Kev hloov pauv mus rau cov roj teeb hauv lub xeev Li-ion yuav ua rau muaj kev vam meej mus rau lub zog ceev ntawm 1000 W·hour / liter thiab tshaj.Composites ntawm ib tug mesoporous oxide matrix uas muaj cov nonvolatile ionic kua electrolyte muab tub lim tau tshawb nrhiav raws li ib qho khoom siv electrolyte.Txawm li cas los xij, qhov yooj yim kaw ntawm cov tshuaj electrolyte hauv nanometer qhov pores ua rau qis ion conductivity raws li viscosity nce.Ntawm no, peb qhia tau hais tias Li-ion conductivity ntawm nanocomposites muaj ib tug mesoporous silica monolith nrog ib tug ionic kua electrolyte muab tub lim yuav ua tau ob peb zaug siab tshaj li cov ntshiab ionic kua electrolyte los ntawm cov kev taw qhia ntawm ib tug interfacial ice txheej.Muaj zog adsorption thiab kev txiav txim ntawm ionic kua molecules ua rau lawv immobile thiab khoom zoo li rau lub interfacial ice txheej nws tus kheej.Lub dipole tshaj lub adsorbate mesophase txheej ua rau kev daws teeb meem ntawm Li + ions rau kev txhim kho conduction.Lub hauv paus ntsiab lus qhia txog kev txhim kho ion conduction tuaj yeem siv rau ntau lub tshuab ion.

Solid-state electrolytes yuav tsum tau muab kev txhawb nqa ntxiv rau Li-ion roj teeb kom tshaj li qhov ua tau zoo ntawm 800 W·hour / liter lossis 300 W·hour / kg imposed tam sim no muaj cathode thiab anode chemistry.Qhov kev xav tau nce ntxiv ntawm lub zog ceev rau cov roj teeb uas muaj zog los ntawm ntau qhov kev koom tes, tag nrho cov phiaj xwm nce qhov ntim feem pua ​​​​ntawm cov khoom siv hauv lub cell.Qhov tshaj tawm tshaj tawm yog kev taw qhia ntawm lithium hlau los hloov graphite thiab graphite / silicon ua anode.Ntshiab lithium hlau muaj lub zog siab tshaj plaws ua tau thiab yog li xav tau qhov chaw tsawg tshaj plaws.Txawm li cas los xij, ntau qhov teeb meem tseem yuav tsum tau daws, xws li cov tshuaj tiv thaiv tsis tuaj yeem (thiab yog li noj) ntawm lithium hlau, tsim dendrite, qhov nce ntawm qhov ceev tam sim no rau planar lithium foils piv rau cov ntxeem tau graphite (silicon) electrodes, thiab, kawg. tab sis tsis tsawg, qhov "tso lawm" ntawm lithium thaum tawm (deplating) thiab yog li poob ntawm kev sib cuag nrog cov khoom electrolyte.Cov txheej txheem nruj ntawm cov khoom siv hluav taws xob cov khoom siv hluav taws xob tiag tiag muaj xoom ua raws, thiab kev kub ntxhov hnyav yuav tsum tau siv los nias lub lithium kom ruaj khov tiv thaiv cov khoom electrolyte.Cov ntsiab lus siab tsis sib xws txo qis qhov zoo ntawm thaj chaw ntau dua, ua rau lub zos dendrite tsim thiab spongy deposits.Polymer electrolytes yog ntau mechanically raws tab sis tseem tsis tau muaj siab txaus ionic conductivity ntawm chav tsev kub.Cov ntaub ntawv tshiab nthuav dav hauv qhov no yog silica gel electrolytes, uas tau raug hu ua "ionogels," qhov twg ionic kua electrolyte (ILE) raug kaw hauv nanoporous silica matrix (1).Qhov porosity siab heev ntawm silica matrix (70 mus rau 90%) muab cov ntaub ntawv nanocomposite electrolyte zoo ib yam li gel thiab yog li ua rau lawv mechanically raws li polymer electrolytes.Cov silica gels no qee zaum qhia tias yog cov khoom siv hluav taws xob sib txuas, vim lawv muaj cov kua dej.Txawm li cas los xij, rau cov silica nanocomposites, raws li tau piav qhia hauv daim ntawv no, ionic "kua" electrolyte ua cov khoom zoo li thaum kaw hauv kaum ntawm nanometer-qhov loj me raws ob qho tib si los ntawm kev nce hauv viscosity thiab los ntawm adsorption ntawm silica phab ntsa kaw. channel.Yog hais tias silica matrix yuav ua raws li ib tug ntxeem tau cais, ces qhov nce nyob rau hauv viscosity rau cov kua electrolyte confined yuav ua rau ib tug txo nyob rau hauv ionic conductivity.Hloov chaw, kev sib cuam tshuam ntawm ILE molecules thiab silica pore phab ntsa ua rau cov khoom ntawm nanocomposite txawv ntawm qhov sib npaug ntawm nws cov khoom.Adsorption ntawm ionic kua ntawm oxides nrog tsim ntawm cov khoom mesophase txheej mus txog rau ob peb nanometers nyob rau hauv thickness tau pom nyob rau hauv cov ntaub ntawv uas muaj atomic force microscopy (2).Cov kev xaiv adsorption ntawm ionic kua anions thiab cations ntawm oxide nto tuaj yeem ua rau txhim kho Li + conductivity raws cov kev sib tshuam no.Tau kawg, kev txhim kho raws li oxide interfaces yuav tsum tau them nyiaj rau lossis txawm tias tshaj qhov txo qis ntawm ILE nyob rau hauv cov tub ntxhais ntawm cov pores.Yog li ntawd, qhov me me pore loj thiab qhov siab ntawm qhov chaw-rau-ntim piv yog xav tau.Txog tam sim no, ionogels nrog ion conductivities mus txog ntawm ILE nws tus kheej tau pom los ntawm kev ua kom zoo ntawm cov qauv mesoporous (3).Qhov no txhais tau hais tias kev txhim kho interface twb muaj lawm tab sis tsis yog mus rau qhov ntau tshaj qhov kev coj ua.

Kev npaj ntawm ionogels pib los ntawm homogeneous kua sib tov, nyob rau hauv uas ib tug ILE yog ntxiv rau ib tug sol-gel precursor tov rau cov synthesis ntawm oxide matrix (4, 5).Nyob rau hauv txoj kev no, ILE thiab matrix tsim ib qho kev sib xyaw ua ke nyob rau hauv "nyob rau hauv situ" yam: Cov precursors nyob rau hauv cov tshuaj react rau tsim ib tug oxide matrix nyob ib ncig ntawm lub ionic kua template, encapsulating nws nyob rau hauv cov txheej txheem.Raws li qee qhov kev sib xyaw ua ke, qhov npaj ILE-SCE (cov khoom sib xyaw electrolyte) tuaj yeem ua rau hauv daim ntawv ntawm monolith nrog ILE embedded nyob rau hauv ib tug tas mus li mesoporous inorganic oxide network.Txog tam sim no, feem ntau silica-raws li ILE-SCEs tau npaj ua li no, txawm hais tias piv txwv kuj tau ua nrog alumina (6), titania (7), thiab txawm tias tin oxide (8).Feem ntau tshaj tawm sol-gel formulations muaj ILE, ib qho alkyl-silicate xws li tetraethyl orthosilicate (TEOS) li silica precursor, thiab formic acid li reagent thiab hnyav (9, 10).Raws li lub tswv yim txheej txheem (11) rau cov txheej txheem sol-gel no, silica feem ntau yog tsim los ntawm cov tshuaj tiv thaiv ntawm TEOS thiab formic acid, txawm hais tias dej yog tsim thaum lub sij hawm sol-gel txheej txheem.Dhau li ntawm cov formic acid-raws li "nonaqueous" mixs, aqueous sol-gel formulations nrog HCl raws li ib tug catalyst thiab H2O raws li ib tug reagent (ntxiv rau cov organic hnyav) kuj tau piav, Txawm li cas los, nyob rau hauv no tshwj xeeb cov ntaub ntawv rau lub synthesis ntawm ib tug silica composite nrog. ionic kua (12-15).

