Silica jel adag nanocomposite electrolytes oo leh kor u qaadida hagaajinta waji ee ka badan inta badan Li-ion conductivity ee buuxinta dareeraha dareeraha ionic

U gudubka baytariyada Li-ion-ka adag waxay awood u siinaysaa horumarka xagga cufnaanta tamarta ee 1000 Wakh/litir iyo wixii ka dambeeya.Isku-dhafka shaxanka oksaydhka mesoporous oo ay ka buuxaan buuxinta dareeraha dareeraha ionic ee aan isbeddelayn ayaa loo sahamiyay sidii doorasho adag oo elektrolyt ah.Si kastaba ha noqotee, xaddidaadda fudud ee xalalka elektrolytka ee gudaha daloolada cabbirka nanometer-ka ah waxay keenaysaa hoos u dhigista ion-ku-shaqaynta maaddaama viscosity-ku kordho.Halkan, waxaan ku muujineynaa in conductivity Li-ion ee nanocomposites ka kooban mesoporous silica monolith leh ion dareere electrolyte filler noqon kartaa dhowr jeer ka badan ka mid ah electrolyte dareere ionic saafi ah iyada oo hordhaca ah ee lakabka barafka interfacial.Adsorption xoog leh iyo dalbashada molecules dareeraha ionic waxay ka dhigtaa kuwa dhaqaaqi kara oo adag sida lakabka barafka dhexda laftiisa.Dufanka ka sarreeya lakabka mesophase-ka adsorbate wuxuu keenaa xallinta ion-yada Li+ si loo hagaajiyo.Mabda'a la soo bandhigay ee kor u qaadista ion waxaa lagu dabaqi karaa nidaamyada kala duwan ee ion.

Electrolytes-ka adag ayaa la filayaa inay bixiyaan kobcinta soo socota ee baytariyada Li-ion si ay u dhaafaan saqafka dhabta ah ee 800 Wa·hour/litir ama 300 W·hour/kg oo lagu soo rogay cathode iyo kiimikooyinka anode ee hadda jira.Korodhka la filayo ee cufnaanta tamarta ee baytariyada adag ee gobolka waxay ka timaadaa tabarucyo dhowr ah, oo dhan oo la beegsanayo kordhinta boqolkiiba mugga walxaha firfircoon ee unugyada.Inta ugu badan ee la dacaayadeeyay waa soo bandhigida birta lithium si loogu beddelo garaafka iyo garaafka/silikoon sidii anode ahaan.Birta lithium-ka saafiga ah waxay leedahay cufnaanta tamarta ugu sareysa ee suurtogalka ah sidaas darteed waxay u baahan doontaa meesha ugu yar.Si kastaba ha ahaatee, arrimo badan ayaa weli u baahan in la xalliyo, sida falcelinta aan la bedeli karin (iyo sidaas isticmaalka) ee birta lithium, samaynta dendrite, kororka cufnaanta hadda wax ku ool ah ee foils lithium planar marka la barbar dhigo garaafyada graphite (silicon) electrodes, iyo, ugu dambeeya. laakiin ugu yaraan, "la'aanta" lithium inta lagu jiro dheecaanka (deplating) oo sidaas darteed luminta xiriirka korantada adag.Dabeecadda qallafsan ee makaanikada ah ee dhoobada adag ee elektrolytka runtii waxay leedahay u hoggaansanaan eber, iyo cadaadis aad u ba'an ayaa loo baahan yahay in lagu dhaqo si lithium adag loogu cadaadiyo qaybta adag ee korantada.Dhibcaha cadaadiska kala duwan ayaa hoos u dhigaya aagga dusha sare ee waxtarka leh xitaa in ka badan, taasoo keentay samaynta dendrite degaanka iyo kaydka isbuunyada.Electrolytes-ka polymer-ka ah ayaa si farsamaysan ugu hoggaansan laakiin weli ma soo bandhigin koror ku filan oo ku filan heerkulka qolka.Qalab cusub oo aad u xiiso badan oo arrintan ku saabsan waa silica gel electrolytes, kuwaas oo sidoo kale loo yaqaan "ionogels," halkaas oo dareeraha dareeraha ionic (ILE) uu ku xaddidan yahay matrix silica nanoporous (1).Borosintiga aadka u sarreeya ee matrix-ka silica (70 ilaa 90%) wuxuu siinayaa agabkan nanocomposite electrolyte-ka ah joogteynta jel oo kale sidaas darteedna ka dhigaya inay si farsamaysan u hoggaansamaan oo la mid ah electrolytes polymer.Jeelyada silica waxaa mararka qaarkood lagu tilmaamaa inay yihiin elektrolytes adag oo isku-dhafan, maadaama ay ka kooban yihiin dareere.Si kastaba ha ahaatee, silica nanocomposites, sida kuwa lagu sharaxay warqadan, ionic "dareere" electrolyte waxay noqotaa mid adag marka lagu xidho tobanaan kanaal oo nanometer ah labadaba kororka viscosity iyo xayeysiinta derbiga silica ee xaddidaya kanaalka.Haddii matrix-ka silica uu u dhaqmo oo kaliya sida kala-soocida daloolsan, markaa kororka viscosity ee korantada dareeraha ah ee xaddidan waxay u horseedi doontaa hoos u dhaca korantada ionic.Taa baddalkeeda, isdhexgalka u dhexeeya molecules ILE iyo derbiga silica pore ayaa ka dhigaya sifooyinka nanocomposite ka duwan wadarta qaybaha gaarka ah.Ku dhejinta dareeraha ionic ee oksaydhyada oo leh samaynta lakabyo mesophase adag ilaa dhowr nanometer oo dhumucdiisuna tahay ayaa lagu muujiyay sagxadaha qorshaysan ee leh microscopy xoogga atomiiga (2).Xoojinta xulashada ee anions dareeraha ionic iyo cations ee sagxadaha oksaydhku waxay u horseedi kartaa kor u qaadida dhaqdhaqaaqa Li+ ee dhinacyadan.Dabcan, kor u qaadida is-dhexgalka oksaydhka waa inay magdhowdaa ama xitaa ka badataa dhaqdhaqaaqa hoos u dhaca iyada oo loo marayo ILE ku xaddidan xudunta daloollada.Sidaa darteed, cabbirka daloolka yar iyo saamiga sare-ilaa-mugga ayaa la rabaa.Ilaa hadda, ionogels oo leh hawo-qaadayaal ion oo ku soo wajahan ILE lafteeda ayaa lagu muujiyey hagaajinta qaab-dhismeedka mesoporous (3).Tani waxay ka dhigan tahay in kor u qaadida interface ay horeba u jirtay laakiin ma aha ilaa xad dhaafka korantada bulk.

Diyaarinta ionogels waxay ka bilaabataa isku dhafka dareeraha ah ee isku midka ah, kaas oo ILE lagu daro sol-gel precursor solution for synthesis of the matrix oxide (4, 5).Habkan, ILE iyo matrix waxay u sameeyaan isku-dhafan qaab "meel ku yaal": Horudhacyada xalka ayaa ka falceliya si ay u sameeyaan matrix oksaydh ah oo ku wareegsan qaabka dareeraha ionic, iyaga oo ku dhejinaya habka.Marka la eego xaaladaha isku-darka qaarkood, ILE-SCE ee la diyaariyey (electrolyte-ka isku dhafan ee adag) waxay noqon kartaa qaab monolith ah oo leh ILE oo ku dhex jira shabakad oksijiin ah oo mesoporous joogto ah.Ilaa hadda, inta badan ILE-SCE-yada silica-ku-salaysan ayaa sidan loo diyaariyey, in kasta oo tusaalooyin sidoo kale lagu sameeyay alumina (6), titania (7), iyo xitaa tin oxide (8).Inta badan hababka sol-gel ee la soo sheegay waxaa ku jira ILE, alkyl-silicate sida tetraethyl orthosilicate (TEOS) sida silica precursor, iyo formic acid sida reagent iyo dareere (9, 10).Marka loo eego habka la soo jeediyay (11) ee geeddi-socodkan sol-gel, silica waxaa inta badan soo saara falcelinta TEOS iyo formic acid, in kasta oo biyaha la soo saaro inta lagu jiro habka sol-gelka.Ka sokow kuwan formic acid-ku-salaysan ee isku-dhafka ah ee "nonaqueous", hababka sol-gelka biyaha leh ee leh HCl sida kicinta iyo H2O sida reagent (oo lagu daray dareeraha organic) ayaa sidoo kale lagu tilmaamay, si kastaba ha ahaatee, kiiskan gaarka ah ee isku dhafka silica oo leh dareeraha ionic kaliya (12-15).

Caadi ahaan, ionogels waxay muujinayaan kororka ion ka hooseeya kan tixraaca ILE.Jiilkii ugu horreeyay ee ionogels waxay lahaayeen heerkulka qolka caadi ahaan qiyaastii 30 ilaa 50% ee qiimaha ILE ee badan, in kasta oo tusaalooyin gaar ah ilaa 80% la soo sheegay (9, 10, 16, 17).Saamaynta nuxurka ILE iyo natiijada morphology-ga dalool ee ku saabsan dhaqdhaqaaqa ionogel ayaa mar hore si faahfaahsan loo baaray (3);si kastaba ha ahaatee, ma jiro daraasad nidaamsan oo ku saabsan saamaynta kor u qaadida isdhexgalka lama yaqaan.Wu iyo al.(18) dhawaan ayaa laga soo sheegay goobta ku shaqaynaysa ionogel, kaas oo sidoo kale bixiyay kor u qaadida dhaqdhaqaaqa marka la barbar dhigo tirada badan ee ILE.Kobcinta waxaa loo aaneeyay isdhexgalka ka dhexeeya anion iyo kooxda 3-glycidyloxypropyl ee shaqada ee dusha silica.Helitaankani waxa uu taageerayaa fikradda ah in shaqaynta dusha sare ay runtii kor u qaadi karto dhiirrigelinta hagida interface.

Shaqadan, waxaan ku muujineynaa goobta goobta ee lakabka biyaha barafka adag ee silica iyo faahfaahinta habka isdhexgalka Li-ion-ka ee isdhexgalka korodhka ah ee u dhexeeya lakabka shaqada ee barafka iyo lakabka dareeraha ionic ee mesophase.Isku darka dusha sare ee gudaha gudaha iyo lakabka shaqeynta barafka cufan, nanocomposite electrolytes adag (nano-SCE) oo leh 200% ka sarreeya Li-ion conductivity marka loo eego tixraaca ILE ee badan ayaa la gaaray.Matrixka silica waxaa lagu muujiyay inuu leeyahay qaab-dhismeed mesoporous ah oo monolithic ah oo leh mugga daloolka iyo meelaha dusha sare ilaa 90% iyo 1400 m2/g, sidaas darteed bixinta saamiga dusha-ilaa-mugga ee xad-dhaafka ah taas oo u oggolaanaysa qayb weyn oo ka mid ah hagaajinta korantada ee dhinacyadan.Iyada oo la wanaajiyay shaqeynta dusha sare ee silica oo ay weheliso kordhinta saamiga dusha-ilaa-mugga, nano-SCE oo leh koronto ion ah oo ka sarreeya 10 mS/cm ayaa suurtagal ah in la farsameeyo oo sidaas awgeed aad u soo jiidasho leh baytariyada awoodda weyn ee codsiyada baabuurta.

Diirada warqadeena waxay ku saabsan tahay habka korriinka is-dhexgalka ee la xoojiyey iyada oo loo marayo samaynta lakabka mesophase oo leh caddaynta Raman, Fourier transform infrared (FTIR), iyo nukliyeerka magnetic resonance (NMR) spectroscopy.Xasiloonida is dhexgalka walxaha nano-SCE ee tamarta sare waxaa lagu muujiyay iyadoo la isticmaalayo elektrodes-ka lithium manganese oxide (LMO).Sidan oo kale, diiradda ayaa ku ilaalinaysa walxaha halkii ay ka ahaan lahayd isdhexgalka korantada iyo arrimaha isu-ururinta unugga.Sidoo kale, daaqada korantada kiimikada iyo xasiloonida ka dhanka ah birta lithium ayaa si buuxda loogu sifeeyay.Shaqeynta iyo is dhexgalka nano-SCE waxaa lagu muujiyay isu imaatinka iyo imtixaanada waxqabadka ee lithium iron phosphate (LFP) iyo unugyada lithium titanate (LTO).Deganaanshaha elektrolytkayaga iyo firfircoonida kiimikaad la'aanta korantada ee biyaha barafka ayaa lagu muujiyay baaskiil wadida muddada dheer ee unugyada Li-SCE-Li.Hagaajinta cufnaanta tamarta, waxqabadka heerka, iyo waxqabadka baaskiilka ee unugyada si buuxda la isugu keenay ayaa noqon doona diiradda waraaqaha dabagalka (19, 20).

