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US 10,695,694B2 78 LiSiO3,Li,Si,Os,LiMnOz,ZrSiO4,AIPO4,LaPO4, oxidants,reductants,acids,bases,orcombinationsthereof. ZrP,O,MOP,0%,Mo,P,0,2,BaSO4,AlF3,Sic,Tic,Zrc, Insomeembodiments,thereagentsareadedinthepres SizN4,ZrN,BN,carbon,graphiticcarbon,amorphouscar enceofcatalystssuchasacids,bases,orcombinations bon,hardcarbon,diamond-likecarbon,solidsolutions thereof.Insomeembodiments,thereagentsareaded thereof,orcombinationsthereof.Insomeembodiments,the 5 duringatimeperiodoflesthan1minute,lesthan1hour, coatingmaterialcomprisespolyvinylidenedifluoride,poly lesthan1day,lesabout1week,morethan1minute,more vinylchloride,afluoro-polymer,achloro-polymer,ora than1hour,morethan1day,fromabout1minutetoabout fluoro-chloro-polymer.Insomeembodiments,thecoating 60minutes,fromabout1hourtoabout24hours,orfrom materialcomprisesTiO2,ZrO2,SiO2M002,LiTiO3, about1daytoabout7days.Insomeembodiments,the LiZr03,Li,MnO3,ZrSiO4,orLiNbO3,AlF3,Sic,SizN4,10reagentsaredripedintothereactorcontinuouslyorat graphiticcarbon,amorphouscarbon,diamond-likecarbon, intervals.Insomeembodiments,multiplereagentsareaded orcombinationsthereof.Insomeembodiments,thecoating tothereactoratdiferentrates.Insomeembodiments,some materialcomprisesTiO2,SiO2,orZrO2.Insomeembodi reagentsarecombinedseparatelyandreactedtoformagel ments,thecoatingmaterialcomprisesTiO2.Insome orpolymerpriortoaditiontothereactor. embodiments,thecoatingmaterialcomprisesSiO2.Insome15 Insomeembodiments,thefreshlycoatedionexchange embodiments,thecoatingmaterialcomprisesZroz. materialisheatedtooneormoretemperaturestoage,dry, Insomeembodiments,thecoatingcoatsprimaryion react,orcrystalizethecoating.Insomeembodiments,the exchangeparticlesorsecondaryionexchangeparticles.In freshlycoatedionexchangematerialisheatedtoatempera someembodiments,thecoatingcoatsboththeprimaryion tureoflesthanabout10°C.,lesthanabout20°C.,les exchangeparticlesandthesecondaryionexchangeparticles.20thanabout30°C.,lesthanabout40°C.,lesthanabout Insomeembodiments,theprimaryionexchangeparticles 50°C.,lesthanabout600°C.,lesthanabout70°C.,or haveafirstcoatingandthesecondaryionexchangeparticles lesthanabout800°C.Insomeembodiments,thefreshly haveasecondcoatingthatisidentical,similar,ordiferent coatedionexchangematerialisheatedtoatemperatureof in composition to the first coating. more than about 100° C.,more than about 200° C.,more Insomeembodiments,thecoatingmaterialhasathick-25 thanabout300°C.,morethanabout400°C.,morethan nessoflesthan1nm,lesthan10nm,lesthan100nm, about500°C.,morethanabout600°C.,morethanabout lesthan1,0nm,lesthan10,0nm,morethan1nm, 700°C.,ormorethanabout80°C.Insomeembodiments, morethan10nm,morethan10nm,morethan1,0nm, thefreshlycoatedionexchangematerialisheatedtoa morethan10,0nm,fromabout1nmtoabout10,0nm, temperaturefromabout100°C.toabout800°C.,fromabout fromabout10nm,toabout1,0nm,orfromabout10to3020°C.toabout80°C.,fromabout30°C.toabout70° about1,0nm.Insomeembodiments,thecoatingmaterial C.,fromabout400°C.toabout70°C.,fromabout500°C. hasathicknesoflesthan5nm,lesthan10nm,lesthan toabout700°C.,fromabout10°C.toabout300°C.,from 50nm,lesthan10nm,lesthan500nm,morethan1nm, about200°C.toabout400°C.,fromabout300°C.toabout morethan5nm,morethan10nm,morethan50nm,more 50°C.,fromabout400°C.toabout600°C.,fromabout