Feem ntau, ionogels qhia ion conductivity qis dua li ntawm ILE siv.Thawj tiam ntawm ionogels muaj chav kub conductivities feem ntau tsuas yog li 30 mus rau 50% ntawm cov nqi ILE ntau, txawm hais tias qee qhov piv txwv txog li 80% tau tshaj tawm (9, 10, 16, 17).Cov txiaj ntsig ntawm ILE cov ntsiab lus thiab ua rau qhov pore morphology ntawm ionogel conductivity twb tau tshawb xyuas kom meej (3);Txawm li cas los xij, tsis muaj kev tshawb fawb txog kev cuam tshuam txog kev cuam tshuam tau paub.Wu et al.(18) tsis ntev los no tau tshaj tawm nyob rau hauv ib qho chaw ua haujlwm ionogel, uas kuj tau muab kev ua kom zoo dua qub piv rau cov ILE ntau.Qhov kev txhim kho tau raug ntaus nqi los ntawm kev sib cuam tshuam ntawm anion thiab 3-glycidyloxypropyl ua haujlwm pab pawg ntawm silica nto.Qhov kev tshawb pom no txhawb nqa lub tswv yim tias qhov chaw ua haujlwm tau zoo tuaj yeem txhim kho qhov kev sib txuas lus txhawb nqa.

Hauv kev ua haujlwm no, peb ua kom pom qhov tsim ntawm cov dej khov nab kuab txheej ntawm silica thiab nthuav dav cov txheej txheem ntawm kev cuam tshuam ntawm Li-ion conduction los ntawm kev sib cuam tshuam ntawm dipole ntxiv ntawm cov dej khov dej ua haujlwm thiab cov txheej txheem adsorbed ionic kua mesophase.Los ntawm kev sib xyaw ua ke ntawm thaj chaw siab sab hauv thiab cov dej khov khov ua haujlwm, cov khoom siv nanocomposite electrolytes (nano-SCE) nrog 200% siab dua Li-ion conductivity dua li cov ntaub ntawv ILE tau ua tiav.Cov silica matrix tau pom tias muaj cov qauv monolithic mesoporous tiag tiag nrog cov pore ntim thiab thaj chaw saum npoo txog li 90% thiab 1400 m2 / g, yog li muab qhov sib txawv ntawm qhov loj-rau-volume tso cai rau kev txhawb nqa loj ntawm kev txhim kho ntawm cov kev cuam tshuam no.Los ntawm optimized functionalization ntawm silica nto ua ke nrog ua kom qhov chaw-rau-ntim piv, nano-SCE nrog ion conductivities zoo tshaj 10 mS / cm yuav muaj peev xwm yuav engineered thiab yog li zoo nkauj heev rau loj-muaj peev xwm roj teeb rau automotive daim ntaub ntawv.

Lub hom phiaj ntawm peb daim ntawv yog nyob rau hauv lub mechanism ntawm enhanced interface conductivity los ntawm tsim ib tug mesophase txheej nrog pov thawj los ntawm Raman, Fourier transform infrared (FTIR), thiab nuclear magnetic resonance (NMR) spectroscopy.Lub interface stability ntawm peb cov khoom nano-SCE ntawm high voltages yog qhia siv nyias-film lithium manganese oxide (LMO) electrodes.Nyob rau hauv txoj kev no, tsom ntsoov rau cov khoom siv es tsis yog ntawm kev sib koom ua ke ntawm electrode thiab cov teeb meem ntawm tes sib dhos.Ib yam li ntawd, lub qhov rais electrochemical thiab stability tiv thaiv lithium hlau foils yog tag nrho cov yam ntxwv.Kev ua haujlwm thiab kev koom ua ke ntawm peb cov nano-SCE tau pom los ntawm kev sib dhos thiab ntsuas kev ua haujlwm ntawm lithium hlau phosphate (LFP) thiab lithium titanate (LTO) hlwb.Qhov ruaj khov ntawm peb cov electrolyte thiab electrochemical inactivity ntawm cov dej khov dej tau pom los ntawm kev mus sij hawm ntev ntawm kev sib luag ntawm Li-SCE-Li hlwb.Kev ua kom zoo ntawm lub zog ntom, kev ua tau zoo, thiab kev ua haujlwm cycling ntawm cov hlwb sib sau ua ke yuav yog cov ntsiab lus ntawm cov ntawv rov qab (19, 20, 20).

Interfacial ion conductivity nce qib hauv ob-theem sib xyaw tshuab tau paub txog yuav luag 90 xyoo (21).Piv txwv li, mus txog plaub qhov kev txiav txim ntawm kev nce hauv ionic conductivity tau pom rau cov khoom sib xyaw ntawm cov lithium ntsev yooj yim xws li lithium iodide nrog mesoporous oxide hais xws li silica lossis alumina piv rau cov ion conductivity ntawm cov ntshiab lithium ntsev electrolyte (22).Cov ions hauv SCEs tuaj yeem nthuav dav sai dua raws li Li ion-depleted (los yog cov khoom nplua nuj) hluav taws xob ob txheej tsim ntawm oxide / electrolyte interface.Hmoov tsis zoo, cov ion conductivity tau nyob rau hauv cov yooj yim ob-component inorganic solid-solid composites (1) tsis tau tshaj 1-mS / cm2 pib xav tau los txuas ob peb puas-micrometer deb ntawm cov tam sim no collector daim hlau nyob rau hauv Li-ion roj teeb. .Lub tswv yim ntawm heterogeneous doping nrog ib tug oxide matrix los engineer lub ionic conductivity kuj tau tshawb fawb rau polymer electrolytes (23) thiab ILEs (24), uas muaj ntau dua intrinsic ionic conductivity pib nrog.Tsis tas li ntawd, cov nplua nuj molecular (lub tso suab) chemistry ntawm lub thib peb tivthaiv opens ntxiv ion conduction mechanisms, raws li cov (di) polar solvent zoo li molecules yuav koom nyob rau hauv tsim ntawm hluav taws xob ob txheej.Thaum cov kev daws teeb meem ntawm ether pawg hauv polyethylene oxide polymer electrolytes muab cov khoom siv hauv lub xeev ion conductivities ntawm ~ 10−6 S / cm rau LiClO4 txog ~ 10−5 S / cm rau LiN (SO2CF3) 2, lawv cov khoom sib xyaw nrog silica, alumina , los yog titania nanoparticles muaj tseeb tuaj yeem muab ntau tshaj 10-fold txhim kho hauv kev ntsuas ion conductivity (25), hmoov tsis zoo, tseem zoo hauv qab chav ntsuas kub ntawm 1 mS / cm.ILE cov kev daws teeb meem yog cov khoom sib xyaw ntawm Li-ntsev solute thiab ionic kua hnyav, uas tuaj yeem muaj cov khoom siv hluav taws xob siab ntawm 0.1 thiab 10 mS / cm (26, 27).Ntau qhov kev sim tau ua los txhim kho cov ion conductivity los ntawm kev sib xyaw lossis gelling nrog oxide nanoparticles lossis kom kaw cov ILE hauv mesoporous microparticles (9, 16, 28, 29).Txawm li cas los xij, txog tam sim no, tsis muaj kev txhim kho ntawm cov ion conductivity tau raug soj ntsuam rau peb cov khoom Li-ntsev / ionic kua / oxide composites (daim duab S1).Txawm hais tias kev siv mesoporous silica microparticles ua rau muaj kev ua tau zoo dua piv rau cov khoom sib xyaw nrog cov khoom nanoparticles, thaj tsam ntawm qhov chaw ntawm lub ntsej muag thiab ion conduction nce qib tsis txaus siab tshaj qhov ILE conductivity.