Dhiirigelinta conductivity ion ee labada weji ee hababka isku dhafan ayaa la yaqaanay ku dhawaad 90 sano (21).Tusaale ahaan, ilaa afar amar oo kor u kaca korriinka ionic ayaa lagu muujiyay isku-dhafka milixda fudud ee lithium sida lithium iodide oo leh qaybo oksaydh ah oo mesoporous ah sida silica ama alumina marka la barbar dhigo ion conductivity ee lithium cusbo electrolyte saafi ah (22).Ionyada ku jira SCE-yadan waxay si degdeg ah ugu faafi karaan lakabka labanlaab koronto ee Li ion-ku-dhamay (ama bannaan-qaadka)Nasiib darro, kororka ion ee laga helay kuwan fudud ee laba-qaybood ah ee isku-dhafan ee adag ee aan noolayn (1) kama gudbin marinka 1-mS/cm2 ee loo baahan yahay in lagu xidho dhawrka boqol-mikromitir ee u dhexeeya taarikada ururiyaha hadda ee batteriga Li-ion. .Fikradda doping heterogeneous oo leh matrix oksaydh ah oo loogu talagalay injineerka conductivity ionic ayaa sidoo kale lagu sahamiyay polymer electrolytes (23) iyo ILEs (24), kuwaas oo leh kororka ionic sare oo gudaha ah oo lagu bilaabo.Intaa waxaa dheer, kiimiko hodan ah (stereo) ee qaybta saddexaad waxay fureysaa habab koronto oo dheeraad ah, maaddaama (di) unugyadu ay u eg yihiin unugyadu ay ka qayb qaadan karaan samaynta lakabka korantada ee labajibbaaran.Iyadoo ficilka xalinta kooxaha ether-ka ee polyetylen oxide polymer electrolytes ay bixiso ion-dabiiciga adag ee ~ 10-6 S / cm ee LiClO4 ilaa ~ 10-5 S / cm ee LiN (SO2CF3) 2, isku-dhafka ay ka kooban yihiin silica, alumina , ama nanoparticles titania waxay runtii ku siin karaan wax ka badan 10-laab kor u qaadis ah oo lagu cabiray ion conductivity (25), nasiib daro, wali waxay ka hoosaysaa heerka heerkulka qolka ee 1 mS/cm.Xalalka ILE waa isku dhafka Li-milix solute iyo dareeraha dareeraha ionic, kaas oo horey u lahaan kara dhaqdhaqaaqyo ionic sare ah oo u dhexeeya 0.1 iyo 10 mS/cm (26, 27).Dhowr isku day ayaa la sameeyay si kor loogu qaado conductivity kaamerada iyadoo la isku darayo ama lagu shiilay nanoparticles oksaydh ah ama in lagu xaddido ILE ee unugyada yaryar ee mesoporous (9, 16, 28, 29).Si kastaba ha ahaatee, ilaa hadda, wax wanaajin ah oo ku saabsan korantada ion looma arag saddexda qaybood ee Li-salt/ionic dareeraha / oksaydhka (fig. S1).Inkasta oo isticmaalka microparticles silica mesoporous ay keenayso korriin sare marka la barbar dhigo isku-dhafka leh nanoparticles adag, aagga dusha sare ee wajiga iyo kor u qaadista ion kuma filna in ay dhaafto kororka ILE.

Mesoporous silica waa shay caan ah oo loo isticmaalo kicinta.Caadi ahaan waxa lagu sameeyaa hydrothermal ama isku xidhka sol-gel fudud.Nidaamyada Hydrothermal waxay caadi ahaan u horseedaan budada mesoporous, laakiin iyada oo si taxadar leh loo koontaroolayo habka heerkulka qolka sol-gel, monoliths galaas dalool ah ama aerogels ayaa sidoo kale la soo saaray.Matrixka silica waxa uu ku samaysma hydrolysis iyo falcelinta uumi ee tetra-alkyl orthosilicates (30).Furaha xakamaynta qaab dhismeedka daldaloolada ayaa ah isticmaalka qaab-dhismeedka, tusaale ahaan, micele-nooca surfactant ah, kaas oo uu ku wareegsan yahay matrix silica ah.Marka dareeraha ionic lagu daro unugyadi qaabaysan, matrixka silica-biyoodka leh ayaa la falgala dareeraha ionic, samaynta jel, iyo ka dib daaweynta iyo qalajinta, dareeraha ionic wuxuu ku kooban yahay matrix silica naporous adag (13).Marka milixda lithium lagu daro qayb saddexaad, ILE ku xaddidan matrix silica waxay samaysaa silica gel electrolyte, kaas oo sidoo kale loo yaqaan ionogel (24).Si kastaba ha ahaatee, ilaa hadda, kuwan silica gel electrolytes waxay muujinayaan hab-dhaqan ku soo wajahan kan badan ee ILE laakiin aan ka badnayn, marka laga reebo hal kiis oo silica ay si kimikal ahaan u shaqaynaysay (eeg Horudhac) (18).

Halkan, waxaan ku tusineynaa, kor u qaadida habaysan ee dhaqdhaqaaqa Li-ion ee nanocomposite si ka baxsan ILE saafi ah.Tusaalaha 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide (BMP-TFSI) ayaa halkan lagu isticmaalaa.Waxaa la soo dhejiyay in isku dhafka molecules dareeraha ionic ee dusha silica ee OH-ka la joojiyay ay kor u qaaddo joogitaanka lakabka biyaha barafka ee wajiga.Isku xidhka hydrogen adag ee ka dhexeeya biyaha barafka iyo TFSI- anion waxay keentaa habaynta molecular ee dareeraha ionic, oo la mid ah qaybaha la amray ee si kedis ah ugu samaysma dareerayaasha ionic (31).Farqiga muhiimka ah ee u dhexeeya xayndaabyada si aan kala sooc lahayn loo sameeyay ee bulk ILE waa in lakabka barafka uu u dhaqmo sida lakab shaqeynaya kaas oo (i) u horseedaya dalbashada molecular ee dusha oksaydhka iyo (ii) soo bandhigaya H-bonding ku filan si ay u kiciso dipoles si loo sii daayo Li+ bilaash ah habdhaqanka la xoojiyey.Marka ku xigta kororka fiirsashada Li + bilaashka ah, waxaan tusi doonaa in tamarta firfircoonida ee faafinta ay hooseyso iyadoo la raacayo isdhexgalka isku dhafan ee leh lakabka ILE ee la isku dhejiyay iyo lakabka biyaha barafka.

Lakabka biyaha dushiisa ee dhowr- monolayers-dhuuban ee silica waa lakab adag oo la mid ah, maadaama ay si xoog leh ugu xidhan tahay kooxaha silanol iyada oo loo marayo H-buundooyinka oo sidaas darteed sidoo kale loo tixraaco lakabka barafka (32).Cufnaanteeda iyo dhumucdeeda (oo lagu qiyaasay ilaa saddex ilaa afar monolayers, oo leh ~ 0.25 nm halkii monolayer baraf) waxay ku jiraan dheellitirka heerkulbeegga cadaadiska biyaha ee qayb ahaan (RH) ee deegaanka (fig. S2).Waxaan tusineynaa in korantada ion-ku ay korodho dhumucda lakabka biyaha barafka sida isku-xidhka hydrogen-ka ee lakabyada ionic ee la isku dhejiyay ayaa sidoo kale kor u kacaya.Lakabka biyaha barafku waa mid deggan oo la mid ah biyaha crystal ee xeryahooda kiimikada.Tani waxay si weyn uga duwan tahay korantada korantada ama waxa loogu yeero biyaha ku jira isku dhafka milixda, halkaas oo daaqadda korantada ee kimikalka si weyn loo ballaariyay laakiin, ugu dambeyntii, biyuhu wali waa firfircoon yihiin korantada (33).

Si ka duwan cuntooyinka caadiga ah ee formic acid-catalyzed ionogel, waxaan isticmaalnay pH 5 khafiif ah oo leh biyo aad u badan iyo PGME (1-methoxy-2-propanol) oo lagu daray TEOS horudhac leh milix Li-TFSI iyo dareeraha ionic BMP-TFSI.Marka pH-kan la joogo, falcelinta hydrolysis-ku waa gaabis, halka uumigu wanaagsan yahay (30).Li ion-yada waxaa la rumeysan yahay inay u dhaqmaan sida kicinta falcelinta hydrolysis, maadaama aysan jirin wax gelation ah oo dhacay maqnaanshaha milixda lithium-ka halka labaduba ay lahaayeen pH isku mid ah 5. Saamiga molar ee dareeraha ionic ee TEOS (iyo sidaas awgeed silica moieties) waa lagu tilmaamay x qiimaha oo kala duwanaa inta u dhaxaysa 0.25 iyo 2. Saamiga molarka ee BMP-TFSI iyo Li-TFSI waxa lagu hayaa 3 (oo u dhiganta 1 M Li-ion xal).Qalajinta qunyar socodka ah waxay ahayd lama huraan si loo ilaaliyo sharafta qaabdhismeedka qaabdhismeedka monolith (eeg Qalabka iyo Hababka).Jaantuska 1A waxa uu tusinayaa sawir ah pellet monolithic ah oo la helay ka dib marka la qalajiyo faakuumka.Qalajinta faakuumka ee 72-saac ah ayaa ku filnaatay in laga saaro dhammaan qoyaanka ilaa heer laga saaray dhammaan biyaha xorta ah halka lakabka biyaha barafka ee la isku dhejiyay ay si buuxda u sii ahaanayaan, sida ay xaqiijisay FTIR.Wax gariir ah oo biyaha bilaashka ah laguma ogaanin 1635 cm-1 mid ka mid ah muunadaha ka dib tallaabada qalajinta faakuumka (Jaantus. 2).Marka la barbardhigo, FTIR spectrum ee muunad nano-SCE (x = 1.5) lagu kaydiyay 1 usbuuc sanduuqa gacan-gashiga N2 ee 60% RH ayaa la muujiyay.Xaaladdan oo kale, biyaha ugu sarreeya ee bilaashka ah ayaa muuqda.Dhammaan shaybaarada, dhanka kale, waxay muujiyeen calaamad cad oo loogu talagalay shaqeynta dusha sare ee silanol (Si─OH foorarsiga inta u dhaxaysa 950 iyo 980 cm−1) iyo lakabka biyaha barafka (O─H oo ku fidsan ~ 3540 cm-1) oo ku xidhan kooxaha dusha sare ee OH by H-bonding (faahfaahin dheeraad ah hoos).Fijaannada waxaa la miisaamay kahor iyo ka dib tallaabada qalajinta si loo cabbiro biyaha ku jira nano-SCE (miiska S1).Ka dib, waxaanu xisaabin doonaa tirada monolayers ee u dhiganta lakabyada barafka ee dusha sare ee miisaanka xad-dhaafka ah.Pellets-ka vacuum-engegan ayaa la soo galiyay sanduuqa galoofyada [<0.1-ppm (qaybaha halkii milyan) H2O] waxaana lagu kaydiyay fijaanno xiran si loo ilaaliyo nuxurka biyaha asalka ah.Mug yar ayaa laga soo qaatay pellet si loo sii tilmaamo.