than10nm,fromabout1nm toabout50nm,fromabout3550°C.toabout70°C.,orfrom about600°C.toabout 1nmtoabout10nm,fromabout1nmtoabout50nm, 800°C.Insomeembodiments,thefreshlycoatedion fromabout1nmtoabout10nm,fromabout1nmtoabout exchangematerialisheatedinanatmosphereofaircom 5nm,orfrom about5nm toabout10nm. prisingoxygen,nitrogen,hydrogen,argon,orcombinations Insomeembodiments,thecoatingmaterialisdeposited thereof.Insomeembodiments,thefreshlycoatedion byamethodsuchaschemicalvapordeposition,atomiclayer40exchangematerialisheatedforatimeperiodoflesthan deposition,physicalvapordeposition,hydrothermal,solvo about1hour,lesthanabout2hours,lesthanabout4hours, thermal,sol-gel,solidstate,moltensaltflux,ionexchange, lesthanabout8hours,lesthanabout24hours,morethan microwave,chemicalprecipitation,co-precipitation,bal 1hour,morethan2hours,morethan4hours,morethan8 miling,pyrolysis,orcombinationsthereof.Insome hours,fromabout0.5hourstoabout24hours,fromabout embodiments,thecoatingmaterialisdepositedbyamethod450.5hourstoabout8hours,fromabout0.5hourstoabout4 suchaschemicalvapordeposition,hydrothermal,solvother hours,fromabout0.5hourstoabout2hours,orfromabout mal,sol-gel,precipitation,microwavesol-gel,chemical 0.5hourstoabout1hour. precipitation,orcombinationsthereof.Insomeembodi Insomeembodiments,thecoatingmaterialisdeposited ments,thecoatingmaterialsisdepositedinareactorthatis withphysicalcharacteristicssuchascrystaline,amorphous, abatchtankreactor,acontinuoustankreactor,abatch 50fulcoverage,partialcoverage,uniform,non-uniform,or furnace,acontinuousfurnace,atubefurnace,arotarytube combinationsthereof.Insomeembodiments,multiplecoat furnace, or combinations thereof. ings are deposited on the ion exchange material in an Insomeembodiments,thecoatingmaterialisdepositedin arangementsuchasconcentric,patchwork,orcombinations areactorbysuspendingtheionexchangematerialina thereof. solventwithreagentsthatisadedalatonceoradedover5IonExchangeMaterialofCoatedIonExchangeParticle time.Insomeembodiments,thereagentsareadedina Insomeembodiments,theionexchangematerialissuit specifictimeseriestocontrolreactionratesandcoating ableforhighlithiumabsorptioncapacityandforlithium depositions.Insomeembodiments,thesolventisaqueousor ionsinaliquidresourcerelativetootherionssuchassodium non-aqueous.Insomeembodiments,thesolventisanalco ionsandmagnesiumions.Insomeembodiments,theion holsuchasethanol,propanol,butanol,pentanol,hexanol,60 exchangematerialissuitableforstronglithiumionuptakein septanol,oroctanol.Insomeembodiments,thereagents liquidresourcesincludingthosewithlowconcentrationsof includemetalchlorides,metaloxides,metalalkoxides, lithiumions,facileelutionoflithiumionswithasmal metaloxychlorides,metaloidoxides,metaloidalkoxides, excesofacid,andfastionicdifusion. metaloidchlorides,metaloidoxychlorides,orcombina Insomeembodiments,theionexchangematerialcom tionsthereof.Insomeembodiments,thereagentsinclude65prisesanoxide,aphosphate,anoxyfluoride,afluorophos monomers,oligomers,polymers,gels,orcombinations phate,orcombinationsthereof.Inafurtherembodiment,the thereof.Insomeembodiments,thereagentsincludewater, ionexchangematerialcomprisesLiFePO4,LiMnPO4,PDF Image | Patent Lithium Extraction with coated ion exchange particles
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