Mesoporous silica yog cov khoom siv paub zoo siv hauv catalysis.Nws feem ntau yog ua los ntawm hydrothermal lossis yooj yim sol-gel synthesis.Cov txheej txheem Hydrothermal feem ntau ua rau cov hmoov mesoporous, tab sis nrog kev ceev faj tswj ntawm chav tsev kub sol-gel txheej txheem, cov iav loj porous monoliths lossis aerogels kuj tau tsim.Lub silica matrix yog tsim los ntawm hydrolysis thiab condensation tshua ntawm tetra-alkyl orthosilicates (30).Qhov tseem ceeb hauv kev tswj cov qauv pore yog kev siv cov qauv, piv txwv li, ib qho surfactant-type micelle, nyob ib ncig ntawm cov silica matrix yog tsim.Thaum cov kua ionic ntxiv raws li templateing molecule, cov hydrated silica matrix cuam tshuam nrog cov kua ionic, tsim cov gel, thiab tom qab kho thiab ziab, cov kua ionic yog nyob rau hauv cov khoom nanoporous silica matrix (13).Thaum lithium ntsev ntxiv los ua ib feem thib peb, ILE nyob rau hauv silica matrix tsim ib silica gel electrolyte, uas kuj tau raug xa mus rau ionogel (24).Txawm li cas los xij, kom deb li deb, cov silica gel electrolytes no qhia txog kev coj mus rau qhov loj ntawm ILE tab sis tsis tshaj nws, tshwj tsis yog rau ib rooj plaub uas cov silica tau siv tshuaj ua haujlwm (saib Taw Qhia) (18).

Ntawm no, peb qhia, kev txhawb nqa ntawm Li-ion conductivity ntawm nanocomposite zoo tshaj li ntawm cov ntshiab ILE.Piv txwv ntawm 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide (BMP-TFSI) yog siv ntawm no.Nws yog postulated tias qhov adsorption ntawm ionic kua molecules ntawm OH-tawm silica nto yog txhawb los ntawm lub xub ntiag ntawm interfacial ice dej txheej.Muaj zog hydrogen kev sib raug zoo ntawm cov dej khov nab kuab thiab TFSI- anion induces molecular ordering ntawm cov kua ionic, zoo ib yam li cov txiav txim domains uas spontaneously tsim nyob rau hauv ionic kua (31).Qhov sib txawv tseem ceeb nrog qhov sib txawv tsim nyob rau hauv bulk ILE yog tias cov dej khov txheej ua raws li cov txheej txheem ua haujlwm uas (i) induces lub molecular ordering ntawm oxide nto thiab (ii) qhia muaj zog txaus H-bonding rau induce dipoles tso tawm dawb Li + rau txhim khu kev qha.Tom ntej no mus rau qhov nce hauv Li + concentration dawb, peb yuav qhia tau tias lub zog ua kom muaj zog rau kev nthuav tawm qis dua nrog cov sib xyaw ua ke nrog cov txheej txheem ILE adsorbed thiab dej khov txheej.

Ob peb-monolayers-thick deg dej txheej ntawm silica yog ib txheej zoo li cov khoom, raws li nws muaj zog sib koom ua ke rau silanol pawg los ntawm H-bridges thiab yog li kuj hu ua ice txheej (32).Nws qhov ntom ntom thiab tuab (kwv yees li ntawm peb mus rau plaub monolayners, nrog ~ 0.25 nm rau ib nrab ntawm dej siab [relative noo (rh)] nyob rau hauv ib puag ncig (Daim duab S2).Peb qhia tau hais tias ion conductivity nce nrog lub thickness ntawm cov dej khov txheej raws li hydrogen bonding nrog cov adsorbed ionic txheej kuj nce.Cov dej khov txheej yog ruaj khov zoo li cov dej siv lead ua hauv cov tshuaj sib xyaw.Qhov no yog qhov tsis sib xws nrog super concentrated aqueous electrolytes los yog hu ua dej hauv cov ntsev sib tov, qhov twg lub qhov rais electrochemical yog qhov dav dav, tab sis, thaum kawg, cov dej tseem yog electrochemically active (33).

Qhov sib txawv ntawm cov zaub mov txawv ntawm formic acid-catalyzed ionogel, peb siv me me pH 5 sib tov nrog dej ntau dhau thiab PGME (1-methoxy-2-propanol) ntxiv rau TEOS precursor nrog Li-TFSI ntsev thiab BMP-TFSI ionic kua.Ntawm qhov pH no, cov tshuaj tiv thaiv hydrolysis qeeb, thaum lub condensation yog qhov zoo (30).Li ions ntseeg tau tias ua tus catalyst rau cov tshuaj tiv thaiv hydrolysis, vim tsis muaj gelation tshwm sim thaum tsis muaj lithium ntsev thaum ob leeg muaj tib pH ntawm 5. Cov molar ratio ntawm ionic kua rau TEOS (thiab yog li silica moieties) yog. qhia raws li x tus nqi thiab tau sib txawv ntawm 0.25 thiab 2. Qhov molar ratio ntawm BMP-TFSI rau Li-TFSI tau khaws cia ntawm 3 (suav nrog 1 M Li-ion tov).Kev ziab qeeb qeeb yog tsim nyog los tswj cov qauv kev ncaj ncees ntawm cov qauv monolith (saib Cov Khoom Siv thiab Cov Txheej Txheem).Daim duab 1A qhia ib daim duab ntawm ib tug monolithic pellet tau tom qab lub tshuab nqus tsev ziab.Lub tshuab nqus tsev 72-teev kom qhuav yog txaus kom tshem tawm tag nrho cov dej noo mus rau qhov chaw uas tag nrho cov dej dawb raug tshem tawm thaum cov dej khov nab kuab adsorbed tseem zoo tag nrho, raws li tau lees paub los ntawm FTIR.Tsis muaj kev vibration rau cov dej dawb tau kuaj pom ntawm 1635 cm-1 hauv ib qho ntawm cov qauv tom qab lub tshuab nqus tsev ziab (Fig. 2).Rau kev sib piv, FTIR spectrum rau cov qauv nano-SCE (x = 1.5) khaws cia rau 1 lub lis piam hauv lub hnab looj tes N2 ntawm 60% RH yog qhia.Hauv qhov no, lub ncov dej ntshiab dawb tshwm.Tag nrho cov qauv, ntawm qhov tod tes, tau qhia meej meej rau silanol nto functionalization (Si─OH dabtsi yog khoov ntawm 950 thiab 980 cm-1) thiab ib tug adsorbed dej khov txheej (O─H stretching ntawm ~ 3540 cm-1) bonded rau cov ─OH nto pawg los ntawm H-bonding (ntxiv cov ntsiab lus hauv qab no).Cov vials tau hnyav ua ntej thiab tom qab cov kauj ruam kom qhuav los ntsuas cov dej khaws cia hauv nano-SCE (table S1).Tom qab ntawd, peb yuav suav cov naj npawb ntawm cov monolayers sib thooj ntawm cov dej khov nab kuab los ntawm qhov hnyav tshaj.Lub tshuab nqus tsev pellets tau coj mus rau hauv lub hnab looj tes [<0.1-ppm (qhov ib lab) H2O] thiab khaws cia rau hauv cov vials kaw kom tswj tau cov dej qub.Ib lub ntim me me tau muab coj los ntawm cov pellet rau kev ua yeeb yam ntxiv.