(A) Sawirka laba nano-SCE pellets (bidix) oo lagu dhex sameeyay fijaan;Gelation ka dib, pellet hufan ayaa la helaa.Ogsoonow in pellet-ku si buuxda u hufan yahay oo sidaas awgeed la siiyay midab buluug ah oo muuqaal ah.Marka ILE meesha laga saaro, pellet cad oo jajaban ayaa u hadhi doona matrix silica aadka u daloola (midig).(B) Sawirka mikroskoobyada elektarooniga ah (SEM) ee sawirka SiO2 ee hadha ka dib markii meesha laga saaro ILE.(C) Soo-dhoweynta sawirka lagu muujiyey (B) oo muujinaya dabeecadda mesoporous ee walxaha matrixka oo leh qaar ka mid ah makropores.(D) Sawirka gudbinta elektarooniga ah ee microscopy (TEM) oo muujinaya xirmo cufan oo ah 7- ilaa 10-nm nanoparticles silica nanoparticles oo ah xirmooyinka dhismaha ee matrixka daloolka leh.(E) Baaxadda qaab dhismeedka matrixka ee loo qoondeeyay saamiga molar ee kala duwan ee ILE marka loo eego SiO2 (qiimaha x).Xariiqda jajaban waxay siinaysaa porosity-ka aragtida ee laga go'aamiyay jajabka mugga ee ILE iyo silica.Muunadaha acetone-luqashada (geesooyinka madow) ayaa lagu engejiyey hawada, taas oo qayb ahaan burburinaysa qaabdhismeedka x> 0.5.CO2 qallajin heer sare ah ee ethanol-luqashada nano-SCE (goobab cagaaran) waxay ka hortagtaa burburka ilaa x = 2 si tartiib tartiib ah looga saaro CO2 (goobo furan).BET, Brunauer-Emmett-Teller.Xuquuqda sawirka: Fred Loosen, imec;Akihiko Sagara, Panasonic.

(A) Muuqaalka IR ee nano-SCE sidii lagu qallajiyey faakuum (madow) ka dibna lagu sii qallajiyey sanduuqa galoofyada oo leh 0.0005% RH 9 maalmood (buluug) oo u bannaan 30% RH 4 maalmood (casaan) iyo ilaa 60 % RH ilaa 8 maalmood (cagaar), siday u kala horreeyaan.au, unugyo aan sabab lahayn.(B) Voltammograms wareeg ah ee xidhmo Li/SCE/TiN ah oo leh x qiimahoodu 1.0 (buluug), 1.5 (cagaaran), iyo 2.0 (casaan) iyo tixraac ILE (madow);Inset-ku wuxuu muujinayaa heerka hadda jira ee miisaanka logarithmic.(C) Voltammograms wareegta ah ee Li/SCE (x = 2)/40-nm TiO2 xidhmo (casaan), ILE (dhibic madow), iyo ILE oo lagu beeray miisaan 5% (wt %) H2O (khad buluug ah oo dhidibo leh);gudaha (B) iyo (C), cabbirada ILE iyo ILE oo leh H2O ayaa lagu sameeyay qaabeynta saddex-electrode oo leh TiN oo ah koronto shaqeynaya iyo Li oo ah counter iyo electrodes tixraac.SCE waxaa lagu engejiyey 2 maalmood sanduuqa galoofyada ka dib markii faakuumku qalajiyey.

Dhaqdhaqaaqa ionic (σi) ee vacuum-annealed nano-SCE waxay ku korodhay jajab mugga ILE (qiimaha x) marka loo eego qaybaha walxaha (fig. S1).Si kastaba ha ahaatee, kiiskan, conductivity ionic ayaa dhaaftay kan ILE saafi ah laftiisa in ka badan 200% ee qiimaha x ugu sarreeya (Jaantus. 3).Intaa waxaa dheer, ku-tiirsanaanta heerkulka nano-SCE oo leh kororka ion conductivity wuxuu muujiyay dabeecad ka duwan kan ILE saafiga ah: Halka Li-TFSI ee BMP-TFSI ILE ay muujinayso isbeddel cad oo ku saabsan dhaqdhaqaaqa iyo tamarta firfircoonida (jiirada) agagaarka dhalaalka barta isku dhafka ah ee 29°C, nano-SCE ee leh korriinka la xoojiyey ma laha.Taa baddalkeeda, waxay muujinaysaa kala duwanaansho joogto ah oo ku jirta σi oo leh heerkul, taas oo muujinaysa in nooc hore oo aan la aqoonsan oo weji ah ama mesophase la sameeyay, kaas oo markaa mas'uul ka ah korriinka la xoojiyay.Waxaa intaa dheer, jiirada yar iyo sidaas hoos tamarta firfircoonida faafinta ee nano-SCE marka la barbar dhigo ILE muujinaysaa sifooyinka alaabta kala duwan (fig. S3).Waxaa la dhajiyay in isdhexgalka xooggan ee u dhexeeya molecules dareeraha ionic iyo lakabka barafka adag ee silica scaffold ay mas'uul ka tahay habdhaqanka mesophase ee la arkay, sida looga hadli doono qaabka la soo jeediyay ee hoose.

(A) Ku-tiirsanaanta heerkulka ku-tiirsanaanta nano-SCE-yada ayaa la qalajiyey 8 maalmood sanduuqa galoofyada (GB) oo leh x qiyamka 2 (geesooyinka madow), 1.75 (goobo orange), 1.5 (saddex xagalka buluuga ah), iyo 1.0 (saddex xagalka cagaaran) ) iyo tixraaca ILE (geesooyinka furan).(B) Hab-dhaqanka nano-SCE-yada sidoo kale waxaa lagu qallajiyey GB 0 maalmood (geesooyin cagaaran), 10 maalmood (saddex xagalka madow), iyo 138 maalmood (saddex xagal buluug).(C) Hab-dhaqanka iyo xidid laba jibaaran ee wakhtiga qalajinta ee nano-SCE oo leh x qiyamka 2 (geesooyinka madow), 1.5 (saddex xagalka buluuga ah), 1.0 (saddex xagalka cagaaran), iyo 0.5 (dheeman brown).(D) Hab-dhaqanka nano-SCE oo leh x = 2 (geesooyin madow), 1.5 (saddex xagalka buluuga ah), iyo 1.0 (saddex xagal cagaaran) oo bannaanka ka ah qolka qoyaanka ee N2-buuxa.

Jawiga argon ee sanduuqa galoofyada waxa ku jira wax ka yar 0.1 ppm oo biyo ah, taas oo u dhiganta 0.0005% RH, cadaadiska biyaha qayb ahaan 0.01 Pa, ama barta sayaxa -88°C.Maaddaama tirada lakabyada biyaha ee la isku dhejiyay ee silica-la joojiyay ay u siman yihiin cadaadiska qayb ahaan biyaha (berdaha. S2), biyaha dusha sare waxay si tartiib tartiib ah uga soo baxayaan nano-SCE waxayna hoos imanayaan cidhifyada.Jaantuska 3C waxa uu muujinayaa isbeddelka hab-dhaqanka 23 μl ee nano-SCE oo ah shaqada wakhtiga joogista ee sanduuqa galoofyada.Conductivity ion waxay hoos u dhigtaa qalajinta ilaa ay ka soo baxdo qiimo u dhigma dusha silica ee dheellitirka cadaadiska qayb ka mid ah biyaha ee 0.01 Pa ee sanduuqa galoofyada.Xataa marka lagu hoos jiro xaaladaha qallalan ee ba'an ee sanduuqa galoofyada, ugu yaraan, qayb ka mid ah monolayer ee biyaha la isku dhejiyay ee silanol ayaa jooga, sida Raman spectroscopy ayaa weli muujiyay calaamadda 3524 cm−1, taas oo u gaar ah monolayerka ugu horreeya ee biyaha la isku dhejiyay ee silanol. (Jaantus. 4B).Dhaqdhaqaaqa ion ee ku jira xaaladaha buuxa ayaa aad uga hooseeya kan ILE ee shakhsi ahaaneed dhammaan kiisaska.Sidaa awgeed, kobcintu kuma filna inay magdhabiso khasaaraha ku yimi hab-dhaqanka ionic ee ILE-ga xaddidan ee xudunta daloolka.

(A) Muuqaalka IR ee nano-SCE oo leh x qiimaha 1.5 (casaan), tixraac ILE (madow), iyo SiO2 (buluug), oo muujinaya in kooxda O═S═O (1231 cm-1) ay ku lug leeyihiin la falgalka kooxaha OH ee dusha sare ee silica.(B) Raman spectra ee nano-SCE oo leh x qiyamka 2 (madow), 1.5 (casaan), iyo 0.5 (buluug), oo muujinaya joogitaanka biyaha barafka ee ku xiran silica-la joojiyay xitaa nano-SCE ee u dhow saturation (0.0005) % RH) ku jira sanduuqa galoofyada (30 maalmood).(C) Qaabka la soo jeediyay ee is dhexgalka interface ee nano-SCE oo leh kala-baxa Li-TFSI ee Li+ bilaashka ah maadaama TFSI- anion ay la wadaagto qayb ka mid ah kharashkeeda taban lakabka barafka-TFSI-BMP;midabadu waxay ka dhigan yihiin walxo kala duwan oo leh guduud (silicon), casaan (lithium), jaalle madow ( baaruud), oranji (oxygen), buluug (nitrojiin), caddaan (hydrogen), iyo cagaar (fluorine).Xariiqyada guduudan ee dahaaran waxay ka dhigan yihiin isku-xidhka hydrogen-ka ee u dhexeeya kooxda O═S ee TFSI anion iyo kooxaha OH ee dusha sare ee silica hydroxylated.Ion-yada Li+ ee ay xoreeyeen dipole ee ka sarreeya lakabka la isku dhejiyay waxay u guuri karaan moobilka xiga ama lakabyada dareeraha ionic ee ka sarreeya lakabyada interface.Ogsoonow in iyadoo ku xiran xoogga curaarta hydrogen iyo kharashka u dhigma ee silica, lakabyo badan oo la isku dhejiyay ayaa la samayn karaa sidoo kale.Muuqaal buuxa ayaa lagu muujiyay berdaha.S8.

Daawasho xiiso leh ayaa ah xidhiidhka tooska ah ee xididka labajibbaaran ee wakhtiga qalajinta sida ku cad sawirka 3C, taas oo muujinaysa in isbeddelka korantada uu si toos ah ula mid yahay isbeddelada qadarka biyaha barafka ee silica iyo in ka saarista biyahan dusha sare ay tahay faafinta xaddidan.Ogsoonow in "qallajinta" ay ku dhacdo kaliya jawi furan halkaasoo RH ay ka hooseyso lakabka barafka ee dheellitirka.Dareen-celinta ma beddelin wax muuqda, tusaale ahaan, unugyada qadaadiicda xiran ee loo isticmaalo cabbirrada ku-tiirsanaanta heerkulka.

Ku-tiirsanaanta heerkulka nano-SCE waxaa lagu qiyaasay waqtiyo kala duwan ee qallajinta sanduuqa galoofyada.Sida habdhaqanka nano-SCE ee la qalajiyey ee ILE, joogtada ah ee σi ee ka soo horjeeda 1 / T ee profiles mesophase conductivity ayaa si tartiib tartiib ah u beddelay astaanta ILE, mar kale waxay muujinaysaa hoos u dhaca hareeraha barta dhalaalka (fig. S3).U fiirsashadani waxay sii taageertaa malo-awaalka ah in lakabka barafka uu u dhaqmo sida lakabka shaqeynaya ee isdhexgalka isdhexgalka ee ILE, taasoo keenaysa dabeecadda mesophase ee nano-SCE.Sidaa darteed, marka lakabka shaqaynaya la saaro, ILE waxa ay ku koobnaan doontaa xuubka oksaydhka mesoporous.

