisinganionexchangematerialandacoating45tionsthereof. disolutionoftheionexchangematerial.Insomeembodi penetratequicklyintothebeadanddeliverlithiumionand ments,thecoatingmaterialalowsdifusionoflithiumions hydrogenionstoandfromionexchangeparticlesinthe andhydrogenionstoandfromtheionexchangematerial.50bead.Insomeembodiments,theporousstructurehasa Insomeembodiments,thecoatingmaterialcomprisesa conectednetworkofporesthatarestructuredtoenablefast carbide,anitride,anoxide,aphosphate,afluoride,a infiltrationbyliquidsolutionstocreateliquiddifusion polymer,carbon,acarbonaceousmaterial,orcombinations chanelsfromthebeadsurfacetotheionexchangeparticles thereof.Insomeembodiments,thecoatingmaterialcom inthebead.Insomeembodiments,theporousbeadhasa prisesTiO2,ZrO2,Mo02,SnO2,Nb2O5,Ta2O5,Li,TiO3,5hierarchicalconectednetworkofporeswithadistribution SIO,Li,ZrOz,Li,M002,LiNbO3,LiTaOz,AlPO4,LaPOA, ofporesizessuchthattheporenetworkcreatespathways ZrSiO4,ZrP207,MoP207,Mo2P3012,BaSO4,AlF3,Sic, betwenthesurfaceofthebeadandtheionexchange Tic,Zrc,SizN4,ZrN,BN,carbon,graphiticcarbon,amor particlesinthebead.Insomeembodiments,theporous phouscarbon,hardcarbon,diamond-likecarbon,solidsolu structureincludesporeswithdiametersrangingfromles tionsthereof,orcombinationthereof.Insomeembodiments,60than10umtogreaterthan50um.Insomeembodiments,the thecoatingmaterialcomprisesTiO2.Insomeembodiments, porousstructureincludesporeswithdiametersrangingfrom thecoatingmaterialcomprisesSiO2.Insomeembodiments, morethan1um,morethan2um,morethan4um,morethan thecoatingmaterialcomprisesZro, 6um,morethan8um,morethan10um,morethan15um, Insomeembodiments,theionexchangematerialcom morethan20um,morethan40um,morethan60um,more prisesanoxide,aphosphate,anoxyfluoride,afluorophos-65than80um,morethan10um,lesthan2um,lesthan4 phate,orcombinationsthereof.Insomeembodiments,the um,lesthan6um,lesthan8um,lesthan10um,lesthan ionexchangematerialisselectedfromLi_Mn3012, 15um,lesthan20um,lesthan40um,lesthan60um, material. Insomeembodiments,thecoatingmaterialprevents nectednetworkofporesthatenablesliquidsolutionsto phenylenesulfide,polytetrafluoroethylene,sulfonatedpoly tetrafluoroethylene, polystyrene, polydivinylbenzene, Insomeembodiments,theporousstructurehasacon

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