(A) Daim duab ntawm ob lub nano-SCE pellets (sab laug) synthesized nyob rau hauv lub vial;Tom qab gelation, pob tshab pellet tau txais.Nco ntsoov tias cov pellet yog pob tshab tag nrho thiab yog li ntawd tau muab lub xim xiav rau kev pom.Thaum ILE raug tshem tawm, ib qho nkig dawb pellet tseem nyob rau qhov ntxeem tau silica matrix (txoj cai).(B) Scanning electron microscopy (SEM) duab ntawm SiO2 matrix uas tseem nyob tom qab tshem tawm ntawm ILE.(C) Zoom ntawm daim duab qhia hauv (B) qhia txog qhov mesoporous ntawm cov khoom siv matrix nrog qee qhov macropores.(D) Transmission electron microscopy (TEM) duab uas qhia cov ntim ntom ntom ntawm 7- txog 10-nm silica nanoparticles raws li lub tsev blocks ntawm cov khoom ntxeem tau matrix.(E) Lub porosity ntawm matrix qauv npaj rau cov molar sib txawv ntawm ILE nrog rau SiO2 (x tus nqi).Cov kab dashed muab qhov theoretical porosity txiav txim siab los ntawm qhov ntim feem ntawm ILE thiab silica.Cov qauv acetone-rinsed (dub squares) tau qhuav hauv huab cua, uas muab ib feem ntawm lub cev qhuav dej rau x> 0.5.Supercritical CO2 ziab ntawm ethanol-rinsed nano-SCE (cov voj voog ntsuab) tiv thaiv kev tawg mus txog x = 2 rau kev tshem tawm qeeb ntxiv ntawm CO2 (qhib lub voj voog).BET, Brunauer-Emmett-Teller.Duab credit: Fred Loosen, imec;Akihiko Sagara, Panasonic.

(A) IR spectra ntawm nano-SCE raws li qhuav hauv lub tshuab nqus tsev (dub) thiab tom qab ntawd qhuav hauv ib lub hnab looj tes nrog 0.0005% RH rau 9 hnub (xiav) thiab raug rau 30% RH rau 4 hnub (liab) thiab mus txog 60 % RH rau 8 hnub (ntsuab), feem.aw, arbitrary units.(B) Cyclic voltammograms ntawm Li/SCE/TiN pawg nrog x qhov tseem ceeb ntawm 1.0 (xiav), 1.5 (ntsuab), thiab 2.0 (liab) thiab ntawm ILE siv (dub);lub inset qhia qhov tam sim no hauv logarithmic nplai.(C) Cyclic voltammograms ntawm Li/SCE (x = 2)/40-nm TiO2 pawg (liab), ILE (dotted dub), thiab ILE spiked nrog 5 nyhav % (wt %) H2O (dash-dotted xiav kab);nyob rau hauv (B) thiab (C), kev ntsuas nrog ILE thiab ILE nrog H2O tau ua tiav nyob rau hauv peb-electrode configuration nrog TiN raws li ib tug ua hauj lwm electrode thiab Li li counter thiab reference electrodes.SCE tau qhuav rau 2 hnub hauv lub hnab looj tes tom qab lub tshuab nqus tsev qhuav.

Lub ionic conductivity (σi) ntawm peb lub tshuab nqus tsev vacuum-annealed nano-SCE tau nce nrog ntim feem ntawm ILE (x tus nqi) raws li cov khoom sib xyaw (daim duab S1).Txawm li cas los xij, nyob rau hauv cov ntaub ntawv no, cov ionic conductivity tshaj qhov ntshiab ILE nws tus kheej los ntawm ntau tshaj 200% rau qhov siab tshaj x qhov tseem ceeb (Fig. 3).Tsis tas li ntawd, qhov kub thiab txias ntawm nano-SCE nrog kev txhim kho ion conductivity tau pom tus cwj pwm txawv dua li ntawm cov ntshiab ILE: Whereas Li-TFSI hauv BMP-TFSI ILE qhia tau hais tias muaj kev hloov pauv hauv kev coj ua thiab kev ua kom lub zog (txoj kab nqes) nyob ib ncig ntawm lub melting. taw tes ntawm qhov sib tov ntawm 29 ° C, nano-SCE nrog txhim kho conductivity tsis.Hloov chaw, nws qhia tau hais tias muaj kev hloov pauv tsis tu ncua hauv σi nrog qhov kub thiab txias, qhia tias yav dhau los tsis paub hom theem lossis mesophase tau tsim, uas yog lub luag haujlwm rau kev txhim kho conductivity.Ntxiv mus, txoj kab me me thiab yog li qis zog ua kom muaj zog rau kev sib kis rau nano-SCE piv rau ILE qhia cov khoom sib txawv (daim duab S3).Nws yog postulated tias muaj zog sib cuam tshuam ntawm cov ionic kua molecules thiab cov dej khov txheej ntawm silica scaffold yog lub luag hauj lwm rau tus cwj pwm mesophase, raws li yuav tau tham nrog cov qauv hauv qab no.

(A) Kub dependence ntawm conductivity ntawm nano-SCEs qhuav rau 8 hnub nyob rau hauv lub hnab looj tes lub thawv (GB) nrog x qhov tseem ceeb ntawm 2 (dub squares), 1.75 (txiv kab ntxwv lub voj voog), 1.5 (xiav daim duab peb sab), thiab 1.0 (daim duab peb sab ntsuab ) thiab ntawm ILE siv (qhib squares).(B) Kev coj ua ntawm nano-SCEs ntxiv rau hauv GB rau 0 hnub (ntsuab squares), 10 hnub (dub daim duab peb sab), thiab 138 hnub (xiav daim duab peb sab).(C) Conductivity piv rau square root ntawm ziab lub sij hawm ntawm nano-SCE nrog x qhov tseem ceeb ntawm 2 (dub squares), 1.5 (xiav daim duab peb sab), 1.0 (ntsuab daim duab peb sab), thiab 0.5 (xim av diamonds).(D) Kev coj ua ntawm nano-SCE nrog x = 2 (dub squares), 1.5 (xiav daim duab peb sab), thiab 1.0 (daim duab peb sab ntsuab) nthuav tawm hauv N2-filled humidity chamber.

Cov huab cua argon hauv lub hnab looj tes muaj tsawg dua 0.1 ppm dej, uas sib haum rau 0.0005% RH, ib nrab ntawm cov dej siab ntawm 0.01 Pa, lossis dej lwg taw tes ntawm -88 ° C.Raws li tus naj npawb ntawm cov dej adsorbed ntawm silanol-terminated silica nyob rau hauv qhov sib npaug nrog ib nrab siab ntawm cov dej (daim duab S2), cov dej saum npoo yuav maj mam diffuse tawm ntawm nano-SCE thiab sublimate ntawm cov npoo.Daim duab 3C qhia txog kev hloov pauv hauv kev coj ua rau 23 μl ntawm nano-SCE raws li kev ua haujlwm ntawm lub sijhawm nyob hauv lub hnab looj tes.Lub ion conductivity txo qis nrog ziab kom txog thaum nws saturates ntawm tus nqi sib haum rau silica nto hauv qhov sib npaug nrog cov dej ib nrab siab ntawm 0.01 Pa hauv lub hnab looj tes.Txawm tias nyob rau hauv cov huab cua qhuav heev ntawm lub hnab looj tes, yam tsawg kawg, ib feem monolayer ntawm adsorbed dej ntawm silanol yog tam sim no, raws li Raman spectroscopy tseem pom lub teeb liab ntawm 3524 cm-1, uas yog tshwj xeeb rau thawj monolayer ntawm adsorbed dej ntawm silanol. (Fig. 4B).Lub ion conductivity nyob rau hauv saturated tej yam kev mob tau zoo hauv qab ntawm tus neeg ILE nyob rau hauv txhua rooj plaub.Yog li, qhov kev txhim kho tsis txaus los them rov qab rau qhov poob hauv ionic conductivity ntawm qhov kaw ILE nyob rau hauv lub hauv paus ntawm lub pore.