Cabbiraadaha daaqadda xasiloonida korantada ayaa xaqiijinaya in biyaha barafka ee nano-SCE ay deggan yihiin, maadaama aan wax sare oo biyo dhimis ah ama oxidization lagu arkay TiN electrode aan la garanayn (Jaantus. 2) ama TiO2 dhuuban-filim electrode ah, taas oo haddii kale u dhaqanta. sida koronto-kicinta biyaha dhimista.Taa baddalkeeda, xasilloonida korantada ee nano-SCE waxay aad ula mid tahay tan ILE oo sidaas awgeed xaddiday oksaydhka TFSI- ee awoodaha korantada> 4.3 V iyo yaraynta TFSI- iyo BMP + awoodaha <1 V iyo Li +/ Li (33).Marka la barbardhigo, voltammogram ayaa lagu tusay ILE oo leh 5 miisaan % (wt%) biyo lagu daray (waxyaabaha la midka ah sida qaar nano-SCE ah; eeg shaxda S1).Xaaladdan oo kale, laan kathodic ah oo loogu talagalay dhimista biyaha ayaa isla markiiba la cabbiraa iyadoo la raacayo heerka ugu sarreeya ee Li-intercalation ee anatase ee 1.5 V oo ka soo horjeeda Li +/Li.

Kuleylka iyo (electro) xasiloonida kiimikaad ee nano-SCE waxaa inta badan go'aamiya buuxinta ILE.Falanqaynta Thermogravimetric (TGA) waxay muujisay xasilloonida kulaylka ee SCE iyo ILE ilaa 320 ° C, iyadoon loo eegin saamiga ILE-ilaa-silica (fig. S4).Heerkulkan ka sarreeya, Li-TFSI iyo BMP-TFSI waxay si buuxda u jajabaan qaybo kacsan, oo kaliya matrixka silica ayaa weli ah qiyaastii 450 ° C.Boqolkiiba tirada badan ee hadhay ka dib burburka kulaylka ayaa runtii si aad u wanaagsan ula mid ahaa jajabka silica ee SCE.

Nano-SCE ma muujin qaab-dhismeed cad oo ku jira mikroskoobyada elektaroonigga ah (SEM) marka laga reebo dusha siman oo leh balastar silica ah oo soo baxay (fig. S5).Cufnaanta gaarka ah ee SCE waxaa lagu go'aamiyay helium pycnometer waxayna ahayd ku dhawaad 1.5 g/cm3 dhammaan qiimayaasha x (miiska S1).Matrixka silica oo buuxa waxa daaha ka qaaday soo saarista caajiska ah ee ILE ee dareeraha (eeg Qalabka iyo Hababka).Marka si taxadar leh loo qalajiyo meesha muhiimka ah ee CO2, airgel monoliths oo sugan ayaa la heli karaa sida tan ku cad sawirka 1A.Kormeerka SEM wuxuu muujinayaa silica mesoporous oo leh dhexroor dalool 10- ilaa 30-nm, kaas oo ku duudduubay makropores waaweyn oo ah 100 ilaa 150 nm, sida lagu arki karo sawirka 1 (B iyo C).Mikroskoobyada elektarooniga ah ee gudbinta xallinta sare ah (TEM) (Jaantus. 1D) ayaa sii daaha ka qaaday qaab-dhismeed yar oo ka kooban nanoparticles silica nanoparticles oo si dhow loo soo buuxiyay.Celceliska dhexroorka walxaha wuxuu u dhexeeyay 7 ilaa 14 nm ee qiimayaasha x u dhexeeya 0.5 iyo 1.5.

Aagga dusha sare ee gaarka ah [Brunauer-Emmett-Teller (BET)], porosity, celceliska cabbirka daloolka, iyo qaybinta cabbirka daloolada ayaa lagu go'aamiyay N2 cabbirada xayeysiinta / desorption (miiska S1 iyo fig. S6).Burburka qayb ka mid ah qaabdhismeedka iyo ka saarista aan dhamaystirnayn ee ILE la isku dhejiyay ayaa laga yaabaa inay si khaldan u muujiso tirooyinka.Si taxadar leh u soo saarista dareeraha ionic iyo qalajinta qunyar socodka ah iyadoo la adeegsanayo CO2 heer sare ah ayaa la bixiyay, si kastaba ha ahaatee, natiijooyin la isku halleyn karo oo ku dhow porosity-ka la filayo ayaa laga xisaabiyaa jajabka mugga ee ILE ilaa silica (Jaantus 1).Bedka BET wuxuu u dhexeeyaa 800 iyo 1000 m2/g.Cabbirka daloolka dhexdhexaadka ah ee laga helay jiirada isotherm-ka wuxuu u dhexeeyay 7 iyo 16 nm.Intaa waxaa dheer, qayb yar oo ka mid ah daloolada waaweyn ee ilaa 200 nm ayaa la qiyaasay (fig. S6), iyada oo la raacayo indho-indheynta SEM.Dhexroorka daloolku wuxuu u dhigmaa si aad u wanaagsan laba jeer dhumucda u dhiganta lakabka ILE ee laga helay jajabka mugga ILE iyo aagga BET, taasoo la micno ah in mesopores ay si buuxda uga buuxsameen ILE.

Aagga dusha sare ee BET ee la sheegay waxaa loogu talagalay mesopores iyo macropores oo keliya.Matrix acetone-luqashada, micropores (~ 0.6 nm) ayaa sidoo kale la qiyaasay.Micropores-yada waxaa laga helaa inta u dhaxaysa nanoparticles silica nanoparticles oo ka samaysan qaab-dhismeedka sida ku cad sawirka TEM ee sawirka 1D.Bedka sare ee dheeraadka ah ee u dhexeeya 650 (x = 0.5) iyo 360 m2/g (x = 1.5) ayaa lagu qiyaasaa (miiska S1).

Labada FTIR iyo Raman spectra waxay muujinayaan caddayn cad oo loogu talagalay kooxaha silanol oo leh unugyo biyo baraf ah oo la isku dhejiyay oo ku yaal matrix silica porosity-sare leh oo leh meelo dusha sare oo waxtar leh oo ka sarreeya 1400 m2 / g marka la tixgelinayo micropores, mesopores, iyo macropores.Inta u dhaxaysa eber iyo saddex koob-biyood ayaa lagu qiyaasay biyaha xad-dhaafka ah ee nano-SCE ee x <1.75.Silica Planar, saddexda monolayer ee ugu horreeya ee biyaha la isku dhejiyay ayaa runtii loo tixgeliyaa kuwa aan dhaqaaqin oo adag sababtoo ah isku xidhkooda xoogga leh ee hydrogen ee dusha OH-la joojiyay (32) (eeg fig. S2).Fidinta O─H ee la xidhiidha silanol hydrogen oo ku xidhan lakabka biyaha barafka ayaa laga helay 3540 cm-1 gudaha FTIR spectra.Dhammaan nano-SCE-yada waxay muujinayaan, runtii, ugu sarreeya 3540 cm-1 ee biyaha barafka ka dib qalajinta faakuumka iyo ka dib qalajinta dheeraadka ah ee sanduuqa galoofyada (Jaantus. 2).Xitaa nano-SCE-da dheellitiran ee 0.0005% RH (sanduuqa galoofyada), Raman spectroscopy ayaa wali muujiyay joogitaanka ugu yaraan monolayer qayb ah (Jaantus. 4B).Hal-abuurka afraad ee silica planar waxa la rumaysan yahay inuu yahay lakab ku-meel-gaar ah, taasoo la macno ah in wali la isku dhejiyay oo la xaddiday laakiin ay yeelan karto xoogaa dhaqdhaqaaq ah.Laga soo bilaabo lakabka shanaad, biyuhu waxay noqonayaan guurguura oo dareere ah.Biyaha dareeraha ah waxay ka soo muuqan doonaan tirooyinka hirarka sare ee spectrum FTIR sababtoo ah heerka hoose ee H-ku-xidhka biyaha dareeraha ah.Nano-SCE-da u soo ban-baxday 60% RH, 3540-cm-1peak runtii waxay muujinaysaa gariir dheeraad ah oo loo beddelay tirooyinka hirarka sare sababtoo ah lakabka biyaha dareeraha ah ee dheeraadka ah.Arrinta xiisaha leh ee arrintan la xidhiidha ayaa ah tijaabadii halka shaybaarku uu gaadhay 30% RH, maadaama aan biyo dareere ah wali laga filaynin silica qoyaankan (fig. S2).Muunaddan, kaliya 3540 cm-1 ugu sarreysa ee biyaha barafka ayaa lagu arkay FTIR.Intaa waxaa dheer, biyaha ugu sarreeya ee bilaashka ah lagama helin 1635 cm-1 xitaa 4 maalmood ka dib 30% RH.Tani waxay ka dhigan tahay in biyaha aan la qaadin hygroscopic Li-TFSI ee ku milma hydrophobic BMP-TFSI marka nano-SCE lagu qalajiyo daaweynta faakuumka.Sidaa darteed, biyo kasta oo dheeri ah oo ku jira SCE ayaa lagu milmi doonaa oogada silica ee OH-ka-baxday.Sidaa darteed, marka loo eego silica planar, matrixka silica ee SCE wuxuu ku siman yahay cadaadiska qayb ahaan biyaha deegaanka.

Si loo tijaabiyo mala-awaalkan dheeraadka ah, ion conductivity of nano-SCE (x = 1, 1.5, iyo 2) ayaa lagu qiyaasay % RH kala duwan;shaybaarada waxaa lagu soo bandhigay gaas N2 ah oo qallalan oo qoyan oo isku jir ah oo ku jira sanduuqa galoofyada muddo 2 maalmood ah si loogu oggolaado daboolka biyaha la isku dhejiyay si loo gaaro dheellitirka (Jaantus. 3D).Dhibcaha ~ 0% RH, dhaqdhaqaaqa nano-SCE ee isku dheelitiran ee sanduuqa galoofyada ayaa la qaaday.Si la yaab leh, ion conductivity ka dhanka ah RH(%) profile raacday habdhaqanka la filayo ee adsorption biyaha on silica planar (fig. S2).Inta u dhaxaysa 0 iyo 30% RH, hab-dhaqanku wuxuu kordhay iyadoo kor u kacday RH.sida la filayo kororka cufnaanta lakabka barafka ee la isku dhejiyay iyo dhumucda (oo u dhiganta hal ilaa saddex lakab oo baraf ah oo ku yaal silica planar).Ogsoonow in FTIR ay muujisay in biyo bilaash ah aysan ku jirin nano-SCE dhowr maalmood oo ah 30% RH.Kala-guurka ayaa la arkaa qiyaastii 50% RH, oo u dhiganta xaaladaha la filayo lakabka biyaha ku-meel-gaadhka ah ee silica.Ugu dambeyntii, koror kala duwan oo kororka ion conductivity ayaa laga helaa 60% iyo qoyaan sare, halkaas oo, la mid ah silica planar, hadda, sidoo kale lakab biyo u eg ayaa laga yaabaa in lagu sameeyo isdhexgalka u dhexeeya silica iyo ILE ee ku xiran.Iyadoo FTIR, lakabka biyaha dareeraha ah ee lakabka barafka ayaa hadda lagu ogaadaa isbedelka silanol / barafka / biyaha ugu sarreeya ee tamarta sare (Jaantus. 2A).Isbeddelka la arkay ee conductivity waa dib loo celin karaa;sidaas darteed, nano-SCE waxay u dhaqmi kartaa sida dareeraha qoyaanka iyo Li-ion electrolyte.Laga soo bilaabo shaxanka. 3D, conductivity ion ee nano-SCE isla markiiba ka dib vacuum anneal waxay u dhigantaa silica fuuqbaxa leh ee ~ 10% RH.Kobcinta ion ee buuxinta xaaladaha qolka engegan (~ 0.5% RH) waxay noqon doontaa agagaarka 0.6 mS/cm (loogu talagalay x = 2).Tijaabadani waxay si cad u muujinaysaa saamaynta biyaha waji-xidhka ahi ku leeyihiin hab-socodka ion.RH> 60%, conductivity ion sare waxaa lagu macnayn karaa fidinta degdega ah ee Li+ la xalliyo iyada oo loo marayo lakabka dareeraha u eg.Si kastaba ha noqotee, marka laga hadlayo lakabka barafka adag, faafinta Li + ion waxay noqon doontaa fidinta nooca-adag oo ka gaabinaysa dareeraha ionic laftiisa.Taa baddalkeeda, kobcinta waxaa loo aaneynayaa xayeysiinta la xoojiyey ee anions organic iyo cations ee Li-salt iyo molecules dareeraha ionic, sida lagu soo jeediyay qaabka hoose.