(A) IR spectra ntawm nano-SCE nrog tus nqi x ntawm 1.5 (liab), ILE siv (dub), thiab SiO2 (xiav), qhia tias pawg O═S═O (1231 cm−1) koom nrog Kev sib cuam tshuam nrog OH-pab pawg ntawm silica nto.(B) Raman spectra ntawm nano-SCE nrog x qhov tseem ceeb ntawm 2 (dub), 1.5 (liab), thiab 0.5 (xiav), qhia pom muaj cov dej khov nab kuab sib koom ua ke ntawm silanol-terminated silica txawm rau nano-SCE ze saturation (0.0005 % RH) hauv hnab looj tes (30 hnub).(C) Cov qauv tsim rau kev sib cuam tshuam hauv nano-SCE nrog kev sib cais Li-TFSI rau hauv Li + dawb li TFSI- anion sib koom ib feem ntawm nws cov nqi tsis zoo nrog cov dej khov adsorbed-TFSI-BMP txheej;Cov xim sawv cev sib txawv nrog cov xim liab (silicon), liab (lithium), tsaus daj (sulfur), txiv kab ntxwv (oxygen), xiav (nitrogen), dawb (hydrogen), thiab ntsuab (fluorine).Cov kab liab liab sawv cev rau hydrogen daim ntawv cog lus ntawm O═S pawg ntawm TFSI anion thiab OH-pab pawg ntawm hydroxylated silica nto.Lub Li + ions teem dawb los ntawm dipole hla lub adsorbed txheej tuaj yeem txav mus los ntawm cov xov tooj tom ntej los yog diffuse ionic kua khaubncaws sab nraud povtseg saum cov khaubncaws sab nraud povtseg.Nco ntsoov tias nyob ntawm lub zog ntawm cov ntawv cog lus hydrogen thiab qhov sib npaug ntawm cov silica, ntau txheej adsorbed tuaj yeem tsim ib yam.Tag nrho spectra yog qhia nyob rau hauv daim duab.S8.

Ib qho kev pom zoo yog qhov kev sib raug zoo nrog lub hauv paus square ntawm lub sij hawm kom qhuav raws li qhia hauv daim duab 3C, qhia tias qhov kev hloov pauv hloov pauv ncaj qha rau cov kev hloov pauv ntawm cov dej khov nab kuab adsorbed ntawm cov silica thiab tshem tawm cov dej saum npoo no. diffusion txwv.Nco ntsoov tias "kev ziab" tsuas yog tshwm sim hauv qhov chaw qhib qhov twg RH qis dua rau txheej txheej dej khov sib npaug.Cov conductivity tsis hloov qhov tseem ceeb, piv txwv li, nyob rau hauv kaw npib hlwb siv rau qhov ntsuas kub-nyob ntawm seb.

Qhov ntsuas kub ntawm nano-SCE tau ntsuas rau lub sijhawm sib txawv ntawm kev ziab hauv lub hnab looj tes.Raws li cov conductivity ntawm qhuav nano-SCE mus txog ntawm lub ILE, qhov nruam σi piv rau 1 / T profiles rau mesophase conductivity maj mam hloov mus rau qhov profile rau lub ILE, dua qhia qhov poob ib ncig ntawm nws melting point (daim duab S3).Qhov kev soj ntsuam no ntxiv txhawb qhov kev xav tias cov dej khov txheej ua haujlwm ua haujlwm rau kev sib cuam tshuam nrog ILE, ua rau tus cwj pwm mesophase hauv nano-SCE.Li no, thaum cov txheej txheem ua haujlwm raug tshem tawm, ILE tsuas yog nyob hauv ib qho mesoporous oxide membrane.

Kev ntsuas ntawm lub qhov rais electrochemical stability paub meej tias cov dej khov hauv nano-SCE yog qhov ruaj khov, vim tias tsis muaj qhov nce siab rau cov dej txo lossis oxidization tau pom ntawm inert TiN electrode (Fig. 2) los yog ntawm TiO2 nyias-film electrode, uas txwv tsis pub ua. raws li ib tug electro-catalyst rau txo dej.Hloov chaw, electrochemical stability ntawm nano-SCE zoo ib yam li ntawm ILE thiab yog li txwv los ntawm oxidation ntawm TFSI- ntawm electrode muaj peev xwm> 4.3 V thiab txo ntawm TFSI- thiab BMP + ntawm qhov muaj peev xwm <1 V piv rau Li + / Li. (33).Rau kev sib piv, ib qho voltammogram qhia rau ILE nrog 5 qhov hnyav % (wt %) dej ntxiv (cov ntsiab lus zoo ib yam li rau qee qhov nano-SCE; saib cov lus S1).Hauv qhov no, cov ceg cathodic rau txo cov dej yog ntsuas tam sim tom qab Li-intercalation ncov ntawm anatase ntawm 1.5 V piv rau Li + / Li.

Lub thermal thiab (electro) tshuaj stability ntawm nano-SCE feem ntau yog txiav txim los ntawm ILE muab tub lim.Thermogravimetric tsom xam (TGA) qhia thermal stability ntawm SCE thiab ILE mus txog 320 ° C, tsis hais tus ILE-rau-silica ratio (daim duab S4).Saum toj no qhov kub thiab txias, Li-TFSI thiab BMP-TFSI decompose tag nrho rau volatile Cheebtsam, thiab tsuas yog cov silica matrix nyob ib ncig ntawm 450 ° C.Qhov feem pua ​​​​ntawm cov khoom seem tom qab thermal decomposition yeej sib tw zoo heev nrog cov feem ntawm silica hauv SCE.

Lub nano-SCE pom tsis muaj qhov pom tseeb ntawm microstructure hauv scanning electron microscopy (SEM) tshwj tsis yog rau qhov chaw du nrog qee qhov silica thaj ua rau pom (daim duab S5).Qhov tshwj xeeb ceev ntawm SCE tau txiav txim siab nrog helium pycnometer thiab nyob ib ncig ntawm 1.5 g / cm3 rau tag nrho x qhov tseem ceeb (table S1).Tag nrho cov silica matrix tau tshwm sim los ntawm kev tawm dag zog ntawm ILE hauv cov kuab tshuaj (saib Cov Khoom Siv thiab Cov Txheej Txheem).Los ntawm kev ua tib zoo ziab ntawm qhov tseem ceeb ntawm CO2, cov pa roj carbon monoliths tsis zoo tuaj yeem tau txais zoo li qhov pom hauv daim duab 1A.Kev tshuaj xyuas SEM qhia tau hais tias lub scaffold ntawm mesoporous silica nrog 10- txog 30-nm pore txoj kab uas hla, uas yog qhwv ib ncig ntawm macropores loj ntawm 100 mus rau 150 nm, raws li tau pom hauv daim duab 1 (B thiab C).High-resolution kis tau tus mob electron microscopy (TEM) (Fig. 1D) ntxiv nthuav tawm ib tug microstructure uas muaj nyob rau hauv packed silica nanoparticles.Qhov nruab nrab particle inch ranges ntawm 7 mus rau 14 nm rau x qhov tseem ceeb ntawm 0.5 thiab 1.5.

Qhov tshwj xeeb thaj chaw [Brunauer-Emmett-Teller (BET)], porosity, qhov nruab nrab pore loj, thiab pore loj faib tau txiav txim siab nrog N2 adsorption / desorption ntsuas (table S1 thiab daim duab S6).Ib feem ntawm lub cev qhuav dej ntawm cov qauv thiab kev tshem tawm tsis tiav ntawm cov adsorbed ILE tej zaum yuav txawv me ntsis ntawm cov lej.Ua tib zoo tshem tawm cov kua ionic thiab qeeb ziab siv supercritical CO2 muab, txawm li cas los xij, txhim khu kev qha tau ze rau qhov xav tau porosity xam los ntawm qhov ntim feem ntawm ILE rau silica (Daim duab 1).BET thaj tsam thaj tsam ntawm 800 thiab 1000 m2 / g.Qhov nruab nrab pore loj tau los ntawm txoj kab nqes ntawm isotherm ranged ntawm 7 thiab 16 nm.Tsis tas li ntawd, ib feem me me ntawm cov pores loj txog li 200 nm tau ntsuas (daim duab S6), raws li SEM kev soj ntsuam.Lub pore txoj kab uas hla sib raug zoo heev nrog ob zaug qhov sib npaug thickness ntawm ILE txheej tau los ntawm ILE ntim feem thiab BET nto thaj tsam, txhais tau hais tias cov mesopores tau puv nrog ILE.

Qhov chaw tshaj tawm BET yog rau cov mesopores thiab macropores nkaus xwb.Rau acetone-rinsed matrix, micropores (~ 0.6 nm) kuj tau ntsuas.Cov micropores muaj nyob nruab nrab ntawm tus neeg silica nanoparticles ua tus qauv raws li cov uas pom hauv daim duab TEM ntawm daim duab 1D.Qhov siab tshaj qhov chaw ntxiv ntawm 650 (x = 0.5) thiab 360 m2 / g (x = 1.5) yog kwv yees (cov lus S1).

Ob leeg FTIR thiab Raman spectra qhia meej cov pov thawj rau cov pab pawg silanol nrog adsorbed dej khov dej molecules ntawm lub siab porosity silica matrix nrog cov cheeb tsam zoo heev tshaj 1400 m2 / g thaum noj rau hauv micropores, mesopores, thiab macropores.Nruab nrab ntawm xoom thiab peb cov dej monolayers yog kwv yees los ntawm cov dej ntau dhau hauv nano-SCE rau x <1.75.Rau planar silica, thawj peb lub monolayers ntawm cov dej adsorbed tiag tiag suav tias yog qhov tsis muaj zog thiab zoo li vim tias lawv muaj zog hydrogen bonding rau OH-terminated nto (32) (saib daim duab S2).Lub O─H stretch txuam nrog silanol hydrogen bonded rau cov dej khov txheej yog pom ntawm 3540 cm-1 hauv FTIR spectra.Tag nrho cov nano-SCEs qhia, qhov tseeb, qhov sib txawv ntawm qhov siab ntawm 3540 cm-1 rau cov dej khov dej tom qab lub tshuab nqus tsev qhuav thiab tom qab ziab ntxiv rau hauv lub hnab looj tes (Daim duab 2).Txawm tias qhov sib npaug nano-SCE ntawm 0.0005% RH (lub thawv hnab looj tes), Raman spectroscopy tseem pom tias muaj tsawg kawg yog ib feem monolayer (Fig. 4B).Qhov thib plaub monolayer ntawm planar silica ntseeg tau tias yog txheej txheej hloov pauv, txhais tau hais tias nws tseem adsorbed thiab txwv tab sis tuaj yeem muaj qee qhov txav mus los.Los ntawm txheej thib tsib rau, cov dej yuav ua rau txawb thiab ua kua zoo li.Cov dej zoo li cov kua dej yuav tshwm sim ntawm cov lej nthwv dej ntau dua hauv FTIR spectrum vim qhov qis dua ntawm H-bonding hauv cov dej ua kua.Rau nano-SCE raug rau 60% RH, 3540-cm-1peak tseeb qhia tau hais tias ntxiv kev co hloov mus rau ntau dua yoj tus lej vim yog cov dej adsorbed ntxiv.Txaus siab rau qhov no yog qhov kev sim uas tus qauv raug rau 30% RH, vim tias tsis muaj cov dej ua kua dej tseem xav tau ntawm silica ntawm qhov av noo (daim duab S2).Rau cov qauv no, tsuas yog 3540 cm-1 ncov rau dej khov yog pom hauv FTIR.Tsis tas li ntawd, tsis muaj dej dawb tau kuaj pom ntawm 1635 cm-1 txawm tias tom qab 4 hnub ntawm 30% RH.Qhov no txhais tau hais tias dej tsis tau coj los ntawm hygroscopic Li-TFSI yaj hauv hydrophobic BMP-TFSI ib zaug nano-SCE qhuav los ntawm kev kho lub tshuab nqus tsev.Yog li ntawd, ib qho dej ntxiv hauv SCE yuav raug adsorbed ntawm OH-tawm silica nto.Li no, raws li rau planar silica, SCE silica matrix nyob rau hauv equilibrium nrog ib nrab siab ntawm cov dej nyob rau hauv ib puag ncig.

Txhawm rau ntsuas qhov kev xav no ntxiv, cov ion conductivity ntawm nano-SCE (x = 1, 1.5, thiab 2) raug ntsuas ntawm qhov sib txawv % RH;cov qauv tau raug rau cov kev tswj sib tov ntawm qhuav thiab moistened N2 roj nyob rau hauv ib lub hnab looj tes rau 2 hnub kom tso cai rau cov dej adsorbed kom ncav cuag equilibrium (Fig. 3D).Rau cov ntsiab lus ntawm ~ 0% RH, qhov conductivity rau qhov sib npaug nano-SCE hauv lub hnab looj tes tau muab coj los siv.Astonishingly, ion conductivity piv rau RH (%) profile ua raws li tus cwj pwm xav tau rau cov dej adsorption ntawm planar silica (daim duab S2).Nruab nrab ntawm 0 thiab 30% RH, cov conductivity nce nrog nce RH.Raws li cia siab rau kev nce hauv adsorbed dej khov txheej thiab tuab (sib raug nrog ib mus rau peb txheej dej khov ntawm planar silica).Nco ntsoov tias FTIR tau pom tias tsis muaj dej dawb nyob hauv nano-SCE rau ob peb hnub ntawm 30% RH.Kev hloov pauv tau pom nyob ib puag ncig 50% RH, sib haum nrog cov xwm txheej uas yuav tsum muaj cov txheej txheem hloov pauv dej adsorbed rau planar silica.Nws thiaj li, qhov txawv txav nce ntxiv hauv ion conductivity yog pom mus rau 60% thiab cov av noo siab dua qhov twg, zoo ib yam nrog cov txheej txheem silica, tam sim no, kuj muaj cov kua dej zoo li txheej yuav tsim los ntawm qhov sib cuam tshuam ntawm silica thiab embedded ILE.Nrog FTIR, cov kua dej txheej ntawm cov dej khov yog tam sim no kuaj pom los ntawm kev ua haujlwm ntawm silanol / dej khov / dej vibrational ncov kom muaj zog dua (Fig. 2A).Qhov pom kev hloov pauv hauv conductivity yog thim rov qab;Yog li, nano-SCE tuaj yeem ua raws li cov av noo sensor thiab Li-ion electrolyte.Los ntawm daim duab 3D, ion conductivity ntawm nano-SCE tam sim ntawd tom qab lub tshuab nqus tsev anneal sib haum nrog ib qho equilibrium hydrated silica ntawm ~ 10% RH.Lub ion conductivity rau saturation nyob rau hauv qhuav chav tsev tej yam kev mob (~ 0.5% RH) yuav nyob ib ncig ntawm 0.6 mS / cm (rau x = 2).Qhov kev sim no ua kom pom qhov cuam tshuam ntawm cov dej interfacial ntawm ion conductivity.Rau RH> 60%, qhov siab dua ion conductivity tuaj yeem piav qhia los ntawm kev nthuav dav sai ntawm kev daws Li + los ntawm cov kua zoo li txheej.Txawm li cas los xij, nyob rau hauv cov ntaub ntawv ntawm cov dej khov txheej, Li + ion diffusion yuav yog ib qho khoom siv hauv xeev hom diffusion thiab yog li qeeb dua los ntawm cov kua ionic nws tus kheej.Hloov chaw, qhov kev txhim kho yog los ntawm kev txhim kho adsorption ntawm cov organic anions thiab cations ntawm Li-ntsev thiab ionic kua molecules, raws li tau hais hauv cov qauv hauv qab no.