Waxaan soo jeedinaynaa qaab halka molecules dareeraha ionic lagu dhajiyo dusha silica iyada oo loo sii marayo H-buundooyinka oo leh lakabka barafka ee aan dhaqaaqin ee kooxaha silanol (Jaantus. 4).Dabeecadda gudaha ee falcelinta uumiga hydrolysis waxay bixisaa cufnaanta silanol ee ugu sarreeya (4 × 1014 ilaa 8 × 1014 cm−2, kaas oo si fiican u dhigma cufnaanta hal baraf ah oo leh ~ 8 × 1014 molecules water per cm2) (34).Caddaynta isdhexgalka molecular ee u dhexeeya O atomiyada TFSI anions iyo silica waxaa bixiya FTIR, taas oo muujinaysa labanlaabka O═S═O ugu sarreeya dhammaan nano-SCE marka la barbar dhigo tixraaca ILE (Jaantus. 4A; muuqaal buuxa ee sawirka S8).Isbeddelka sare ee dheeraadka ah ee ku saabsan -5 cm-1 laga bilaabo 1231 cm-1 waxay muujineysaa isku xirnaanta kooxaha O═S═O ugu yaraan qayb ka mid ah anions TFSI.Sidaa darteed, H-ku-xidhka anions TFSI ee lakabka biyaha barafka ayaa loo maleynayaa.Dabadeed, cations-ka weyn ee hydrophobic BMP waxay la xidhiidhaan lakabka ugu horreeya ee TFSI, iyaga oo dhammaystiraya lakabka ugu horreeya ee la isku dhejiyay ee molecules dareeraha ionic.Dhanka lakabka barafka, molecules-yada BMP-TFSI ee la isku dhejiyay ayaa loo maleynayaa inay yihiin kuwa aan dhaqdhaqaaq lahayn, sidaas darteed waxay fidiyaan lakabka barafka u eg ee dusha silica.Maadaama anion-ka TFSI uu leeyahay koox O═S═O-suman, hal atamka oksijiin ayaa la falgali kara dusha sare ee silica hydroxylated halka kan kalena uu sameeyo dhibcaha ku dheggan xargaha BMP.Anion-ka TFSI waxa kale oo uu leeyahay laba kooxood oo O═S═O ah, iyaga oo hubinaya xayeysiis adag iyo dalbashada cufan ee monolayer-ka.Xayeysiintu waxay ugu waxtar badan tahay xaaladda lakabka barafka cufan oo leh cufnaanta ugu sarreysa ee kooxaha OH oo ah dhibco ku dheggan.Marka ay joogaan kooxo silanol oo keliya, xayeysiisku waxa laga yaabaa inaanay ku filayn si ay u sameeyaan lakab adsorbate joogto ah.Intaa waxaa dheer, tirada sii kordheysa ee monolayers barafka ayaa la og yahay inay kordhiso xoogga curaarta hydrogen (35).Ogsoonow in isdhexgalka molecular ee ka dhexeeya cation BMP iyo monolayer-ka TFSI ee la dalbaday uu ka duwanaan doono kan dareeraha ionic halkaasoo anion TFSI uu leeyahay xoriyad wareeg ah oo aan lahayn polarization ka imanaya dusha hoose.Kharashka isku-xidhka weyn ee BMP ayaa runtii loo qaybiyaa atomyada badan iyadoo la eegayo curaarta gudaha iyo isdhexgalka molecular ee deegaankeeda kiimikada iyo, gaar ahaan, anion-ka TFSI ee la isku dhejiyay.Isku-xidhka H ee u dhexeeya kooxda O-kooxda TFSI iyo OH-joojinta lakabka barafka hadda waxay soo bandhigaysaa dipole ka sarreeya lakabka ugu horreeya, taas oo keeneysa dalbashada molecular dheeraad ah ee ururka.Waxaa la rumeysan yahay in meeshan, molecules-ka yar ee Li-TFSI ay ku dhejiyaan lakabka molecular taas oo TFSI anion ay hadda magdhoweyso kharashka ku-meel-gaadhka ah ee ku-meel-gaadhka ah ee mid ama in ka badan oo BMP ah oo ku yaal lakabka sare, sidaas awgeed way dabcaysaa xiriirka ay la leedahay Li. ion.Sidan, fiirsashada Li + bilaashka ah ayaa lagu kordhiyaa is-dhexgalkan, taasoo horseedaysa kororka ion sare.Sidaa darteed, lakabyada barafka cufan iyo dhumuc weyn ayaa markaa soo bandhigaya dipole weyn oo leh kharash hadhaaga ah oo sarreeya si loo magdhabo, taasoo siinaya xad-dhaaf Li+ lacag la'aan ah oo saami ahaan sarreeya sidaas darteed ion conductivity

Dusha sare ee lakabka ILE ee la isku dhejiyay, lakab kale oo ILE ah ayaa isku dhejin kara si la mid ah barafka badan ee silica ama jiidista dipole ee lakabka barafka ayaa ah mid aad u daciif ah oo ILE si khafiif ah ayaa korka ku yaal, kaas oo markaa bixin kara dareeraha u eg. ion-yada Li+ ee lagu sii daayo lakabka hoose ee xamaasadda leh (Jaantus. 4C).Isbeddelka xoogga saarista Li+ ion ee bilaashka ah waxaa xaqiijiyay NMR iyo cabbirada Raman spectroscopy labadaba.Cabbirrada Raman waxay si dadban u muujinayaan in qayb weyn oo Li+ ion bilaash ah ay dhab ahaantii ku jiraan nano-SCE oo leh lakabyo badan oo baraf ah oo ku xidhan silica (Jaantus. 5).Ramanku waxa uu cabbiraa xidhiidhka cation ee TFSI isagoo baadhaya gariirka kooxda N-ga ah ee TFSI anion (36).Dareeraha ionic BMP-TFSI ee saafiga ah, kaliya hal ugu sarreeya oo ah 741 cm-1 ayaa la arkaa.Xaaladda ILE saafiga ah, ugu sarreeya ayaa lagu arkay 746 cm−1 halkaas oo laba TFSI anions ay isku dubaridaan hal Li + ion [eeg xisaabinta farsamada shaqada (DFT) ee Qalabka iyo Hababka].Dhammaan nano-SCE-yada, xoogga ugu sarreeya ee 746 cm−1 wuu ka daciifsan yahay kan ILE, taas oo muujinaysa qayb yar oo Li-TFSI ah oo la xidhiidha iyo, sidaas awgeed, qayb weyn oo aan xidhiidhin ama bilaash ah Li+ cations.Heerka ugu sarreeya ayaa si aad ah hoos ugu dhacaya kuwa nano-SCE ee muujinaya kor u qaadida dhaqdhaqaaqa ugu sarreeya, ie, kuwa leh lakabka barafka ee ugu dhumuc weyn.Marka loo eego nano-SCE ee dheellitirka sanduuqa galoofyada, weli, qayb Li+ bilaash ah ayaa lagu cabbiraa in kasta oo aad uga yar shaybaarrada vacuum-annealed.Saamiga xoogga ugu sarreeya ee 746 ee ka sarreeya 741 cm-1 Raman beddelka markaas waa cabbirka saamiga bilaashka ah iyo Li-ions ee la xidhiidha TFSI (Jaantus. 5B).Korodhka tooska ah ee jajabka Li+ ion ee bilaashka ah ee x qiimihiisu wuxuu si wacan ula socdaa isbeddelka kor u qaadida tayada tayada x ee sawirka 3B, labadaba faakuumka la qalajiyey nano-SCE (maalin 0) iyo SCE marka la siman yahay sanduuqa galoofka qallayl (maalin 138).

(A) Muuqaalka Raman ee dareeraha ionic (IL; khad buluug ah oo dhibco leh) iyo ILE tixraaca (ILE; xariiq dhibco leh) oo nano-SCE ah oo diyaarsan , iyo 2 (brown) iyo nano-SCE (x = 1.5) oo sidoo kale lagu qalajiyey sanduuqa galoofyada 30 maalmood ama u dhow saturation at 0.0005% RH (casaan).Xadadka toosan waxay ku calaamadiyaan isbeddelka Raman ee TFSI iyadoo xarunteeda N ay isku dubariday Li+ (746 cm−1) oo aan la isku xidhin Li+ (741 cm−1), siday u kala horreeyaan.(B) Qiyaasta bilaashka ah ee isku xirka Li + ee nano-SCE sida la farsameeyey (vacuum engejiyey, wareegyo madow) oo weliba lagu qalajiyey sanduuqyada galoofyada leh 0.0005% RH 30 maalmood (dheeman buluug ah), oo u dhiganta saamiga isku dhafan ee xoojinta Meelaha ugu sarreeya ee Raman (746 cm-1 ka sarreeya 741 cm-1).(C) PFG-NMR-ku-soo-baxa Li+ isku-darka is-faafinta ee nano-SCE (dheeman cas) iyo ILE ref.(geesooyin madow) oo ah shaqada u dhaxaysa inta u dhaxaysa garaaca magnetic field gradient.Aragtida ugu sarreysa ee Raman spectra waxaa lagu sawiray iyadoo la isticmaalayo xisaabinta DFT.

Laga soo bilaabo pulsed-field gradient NMR (PFG-NMR), isku dhafka is-fidinta ee noocyada kala duwan ee Li-ion mobile waxaa loo go'aamiyay iyadoo ay tahay shaqada u dhexeysa garaaca magnetic field gradient ∆ tixraaca dareeraha ILE iyo nano- SCE (x = 1.5) oo leh ion isku mid ah 0.6 mS/cm (Jaantus. 5C).Isku-dubbaridka is-faafinta Li+ ee tixraaca ILE wuxuu ahaa mid joogto ah, taas oo muujinaysa in hal ama noocyo badan oo Li ah oo dhaqdhaqaaq la mid ah ay ku jiraan dareeraha.Nano-SCE-da, isku-darka is-fidinta ayaa ku kala duwanaa ∆ oo dhaaftay kan ILE ee gaaban ∆, taasoo muujinaysa joogitaanka noocyada dhaq-dhaqaaqa ah ee ka jawaabaya oo kaliya waqtiyo gaaban oo u dhexeeya garaaca magnetic field.Dareemida isku-darka is-fidinta waxay soo jeedinaysaa in marka xigta korodhka xoogga-saarista Li-ion-ka ee bilaashka ah, sida laga soo xigtay Raman spectroscopy, tamarta firfircoonida ee faafinta ayaa hoos loo dhigayaa lakabka interface mesophase sidoo kale.Tani waxay taageertaa kor u qaadida korriinka ee ay soo bandhigtay (in ka badan) ion Li+ oo bilaash ah lakabka mesophase.Waqti ka dheer ∆, isku xirnaanta is-fidinta ayaa ka hooseysay tixraaca ILE.Tani waxay xaqiijinaysaa conductivity ion ee aadka u hooseeya ee sanduuqa galoofka-nano-SCE oo buuxa marka la barbar dhigo ILE.ILE ku xaddidan xudunta mesopores waxay yeelan doontaa viscosity sare sababtoo ah xaddidaadda dhaqdhaqaaqa kelli.Sidaa darteed, kobcinta abuuritaanka Li-ions ee aad u dhaqsaha badan ee silica / barafka / ILE interface waa in ay ka gudubtaa hoos u dhaca dhaqdhaqaaqa xudunta u ah daloolka.Tani waxay sharxaysaa maqnaanshaha kobcinta ee hababka ku salaysan qayb-ku-salaysan halka is-dhexgalyadu aanay bixinayn dhiirrigelinta ion ku filan (fig. S1).

Dejinta xasiloonida korantada ee nano-SCE ee ka dhanka ah birta lithium ayaa la tijaabiyay iyadoo la adeegsanayo qalab saddex-electrode ah (schematic of the setup ayaa lagu muujiyay fig. S7).Sifada hadda- suurtagalka ah ee Li/SCE (x = 1.5) iyo Li/ILE unugga nuska waxa lagu muujiyey sawirka 6A.Dhanka daaqada korantada kiimikaad ee Jaantuska 2, kiimikaalka elektiroonigga ah waxa xaddidaya buuxinta ILE.Dahaarka lithium-ka dib loo rogi karo ayaa la arkayaa.Lakabka adag ee interphase electrolyte (SEI) ayaa lagu sameeyay lithium macdan ah oo leh RSEI qiyaastii 0.9 kilo-ohm · cm2, mas'uul ka ah dhibicda IR weyn ee qalooca iU ee labada dhinac ee cathodic iyo anodic.Xakamaynta cathodic ee xalalka ILE ee saafiga ah ma muujin wax hysteresis ah ilaa -2.5 mA/cm2.Si kastaba ha ahaatee, kala dirida anodic-ku waxay tustay heerka ugu sarraysa ee passivation oo leh qulqulka anodic-goboleed deggan oo kaliya 0.06 mA/cm2.Laanta hadda jirta ee cathodic ee isku xidhka adag ee Li/SCE ma muujin wax hysteresis ah qulqulka cathodic ka yar -0.5 mA/cm2.Si kastaba ha ahaatee, iska caabinta SEI waxay ahayd, si kastaba ha ahaatee, oo ku saabsan labanlaab.Sidoo kale, heerka ugu sarreeya ee anodicku wuu hooseeyay iyo xaaladda joogtada ah ee hadda jirta ka dib markii heerka ugu sarreeya ee anodic uu ahaa 0.03 mA/cm2, kaliya kala badh xalka ILE ee saafiga ah.Sameynta SEI iyo lakabyada passivation ee daloolada SCE waxay xaddidaysaa hadda birta lithium.Labada Voltammograms ee Li/ILE iyo Li/SCE electrodes waxay ahaayeen kuwo dib loo soo saari karo wareegyo badan, taas oo muujinaysa in lakabka passivation anodic iyo lakabka kiimikaad SEI ay yihiin kuwo dib loo rogi karo oo deggan.Kinetics-ka qunyar socodka ah ee is dhexgalka Li/SCE ayaa si ba'an u xaddidaya waxqabadka unugyada nuska ah ee lagu sameeyay biraha birta ee hoose.

(A) Voltammogram cyclic ee nano-SCE (x = 1.5, sida la sameeyay ka dib markii la qalajiyo vacuum) (casaan) iyo tixraaca ILE (madow) oo lagu qiyaaso qaabeynta saddex-electrode oo leh Li sida shaqada, counter, iyo electrodes tixraac ( iska caabin SEI ayaa lagu qiyaasay Hoos u dhaca IR ee hadda cathodic waa 0.9 iyo 1.8 kilo-ohm·cm2 ee ILE iyo SCE, siday u kala horreeyaan).(B) Qalooca Galvanic-ka/siidaynta ee Li/SCE (x = 1)/100-nm unug-filim khafiif ah LiMn2O4 oo ah shan wareeg oo C-qiimaha 1C, 5C, iyo 20C.(C) Voltammograms wareeg ah ee Li/SCE/40-μm Li4Ti5O12 iyo Li/SCE/30-μm LiFePO4 unugyada korantada budada ah (1 mV/s).(D) Qalooca galvanic-ka-qaadista/siidaynta ee Li/SCE/40-μm Li4Ti5O12 korantada budada ah ee 1C, 0.1C, 0.2C, iyo 0.02C.(E) Qalooca galvanic-ka-baxa ee Li/SCE/30-μm LiFePO4 korantada budada ah ee 1C, 0.5C, 0.2C, 0.1C, 0.05C, iyo 0.01C.(F) Awoodda (dheemanka ka buuxsamay delithiation iyo labajibbaaran furan oo loogu talagalay lithion) oo ka soo horjeeda lambarka wareegga Li/SCE/30-μm LiFePO4 elektrodegga budada ah;dhumucda SCE ee unugyadu waa ilaa 280 μm.Cufnaanta LFP iyo LTO cathode waxay ku saabsan tahay 1.9 iyo 11.0 mg/cm2, siday u kala horreeyaan.(G) Qulqullada suurtagalka ah ee ka soo horjeedda wakhtiga ee xidhmo Li/SCE/Li ah oo baaskiil ku socda cufnaanta hadda ee 0.1, 0.2, 0.5, iyo 0.1 mA/cm2.(H) 1aad, 10aad, 125aad, iyo dabaylaha u dambeeya ee xidhmada Li/SCE/Li ayaa lagu adkeeyay 0.1 mA/cm2, ee lagu muujiyay (G).Marka loo eego (G) iyo (H), SCE-du waxay leedahay koronto dhan 0. 34 mS/cm, dhumucda lakabka SCE waa 0.152 cm.

100-nm LiMn2O4 (LMO) filim khafiif ah ayaa loo adeegsaday qaab korantada togan si loo tijaabiyo labadaba xasilloonida nano-SCE iyo walxaha korantada iyadoo meesha laga saarayo arrimaha is-dhexgalka ee suurtagalka ah ee korantada isku dhafan (37).Waxqabadka baaskiilka ee korantada-filimka khafiifka ah/SCE xirmada waxay muujineysaa xasilloonida is-dhexgalka u dhexeeya korantada iyo korantada.Qaabkan qaab-dhismeedka filimka khafiifka ah, hal kaliya, oo si fiican loo qeexay, iyo xiriir xiriirin qorshe ayaa u dhexeeya electrolyte iyo electrode, ie, waa madal ku habboon in lagu barto kiimikaalka elektrolytka / electrode interface iyada oo aan la helin arrimaha isbeddelka mugga. , iwm. Sidoo kale tijaabadan, waxqabadka heerka laguma xaddido koronto-yaqaanka Li-foil counter, maadaama cufnaanta hadda (6 μA/cm2 ee 1C) uu ka hooseeyo kan taagga hadda anodic-ka-joogta ah ee qeybta lithium- unug (0.03 mA/cm2).Qalloocyada dallacaadda/dejinta ee dib loo soo saari karo iyo xasilloon ayaa lagu helay koronta goynta ah 4.3 V ee heerka C-heerka u dhexeeya 1 iyo 20C in ka badan wareegyada 20 (Jaantus. 6B).LMO kuma degana korantada dareeraha ah ee LiB.Tusaale ahaan, 50% hoos u dhigista awoodda ayaa lagu arkay 100-nm filimka LMO oo lagu dallacay wareegyada 10 ee LiClO4/propylene carbonate electrolyte at 1C (37).Natiijooyinkayagu waxay muujinayaan in nano-SCE uu aad ugu habboon yahay LMO marka loo eego dareeraha caadiga ah.

Si loo muujiyo is dhexgalka nano-SCE, waxaan sidoo kale ka samaysanay unugyo kala bar Li4Ti5O12 (LTO) iyo LiFePO4 (LFP) electrodes budada ah.Xalka horudhaca ah ayaa lagu tuuray unugga lacagta qadaadiicda ah si uu u dhaliyo electrodes-ka daloolsan oo loo daayo gelation dheeraad ah ka hor inta aan la engegin oo aan faakuum-buuxin si la mid ah nano-SCE pellets.Unugyadu waxay muujinayaan lithation/delithiation sifada electrodes u dhigma (Jaantus. 6C).Xawaaraha ugu hooseeya ee LFP marka loo eego LTO waxaa sabab u ah faraqa dhumucda dahaarka.Waxqabadka heerka inta lagu jiro cabbiraadaha lacag-bixinta/daaqadda ayaa hadda xaddiday koronto-yaqaanka Li-foil counter-de oo lagu riixay lakabka nano-SCE ee ka sameysmay dusha sare ee 30- ilaa 40-μm- dhumucdiisuna waxay tahay koodhka korantada (Jaantus. 6, D iyo E).Unugga LTO/nano-SCE/Li waxa uu gaadhay xadiga ugu badnaan ee 160 mA·hour/g kaliya heerka C-hoose ee 0.02C (Jaantus. 6D).Awoodda la heli karo ayaa si degdeg ah hoos ugu dhacda heerka C-ka oo ka yar 10% ee heerarka C-ka ka weyn 0.1C.Sidoo kale, unugga LFP/SCE/Li waxa uu gaadhay xadiga ugu badnaan ee ku saabsan 140 mA·hour/g at 0.01C (Jaantus. 6E).Jaantuska 6F wuxuu muujinayaa waxqabadka heerka wadarta wareegyada 30, oo muujinaya qaabaynta unugga xasilloon.Tijaabooyinku waxay muujinayaan shaqada nano-SCE sida Li-ion electrolyte iyo suurtogalnimada isdhexgalka unugyada Li-ion.

Xasiloonida ama wareegtada nano-SCE ayaa lagu tijaabiyay iyadoo la adeegsanayo xirmo summeedka Li/SCE/Li.Waxaa lagu waday baaskiil in ka badan 120 wareegyo iyadoo cufnaanta hadda ah 0.1 mA/cm2 0.5 saacadood (Jaantus. 6G) iyada oo aan wax arrimo ah ama dendrite samaynta (Jaantus. 6H).Korontada dabaysha ayaa noqotay mid sii yaraanaysa wakhti ka dib, taas oo muujinaysa hagaajinta xidhiidhka.Waxaa intaa dheer, unugga ayaa lagu adkeeyay ilaa cufnaanta hadda ee 0.5 mA / cm2, iyada oo aan la samaynin dendrites lithium ama calaamado sii xumaanaya nano-SCE ama interface (Jaantus. 6G).Lithium bir ah waxaa loo yaqaanaa inuu sameeyo lakab ilaalin ah oo dhexdhexaad ah ama SEI oogada sare ee BMP-TFSI-based ILEs (27).Dareen-celintani waxay sidoo kale ka dhacdaa interface lithium/nano-SCE;sida hoos timaada Jaantuska 6A, SEI waxa laga yaabaa in ay ku koraan gudaha daloolada, taas oo sharxaysa iska caabbinta SEI sare ee nano-SCE marka loo eego ILE (eeg kor).Caddaynta lakabka SEI ayaa laga helay spectra IR (fig. S9).Si la mid ah dahaarka SEI ee LiB-ga caadiga ah, kaas oo ka eegaya graphite electrode ka dareeraha dareeraha ah ee ka fogaanaya falcelin dheeraad ah, waxaan aaminsanahay in SEI halkan sidoo kale ka ilaalinayso lakabka biyaha barafka falcelin dheeraad ah oo ka yimaada macdanta lithium anode.Xakamaynta spectra ka hor iyo ka dib polarization of Li/nano-SCE (x = 1.5) 10 saacadood ma muujin wax isbeddel ah ee caabbinta korantada badan.Cabbirrada waxqabadka baaskiilka ee dheer ayaa loo baahan doonaa si looga saaro qallajinta qunyar ee nano-SCE ee birta lithium, laakiin natiijooyinkani waxay durbaba muujinayaan kartida ay u leedahay wareegga ugu fiican ee SCE ee birta lithium-ku-saleysan baytariyada adag ee gobolka.Si kastaba ha ahaatee, dahaarka interphase-ka macmal ah ayaa loo tixgalin karaa si loo hagaajiyo impedance interface guud ahaan.

Waxaan tusnay in kor u qaadida ion conduction interfaces silica lagu gaari karo hordhaca lakabka biyaha chemisorbed ee dusha silica-ka OH-ka joojisay.Anions TFSI waxay chemisorb ka dhigtaa lakabka shaqaynta biyaha iyada oo loo marayo isku xidhka hydrogen iyo kooxda O═S═O simmetrical ah.Lakabka dusha biyuhu waa mid aan dhaqdhaqaaq lahayn oo markaa sidoo kale wuxuu ku dhejiyaa lakabka TFSI ee la isku dhejiyay oogada.Qaybaha waaweyn ee BMP waxay ku xidhan yihiin monolayer-ka TFSI, sidaas awgeed waxay soo bandhigayaan habaynta molecular ee TFSI-BMP dusha sare.Waxaan aaminsanahay in gelation-ka gaabis ah ee deegaanka aqueous iyo qalajinta gaabis ah ay ka caawiso samaynta wadajirka ah ee lakabka biyaha shaqeynaya iyo lakabka habaysan ee ions organic ee korkiisa.Maaddaama lakabka ugu horreeya ee TFSI anion uu qayb ka mid ah kharashkiisa taban la wadaago silica hydroxylated, lakabka BMP cation ee sare wuxuu raadin doonaa xiriir la leh anion kale oo TFSI ah, taas oo BMP badan ay ku wadaagi karaan kharashkooda aan magdhowga lahayn hal TFSI (malaha saddex ilaa hal sida ku jirta saamiga IL iyo Li-TFSI ee ILE).Maaddaama unugyaraha milixda ee Li-TFSI ay leeyihiin habka ugu dhow, ion-yada Li+ way kala go'i doonaan waxaana loo dejin doonaa si degdeg ah ugu faafidda lakabkan is-dhexgalka.Kor u qaadida, noocyada Li+ ee bilaashka ah waxay u baahan yihiin ugu yaraan hal lakab oo dareere ionic oo dheeri ah si loo dhex maro.Sababtan awgeed, nano-SCE ee leh x-qiimaha hooseeya ee 0.5 ma muujin korriin la xoojiyay, maaddaama mugga ILE / aagga dusha sare ee silica uu ku filan yahay hal monolayer oo xiran.