Peb tawm tswv yim ib qho qauv uas cov ionic kua molecules yog adsorbed ntawm silica nto ntawm H-bridges nrog lub immobile ice txheej ntawm silanol pawg (Fig. 4).Qhov tseeb ntawm cov tshuaj tiv thaiv hydrolysis condensation muab qhov siab tshaj plaws silanol ntom ntom (4 × 1014 txog 8 × 1014 cm-2, uas zoo sib xws nrog qhov ntom ntom ntawm ib lub monolayer ntawm dej khov nrog ~ 8 × 1014 dej molecules ib cm2) (34).Cov ntaub ntawv pov thawj rau kev sib cuam tshuam ntawm molecular ntawm O atoms ntawm TFSI anions thiab silica yog muab los ntawm FTIR, uas qhia tau hais tias muaj ob npaug ntawm O═S═O ncov rau tag nrho nano-SCE piv rau ILE siv (Fig. 4A; tag nrho cov spectra hauv daim duab S8).Qhov kev hloov ntawm lub ncov ntxiv nrog txog −5 cm−1 los ntawm 1231 cm−1 qhia tias kev sib txuas ntawm O═S═O pawg rau tsawg kawg yog ib feem ntawm TFSI anions.Yog li ntawd, H-bonding ntawm TFSI anions ntawm cov dej khov txheej yog xav.Tom qab ntawd, qhov loj hydrophobic BMP cations koom nrog thawj TFSI txheej, ua tiav thawj txheej adsorbed ntawm ionic kua molecules.Raws li rau txheej txheej dej khov, cov adsorbed BMP-TFSI molecules tau xav tias feem ntau tsis muaj zog, yog li txuas ntxiv cov khoom zoo li dej khov rau ntawm silica nto.Raws li TFSI anion muaj cov pab pawg sib luag O═S═O, ib lub atom oxygen tuaj yeem cuam tshuam nrog hydroxylated silica nto thaum lwm qhov tsim cov ntsiab lus sticking rau BMP cations.Lub TFSI anion kuj muaj ob pawg O═S═O, ua kom ruaj khov adsorption thiab ntom xaj ntawm anion monolayer.Adsorption yog qhov ua tau zoo tshaj plaws nyob rau hauv cov ntaub ntawv ntawm cov txheej txheem dej khov uas muaj qhov ntom ntom siab tshaj plaws ntawm OH-pab pawg raws li cov ntsiab lus nplaum.Nyob rau hauv lub xub ntiag ntawm tsuas yog silanol pawg, lub adsorption yuav tsis muaj zog txaus los tsim ib tug nruam adsorbate txheej.Tsis tas li ntawd, ib qho ntxiv ntawm cov dej khov monolayers tau paub tias yuav ua rau kom muaj zog ntawm hydrogen daim ntawv cog lus (35).Nco ntsoov tias cov kev sib cuam tshuam ntawm cov molecular ntawm BMP cation thiab cov xaj TFSI monolayer yuav txawv ntawm qhov hauv cov kua ionic qhov twg TFSI anion muaj kev ywj pheej thiab tsis muaj polarization los ntawm qhov chaw hauv qab.Tus nqi ntawm BMP cation loj yog qhov tseeb muab faib rau ntau lub atoms los ntawm polarization ntawm cov khoom siv hauv nruab nrab thiab los ntawm kev sib cuam tshuam ntawm molecular nrog nws cov tshuaj ib puag ncig thiab, tshwj xeeb, adsorbed TFSI anion.H-bonding ntawm O-pab pawg ntawm TFSI anion thiab OH-txiav ntawm cov dej khov txheej tam sim no qhia txog dipole tshaj thawj txheej adsorbed, inducing ntxiv molecular ordering los ntawm lub koom haum.Nws ntseeg tau tias nyob rau ntawm no, cov me me Li-TFSI molecules adsorb rau ntawm molecular txheej uas TFSI anion tam sim no them cov seem zoo dipolar nqi ntawm ib los yog ntau tshaj ntawm BMP cations nyob rau hauv lub sab sauv txheej, li no loosening nws koom nrog nws Li. ion.Nyob rau hauv txoj kev no, lub concentration ntawm dawb Li + yog nce nyob rau hauv no interface, ua rau siab dua ion conductivity.Yog li ntawd, denser thiab thicker ice khaubncaws sab nraud povtseg ces qhia ib tug loj dipole nrog ib tug ntau dua residual nqi los them, muab ib tug proportionally siab dawb Li + concentration thiab yog li ion conductivity.

Nyob rau sab saum toj ntawm lub adsorbed ILE txheej, lwm txheej ILE tuaj yeem adsorb zoo ib yam li cov dej khov ntau txheej ntawm silica lossis dipole rub ntawm cov dej khov txheej tsis muaj zog heev thiab maj mam khi ILE nyob rau sab saum toj, uas tom qab ntawd tuaj yeem muab cov kua dej zoo li kev coj ua rau cov Li+ ions tso tawm rau hauv qis adsorbed txheej (Fig. 4C).Kev hloov pauv hauv Li + ion concentration dawb tau lees paub los ntawm NMR thiab Raman spectroscopy ntsuas.Kev ntsuas Raman tsis ncaj qha qhia tau tias ib feem loj ntawm Li + ions muaj tseeb muaj nyob hauv nano-SCE nrog cov dej khov nab kuab ntau txuas rau silica (Fig. 5).Lub Raman ntsuas lub koom haum ntawm cation nrog TFSI los ntawm kev soj ntsuam kev co ntawm N-pawg ntawm TFSI anion (36).Hauv cov kua ntshiab BMP-TFSI ionic, tsuas pom ib lub ncov ntawm 741 cm-1.Nyob rau hauv cov ntaub ntawv ntawm cov ntshiab ILE, lub ncov ntxiv yog pom ntawm 746 cm-1 qhov twg ob TFSI anions koom tes nrog ib leeg Li + ion [saib density functional theory (DFT) calculations in Materials and Methods].Rau tag nrho cov nano-SCEs, qhov siab tshaj plaws ntawm 746 cm-1 yog qhov tsis muaj zog dua li ntawd rau ILE, qhia txog ib feem me me ntawm Li-TFSI cuam tshuam thiab, yog li ntawd, ib feem loj ntawm cov tsis koom nrog lossis dawb Li + cations.Qhov siab tshaj plaws txo qis rau cov nano-SCE uas qhia tau hais tias qhov kev ua tau zoo tshaj plaws, piv txwv li, cov uas muaj cov dej khov tuab tshaj plaws.Rau nano-SCE ntawm qhov sib npaug hauv lub hnab looj tes, tseem, ib feem ntawm Li + dawb yog ntsuas txawm tias me dua li cov qauv nqus-nqus tau.Qhov piv ntawm qhov siab tshaj plaws rau qhov 746 tshaj 741 cm-1 Raman hloov ces yog ib qho kev ntsuas ntawm qhov piv ntawm pub dawb rau TFSI-koom nrog Li-ions (Fig. 5B).Qhov linear nce nyob rau hauv dawb Li + ion feem nrog x tus nqi nicely ua raws li tus qauv ntawm conductivity nce nrog x tus nqi hauv daim duab 3B, ob qho tib si rau lub tshuab nqus tsev vacuum qhuav nano-SCE (hnub 0) thiab SCE ntawm equilibrium nrog lub hnab looj tes dryness (hnub 138).