Waxa kale oo la tusay in biyaha dusha adag ee u eg ama lakabka barafka aanu ahayn kiimiko ahaan firfircoon.Halkaa marka ay marayso, kama saari karno in biyaha barafka ee xidhiidhka tooska ah ee dusha sare ee korantada aysan ka falcelinaynin.Si kastaba ha ahaatee, waxaan tusnay in faafinta ka-baxsan ee biyaha dusha sare ay yihiin kuwo gaabis ah oo sidaas darteed si firfircoon u dayacan si loo ogaado.Waxaan ogaanay in wasakheynta biyuhu, xitaa haddii ay yar yihiin, ay had iyo jeer noqon doonto walaac, oo keliya tijaabooyinka meertada nolosha ee dheer ayaa bixin kara jawaab cad oo ku saabsan in biyuhu si ku filan u xidhan yihiin iyo in kale.Si kastaba ha ahaatee, lakabyo kale oo shaqeynaya oo bixiya kor u qaadis la mid ah ama xitaa ka weyn ayaa hadda la horumarin karaa.Marka la eego, kooxda Li ayaa horey u muujisay awoodda lakabka glycidyloxypropyl sida koox hawleed (18).Biyaha barafka waxay asal ahaan ka soo jeedaan silica, sidaas darteed waxay ku habboon yihiin in la barto saameynta shaqeynta dusha sare ee kor u qaadista ion si nidaamsan, sida lagu muujiyay si guul leh halkan.Intaa waxaa dheer, lakabka mesophase iyo dipole waxay ku xirnaan doontaa oksaydhka iyo molecules organic adsorbed sidaas darteedna waa la hagaajin karaa labadaba.Shaybaarka, waxaan horeyba ugu muujinnay kala duwanaansho weyn oo ku saabsan dhiirrigelinta ion conduction ee cabitaannada ionic ee kala duwan.Intaa waxaa dheer, mabda'a la muujiyay waa mid guud oo ku wajahan wareegga ion-ka waxaana sidoo kale lagu dabaqi karaa hababka kala duwan ee ion ee ku habboon, tusaale ahaan, soodhiyam, magnesium, kalsiyum, ama baytariyada aluminium.Gebogebadii, nanocomposite electrolyte oo leh is-dhexgalka is-dhexgalka ee halkan lagu muujiyay waa fikrad halkii laga heli lahaa hal shay, taas oo noqon karta mid dheeraad ah (nano) oo lagu farsameeyo sifooyinka la rabo ee xakamaynta ion, lambarka gaadiidka, daaqada korantada, badbaadada, iyo kharashka jiilka unugyada batteriga mustaqbalka .

Nano-SCE waxaa lagu diyaariyey iyadoo la isticmaalayo habka sol-gel.Lithium bis (trifluoromethylsulfonyl) imide Li-TFSI;Sigma-Aldrich;99.95%), 0.5 ml oo ah H2O deionized, 0.5 ml TEOS (Sigma-Aldrich; 99.0%), 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide (BMP-TFSI; Sigma-Aldrich; 98.5%), iyo 1 ml oo PGME ah ayaa lagu qasay dhalo dhalo ah.Saamiga molarka, x, inta u dhaxaysa [BMP][TFSI] iyo TEOS ee isku dhafka ah ayaa kala duwanaa inta u dhaxaysa 0.25 iyo 2. Saamiga molarka ee Li[TFSI] iyo [BMP][TFSI] waxaa lagu hagaajiyay 0.33:1.Xaddiga Li[TFSI] iyo [BMP][TFSI] ayaa laga go'aamiyey saamiyadan.Tusaale ahaan, marka x = 1, lagu daray [BMP][TFSI] iyo Li[TFSI] ee xalka waxay ahaayeen 0.97 iyo 0.22 g, siday u kala horreeyaan.Isku darka ayaa la ruxay 1 daqiiqo si ay u sameeyaan xalal monophasic.Xalalkaas ayaa markaa lagu kaydiyay fijaannada xiran iyada oo aan la walaaqin si ay u sameeyaan jel-ka-koobeedka heerkulka-iyo qoyaanka lagu xakameeyo (SH-641, ESPEC Corp.) heerkulka iyo RH% ee la dhigay 25 ° C iyo 50%, siday u kala horreeyaan.Iyada oo ku xidhan x, isku darka ayaa qaatay, celcelis ahaan, 5 ilaa 9 maalmood si ay u sameeyaan jel cad.Caleemaha ka dib, fijaannada leh 2.4- ilaa 7.4-ml jel ayaa marka hore la qalajiyey 40 ° C afar maalmood oo buuxa cadaadis yar oo la dhimay (80 kPa) ka dibna loo guuray foornada faakuumka 72 saacadood 25 ° C.Markii qoyaanka soo haray laga saaray, faakuumku wuxuu si tartiib tartiib ah hoos ugu dhacay cadaadiskii ugu horreeyay ee ku wareegsan 50 Pa ilaa cadaadis joogto ah oo kama dambays ah oo 5 Pa qiyaastii 1 maalin ka dib.Sababtoo ah tirada badan ee biyaha iyo PGME ee ay ahayd in la saaro, natiijada SCE pellets ayaa hoos uga dhacay 20% (x = 0.5) ilaa ~ 50% (x = 2) ee mugga jel asalka ah.Miisaanka gelyada ka soo baxay waxaa lagu cabbiray dheellitirka semimicro (SM 1245Di-C, VWR).

TGA waxaa lagu sameeyay Q5000 IR (TA Instruments, New Castle, DE, USA) hoostiisa nitrogen.Inta lagu guda jiro cabbiraadda, muunado ayaa lagu kululeeyay 700°C marka la eego heerka kulaylka ee 2°C/daqiiqo.FTIR spectrometry waxaa lagu sameeyay iyadoo la adeegsanayo Bruker Vertex 70 ee tirada mowjadaha u dhexeeya 4000 ilaa 400 cm-1 ee habka gudbinta.pycnometry waxaa lagu sameeyay iyadoo la adeegsanayo Micromeritics AccuPyc II 1340.

Si loo cabbiro dhaqdhaqaaqa ionic, mug yar oo SCE ah ayaa laga soo qaatay dhalo hooyada gudaha sanduuqa galoofka ee Ar-buuxsan yahay (0.1-ppm H2O iyo 0.1-ppm O2).Qiyaastii 23 μl ee SCE ayaa lagu buuxiyey giraanta polytetrafluoroethylene (PTFE) oo leh dhexroor 4.34-mm ah iyo dherer 1.57-mm ah, taas oo samaynaysa pellet.Pellet-ka giraanta ku jira ayaa markaa la dhex galiyay inta u dhaxaysa laba saxan oo bir ah (SS) (dhammaan 0.2 mm; MTI).Cabbirrada impedance ayaa la sameeyay iyadoo la adeegsanayo PGSTAT302 (Metrohm), oo leh baaxadda AC ee 5 mV oo u dhexeysa 1 MHz ilaa 1 Hz.Ion conductivity (σi) waxaa lagu go'aamiyay isdhexgalka-sare ee soo noqnoqda ee leh dhidibka dhabta ah ee dhulalka Nyquist.Cabbirka korantada ka dib, pellet-ka nano-SCE ayaa loo oggolaaday inuu ku sii qallajiyo sanduuqa galoofyada.Qiyaasta ku-tiirsanaanta heerkulka, xidhmooyinka SS/SCE/SS waxa lagu shaabadeeyey unug qadaadiic ah.Ka dib markii la xidho, conductivity-gu wuxuu ahaa mid joogto ah dhowr maalmood (eeg fig. S3).Heerkulka unugga lacagta qadaadiicda ah waxaa lagu xakameynayaa jaakad kuleyl leh oo leh qubeys kulayl leh iyadoo la adeegsanayo H2O/ethylene glycol sida dhexdhexaadinta shaqada.Unugyada ayaa marka hore la qaboojiyey ilaa -15 ° C ka dibna si caqli-gal ah ayaa loo kululeeyey ilaa 60 ° C.

Pellet kasta oo nano-SCE ah, ku dhawaad 23 μl ayaa la keenay giraan (4.34-mm dhexroorka gudaha ah iyo 1.57-mm) cabirrada korantada si toos ah gudaha sanduuqa galoofyada ee N2-buuxsan yahay oo leh qoyaan kontaroolan.Giraanta leh SCE ayaa markaa la dhex galiyay inta u dhaxaysa labada saxan ee SS (0.2 mm qaro weyn; MTI).Cabbirrada impedance ayaa la sameeyay iyadoo la adeegsanayo PGSTAT302 (Metrohm) oo leh baaxadda AC ee 5 mV iyo inta jeer ee u dhexeysa 1 MHz ilaa 1 Hz oo lagu kontoroolo software Nova.Tijaabooyinku waxa lagu hayaa qiime kasta oo RH% ah 48 saacadood ka hor inta aan la kormeerin socodka hawada ilaa laga xasilinayo.Dhaqdhaqaaqa ionic ee xasiloon ee qiimaha RH% ee la bixiyay (σi) ayaa laga go'aamiyay is-dhex-galka-sare ee soo noqnoqda ee leh dhidibka dhabta ah ee dhulalka Nyquist.

Qaab-dhismeedka pellet oo leh iyo la'aanteed Li[BMP] [TFSI] ILE waxaa lagu hubiyay SEM iyadoo la adeegsanayo aaladda Thermo Fisher Scientific Apreo 1.5 illaa 2.0 kV taasoo ku shaqeyneysa qaab sawir-qaade laba-gees ah iyadoo la adeegsanayo aaladaha T1 iyo T2 oo barbar socda hagaajinta sawirka nool, iyo T2 detector ayaa loo isticmaalay duubista sawirada SEM ee la muujiyay;muunada waxaa lagu hagaajiyay cajalad kaarboonka.TEM waxa lagu sameeyay iyadoo la isticmaalayo Tecnai oo ku shaqaynaysa 300kV.

ILE waxaa looga saaray pellet-ka SCE laba siyaabood oo kala duwan.Mid ka mid ah ikhtiyaarka lagu heli karo silica daloolka leh ayaa la sameeyay iyadoo la gelinayo SCE gudaha acetone 12 saacadood si loo soo saaro Li[BMP][TFSI] ILE.Biyo raacitaan ayaa lagu celceliyay saddex jeer.Doorashada kale waxay ahayd iyadoo lagu qooyay SCE ee ethanol.Xaaladdan oo kale, ethanol ayaa laga saaray iyadoo la adeegsanayo dareeraha CO2 qalajiyaha dhibicda muhiimka ah.

Laba qalab oo kala duwan ayaa loo isticmaalay qalajinta sare, kuwaas oo kala ah, Automegasamdri-916B, Tousimis (habka 1) iyo qalab ay dhistay JASCO Corporation (habka 2).Markaad isticmaalayso qalabka ugu horreeya, isku xigxiga qalajinta wuxuu ku bilaabmay hoos u dhaca heerkulka ilaa 8 ° C.Ka dib, CO2 ayaa lagu nadiifiyay qolka, taas oo kordhinaysa cadaadiska ilaa 5.5 MPa.Talaabada soo socota, CO2 waxaa lagu kululeeyay 41 ° C, kordhinta cadaadiska ilaa 10 MPa, waxaana lagu hayaa sida 5 min.Si loo soo gabagabeeyo, tallaabada dhiigbaxa, cadaadiska ayaa hoos loo dhigay muddo 10 daqiiqo ah.Marka la isticmaalayo qalabka la dhisay, isku xigxig la mid ah ayaa la raacay.Si kastaba ha ahaatee, wakhtiga iyo cadaadiska ayaa si weyn u kala duwanaa.Tallaabada nadiifinta ka dib, cadaadiska ayaa la kordhiyey ilaa 12 MPa heerkul ah 70 ° C wuxuuna ku jiray sida 5 ilaa 6 saacadood.Ka dib, cadaadiska ayaa hoos loo dhigay intii u dhaxaysay 12 ilaa 7 MPa, 7 ilaa 3 MPa, iyo 3 ilaa 0 MPa wakhtiyada 10, 60, iyo 10 min, siday u kala horreeyaan.

Isotherms physisorption Nitrogen ayaa lagu cabiray T = 77 K iyadoo la adeegsanayo falanqeeyaha astaamaha dusha sare ee Micromeritics 3Flex.Silica daloolsan ee la helay ayaa dabadeed laga saaray 8 saacadood 100 ° C iyada oo hoos timaad faaruq 0.1-mbar ah.Silica dabada leh ee ka soo baxday qalajinta aadka u daran ayaa hawada laga saaray 18 saacadood 120°C iyada oo hoos timaada faakuum 0.1-mbar ah.Intaa ka dib, isotherms physisorption nitrogen ayaa lagu cabbiray T = 77 K iyadoo la adeegsanayo Micromeritics TriStar 3000 falanqeeye xayeysiis gaas oo toos ah.

Qiyaasaha PFG-NMR waxaa lagu sameeyay iyadoo la isticmaalayo JEOL JNM-ECX400.Isku xigxiga garaaca garaaca dhawaaqa ee la kiciyay ayaa loo adeegsaday cabbirada fidinta.Attenuation signal echo caadiga ah, E, waxaa lagu qeexay isla'egta (38) E = exp (-γ2g2δ2D (Δ-δ/3)) (1) halka g ay tahay xoogga garaaca garaaca wadnaha, δ waa muddada gradient garaaca garaaca wadnaha, ∆ waa inta u dhaxaysa cidhifyada hogaaminaya garaacyada gradient-ka, γ waa saamiga magnetogyric, iyo D waa isku-darka is-faafinta molecules-ka.Isku-duwayaasha is-faafinta ayaa lagu qiyaasay iyadoo lagu rakibay calaamadaha dhawaaqa ee la helay iyadoo lagu beddelay ∆ Eq.1. 7Li ayaa loo doortay si loo go'aamiyo isku-dhafka fidinta ee ion lithium.Dhammaan cabbirada waxaa lagu sameeyay 30 ° C.

Qalabka spectroscopy ee Raman wuxuu ahaa nidaam guri-guri ah iyadoo la adeegsanayo argon ion awood u leh in lagu hagaajiyo iftiinka 458-nm laser excitation light kaas oo lagu daray mikroskoob Olympus IX71 rogan, iyo iftiinka dambe ee kala firdhiyey ayaa la dhex mariyey TriVista saddex-geesoodka spectrometer set (Princeton Instruments). ), kaas oo loo isticmaalay in lagu kala firdhiyo calaamadaha indhaha ee lagu ogaado iyada oo la isticmaalayo kamarad qalabaysan oo dareere ah oo nitrogen-qaboojiye ah.Marka la eego nuugista indhaha sare ee mawjadahan, awoodaha laysarka oo aad u hooseeya ayaa la isticmaalay si looga fogaado kuleyliyaha laysarka (<100 W · cm-2).

Kobcinta joomatari dhulka ee DFT iyo xisaabinta inta jeer ee gorfaynta waxay adeegsatay shaqada isku-dhafka ah ee B3LYP ee caanka ah iyo 6-311++G** dhigay, oo leh Grimme's atom-pairwise firidhsan sixid (39) oo leh nidaamka qoynta Becke-Johnson (D3BJ), sida lagu fuliyay ORCA 3.0.3 (40).Raman spectra waxaa lagu sawiray iyadoo la isticmaalayo ORCA, iyo aragtida guryaha molecular waxaa lagu gaarey iyadoo la isticmaalayo xirmada software Avogadro (41) oo leh casriyeynta ay taageerto ORCA.

Dhammaan cabbiraadaha korantada iyo diyaarinta muunadda la xidhiidha waxaa lagu sameeyay sanduuqa galoofka ee argon ka buuxo (PureLab, PL-HE-4GB-1800; <1-ppm O2 iyo H2O heerarka) oo loogu talagalay astaamaha korantada.Pellet-ka SCE waxa lagu dhejiyay ribbon Li (Sigma-Aldrich; 99.9%) oo lagu taageeray saxan naxaas ah sida korantada counter-ka iyo laba la tumay Li disks (dhexroor 5-mm) ayaa la dulsaaray dusha sare ee Pellet SCE si loo tixraaco loona shaqeeyo. electrodes.Habaynta waxa lagu muujiyay fig.S7.Biinanka dahabka ah ayaa loo isticmaalay la xidhiidhka tixraaca lithium-ka iyo electrodes-ka shaqeeya.Voltammetry cyclic iyo cabbiraadaha impedance ayaa la sameeyay iyadoo la isticmaalayo PGSTAT302 (Metrohm) oo lagu kontoroolo software Nova.Voltammetry cyclic waxaa lagu sameeyay cabirka sawirka 20mV/s.Cabbirrada impedance ayaa lagu sameeyay baaxadda AC ee 5 mV iyo inta jeer ee u dhaxaysa 1 MHz ilaa 0.1 Hz.

40-nm anatase TiO2 fiilada khafiifka ah ee elektiroonigga ah waxaa lagu shubay kaydinta lakabka atomiga ah (ALD) ee wafer silikoon ah oo 300-mm ah oo leh 40-nm TiN hoosta oo ay sidoo kale kaydisay ALD.Waa koronto tijaabo ah oo aad u fiican oo loogu talagalay muujinta conductivity Li-ion iyada oo loo marayo electrolytes, maadaama TiO2 aysan ka soo gaarin hoos u dhaca kiimikada ama culeyska farsamada (ma jiro isbeddel mug leh) inta lagu jiro baaskiil wadida.Si loo cabbiro unugga Li/SCE/TiO2, ILE-SCE-yada waxaa lagu buuxiyey giraanta PTFE oo leh dhexroor 4.3 mm iyo dhumucdiisu tahay 0.15 cm;ka dib, giraanta ayaa la dhex galiyay inta u dhaxaysa foil Li-foil iyo filimka TiO2.

Nano-SCE/filim-dhuuban korantada nus xidhmooyin ah, oo leh korantada LMO, ayaa la sameeyay iyada oo la abuurayo filimka nano-SCE ee korantada.Wadarta 150 μl ee x = 1.5 xal, oo da'doodu tahay 2 maalmood, ayaa lagu shubay giraanta dhalada ah (dhexroor, 1.3 mm) oo lagu dhejiyay filimada elektrolytka.Ka dibna giraanta ayaa lagu xidhay baallaha, iyo xalalka waxaa lagu hayaa weel xiran oo si gel ah ilaa 4 maalmood.Xidhmada jel/electrode ee la sameeyay sidaan oo kale ayaa la engejiyey si ay u sameeyaan xidhmooyin nano-SCE/electrode ah.Dhumucda nano-SCE, ee lagu go'aamiyay iyadoo la isticmaalayo micrometer, waxay ahayd 300 μm.Ugu dambeyntii, foil lithium ah (1.75 mm dhumucdiisuna, 99.9%; Sigma-Aldrich) ayaa lagu riixay xirmada nano-SCE/electrode sida anode.100-nm LiMn2O4 (LMO) fiilada khafiifka ah ee elektiroonigga ah waxaa lagu shubay qulqulka raadiyaha ee socodka qulqulka Ar ee wafer silikoon oo dahaarka leh 80-nm Pt (DC sputtering)/10-nm TiN (ALD) hoostooda.Xirmadaan waxaa lagu daboolay 20 daqiiqo at 800 ° C jawiga oksijiinta.

LiFePO4 (LFP) filimaanta korantada waxaa lagu diyaariyey dahaarka daabka.Marka hore, kaarboon madow iyo LFP (2 ilaa 3 μm) ayaa lagu daray xal aqueous ka kooban karboxymethylcellulose (CMC) si ay u sameeyaan isku dar ah taas oo ka dib la mid ah iyadoo la isticmaalayo qase meeraha.Dabadeed, badeecada la isku daray ayaa lagu qasay biyo fuuqsamay iyo cinjirka acrylic fluorinated (JSR, TRD202A) ee qasaha faakuumka si uu u sameeyo slurry loogu talagalay dahaarka korantada.Soodhadhka la diyaariyey ayaa lagu tuuray foornada aluminiumka si loogu shubo aflaanta korantada iyadoo la isticmaalayo jaakad daab ah.Electrodes-ka qoyan ee sida-dahaarka leh ayaa isla markiiba lagu sii daayay foorno atmospheric leh hawo fadhiid ah oo ku taal 70 ° C 10 daqiiqo waxaana lagu sii qalajiyey 140 ° C ilaa 4 saacadood foornada faakuumka.Filimada korantada ee la qalajiyey waxay ka koobnaayeen 91 wt % LiFePO4, 3 wt % kaarboon madow, 2 wt % CMC, iyo 4 wt % TRD202A.Dhumucda filimku waa 30 μm (waxaa lagu go'aamiyay iyadoo la isticmaalayo mikrometer iyo iskaanka mikroskoob ee elektarooniga ah).

Li4Ti5O12 (LTO) aflaanta korantada ayaa lagu sameeyay si la mid ah foils copper.Halabuurka electrodes-ka la qalajiyey waa 85 wt % Li4Ti5O12, 5 wt % kaarboon madow, 5 wt % CMC, iyo 5 wt % cinjirka akril ee fluorinated (TRD2001A).Dhumucda filimku waa 40 μm.

Xalka SCE ayaa lagu tuuray qaybta ku salaysan LFP iyo filimka LTO ee korantada.Marka hore, 100 μl x = 1.5 xal, oo da'doodu tahay 2 maalmood, ayaa lagu shubay filimka elektiroonigga ah, oo leh dhexroor 15 mm, oo lagu dhejiyay unug qadaadiic ah (#2032, MTI).Ka dib markii SCE-da uur-ku-jirka ah la jeexay, filimka waxaa lagu qallajiyey 25 ° C ilaa 72 saacadood foornada faakuumka (<5 × 10-2 mbar) si loo sameeyo nano-SCE iyo xirmooyinka korantada.Dhumucda nano-SCE waxay ahayd 380 μm.Ugu dambeyntii, bireed lithium ah ayaa lagu riixay xirmooyinka SCE/electrode sida anode-ka, unugga qadaadiicdana waa la xiray.Cabbiraadaha korantada kiimikaad ayaa lagu sameeyay iyadoo la isticmaalayo a Solartron 1470E potentiostat heerkulka qolka.

Waxyaabaha dheeriga ah ee maqaalkan ayaa laga heli karaa http://advances.sciencemag.org/cgi/content/full/6/2/eaav3400/DC1

Shaxda S1.Sifooyinka qaab dhismeedka matrix silica ee nano-SCE ee kordhinta jajabka molar ee dareeraha ionic ilaa silica (qiimaha x) ee laga go'aamiyay N2 adsorption / desorption ama cabbirada BET iyo indho-indheynta TEM.

Kani waa maqaal gelitaan furan oo lagu qaybiyey shuruudaha Shatiga Hal-abuurka Caadiga ah -Shatiga Aan Ganacsiga ahayn, kaas oo oggolaanaya isticmaalka, qaybinta, iyo taranka meel kasta, ilaa inta isticmaalka natiijadu aanu ahayn faa'iido ganacsi oo ay bixiso shaqada asalka ah ee saxda ah soo xigtay.

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