(A) Raman spectra ntawm cov kua ionic (IL; dotted xiav kab) thiab ILE siv (ILE; dash-dotted kab) ntawm raws li npaj nano-SCE (nqus qhuav) nrog x qhov tseem ceeb ntawm 0.5 (ntsuab), 1.5 (daj) , thiab 2 (xim av) thiab ntawm nano-SCE (x = 1.5) ntxiv rau qhuav hauv hnab looj tes rau 30 hnub lossis ze rau qhov saturation ntawm 0.0005% RH (liab).Cov kab ntsug sau npe Raman hloov pauv rau TFSI nrog nws qhov chaw N chaw ua haujlwm rau Li + (746 cm-1) thiab tsis ua haujlwm rau Li + (741 cm-1), raws li.(B) Qhov sib piv pub dawb rau kev sib koom tes Li + ntawm nano-SCE raws li kev sib xyaw ua ke (lub tshuab nqus tsev qhuav, lub voj voog dub) thiab ntxiv rau hauv cov hnab looj tes nrog 0.0005% RH rau 30 hnub (xiav pob zeb diamond), sib haum rau qhov sib piv ntawm kev sib xyaw ua ke ntawm Raman peaks (746 cm-1 tshaj 741 cm-1).(C) PFG-NMR-derived Li + tus kheej diffusion coefficient ntawm nano-SCE (liab pob zeb diamond) thiab ILE ref.(dub squares) raws li kev ua haujlwm ntawm lub sijhawm nruab nrab ntawm gradient magnetic teb pulses.Lub ncov theoretical ntawm Raman spectra tau simulated siv DFT xam.

Los ntawm pulsed-field gradient NMR (PFG-NMR), tus kheej diffusion coefficient ntawm cov sib txawv mobile Li-ion hom tau txiav txim siab raws li kev ua haujlwm ntawm lub sijhawm nruab nrab ntawm gradient magnetic field pulses ∆ rau ILE kua siv thiab rau nano- SCE (x = 1.5) nrog tib ion conductivity ntawm 0.6 mS / cm (Fig. 5C).Li + tus kheej diffusion coefficient hauv ILE siv tau tas li, qhia tias tsuas yog ib lossis ntau hom Li uas muaj kev txav mus los zoo sib xws muaj nyob hauv cov kua.Rau nano-SCE, tus kheej diffusion coefficient sib txawv nrog ∆ thiab tshaj qhov ntawm ILE ntawm luv ∆, qhia tias muaj cov tsiaj txav ceev uas teb tsuas yog luv luv ntawm cov magnetic pulses.Qhov gradient nyob rau hauv tus kheej-diffusion coefficient qhia tias tom ntej no mus rau qhov kev nce hauv dawb li-ion concentration, raws li inferred los ntawm Raman spectroscopy, lub activation zog rau diffusion yog qis dua nyob rau hauv mesophase interface txheej thiab.Qhov no txhawb kev txhim kho kev ua tau zoo qhia los ntawm (ntau) dawb Li + ions hauv txheej mesophase.Nyob ntev ∆, tus kheej diffusion coefficient qis dua li ntawm ILE siv.Qhov no corroborates qis dua ion conductivity rau lub hnab looj tes-saturated nano-SCE piv rau ILE.ILE nyob rau hauv cov tub ntxhais ntawm mesopores yuav muaj viscosity ntau dua vim qhov txwv ntawm molecular txav.Yog li ntawd, kev txhim kho los ntawm kev tsim kom nrawm dua li diffuse Li-ions ntawm silica / dej khov / ILE interface yuav tsum tau them nyiaj ntau dua qhov txo qis hauv cov khoom siv hauv lub qhov pore.Qhov no piav qhia txog qhov tsis muaj kev txhim kho nyob rau hauv cov kab ke raws li qhov sib cuam tshuam tsis muaj kev txhawb nqa ion txaus (daim duab S1).

Lub electrochemical stability ntawm nano-SCE tiv thaiv lithium hlau tau sim siv ib tug peb-electrode teeb (schematic ntawm teeb yog qhia nyob rau hauv daim duab S7).Cov yam ntxwv tam sim no-muaj peev xwm ntawm Li/SCE (x = 1.5) thiab Li/ILE ib nrab-cell tau qhia hauv daim duab 6A.Raws li rau lub qhov rais electrochemical nyob rau hauv daim duab 2, lub electrochemistry yog txwv los ntawm ILE muab tub lim.Reversible lithium plating thiab stripping yog pom.Ib txheej ruaj khov electrolyte interphase (SEI) txheej yog tsim ntawm metallic lithium nrog RSEI ntawm li 0.9 kilo-ohm·cm2, lub luag haujlwm rau IR poob loj hauv iU nkhaus ntawm ob sab cathodic thiab anodic.Lub cathodic tam sim no nyob rau hauv cov ntshiab ILE cov kev daws teeb meem tsis qhia hysteresis mus rau −2.5 mA / cm2.Txawm li cas los xij, anodic dissolution tau pom qhov siab tshaj plaws passivation nrog qhov tsis tu ncua anodic tam sim no tsuas yog 0.06 mA / cm2.Cov ceg cathodic tam sim no ntawm cov khoom-khoom Li / SCE interface tsis pom hysteresis rau cathodic tam sim no tsawg dua -0.5 mA / cm2.Qhov tsis kam ntawm SEI yog, txawm li cas los xij, txog ob npaug.Ib yam li ntawd, lub ncov anodic tau qis dua thiab qhov ruaj khov-lub xeev tam sim no tom qab anodic passivation ncov yog 0.03 mA / cm2, tsuas yog ib nrab ntawm cov kua ntshiab ILE.Kev tsim ntawm SEI thiab passivation txheej hauv qhov pores ntawm SCE txwv qhov tam sim no ntawm lithium hlau.Ob lub voltammograms rau Li / ILE thiab Li / SCE electrodes tau rov ua dua raws li ntau lub voj voog, qhia tias txheej txheej anodic passivation thiab chemical SEI txheej yog thim rov qab thiab ruaj khov.Qhov kev sib xyaw ua ke qeeb qeeb ntawm Li / SCE interface ua rau txwv tsis pub ua haujlwm ntawm ib nrab ntawm tes ua nrog Li hlau anodes hauv qab no.

(A) Cyclic voltammogram of nano-SCE (x = 1.5, as synthesized after vacuum drying) (liab) thiab ILE reference (dub) ntsuas nyob rau hauv peb-electrode configuration nrog Li ua hauj lwm, txee, thiab siv electrodes (SEI kuj kwv yees los ntawm IR poob ntawm cathodic tam sim no yog 0.9 thiab 1.8 kilo-ohm·cm2 rau ILE thiab SCE, feem).(B) Galvanic nqi / tso tawm nkhaus ntawm Li / SCE (x = 1) / 100-nm nyias-film LiMn2O4 cell rau tsib lub voj voog ntawm C-tus nqi ntawm 1C, 5C, thiab 20C.(C) Cyclic voltammograms ntawm Li/SCE/40-μm Li4Ti5O12 thiab Li/SCE/30-μm LiFePO4 hmoov electrode hlwb (1 mV/s).(D) Galvanic nqi / paug nkhaus ntawm Li / SCE / 40-μm Li4Ti5O12 hmoov electrode ntawm 1C, 0.1C, 0.2C, thiab 0.02C.(E) Galvanic nqi / tso tawm nkhaus ntawm Li / SCE / 30-μm LiFePO4 hmoov electrode ntawm 1C, 0.5C, 0.2C, 0.1C, 0.05C, thiab 0.01C.(F) Muaj peev xwm (tau ntim pob zeb diamond rau delithiation thiab qhib squares rau lithiation) piv rau lub voj voog ntawm Li / SCE / 30-μm LiFePO4 hmoov electrode;Lub thickness ntawm SCE nyob rau hauv lub hlwb yog hais txog 280 μm.Qhov ceev ntawm LFP thiab LTO cathode yog kwv yees li 1.9 thiab 11.0 mg / cm2, feem.(G) Muaj peev xwm piv rau lub sijhawm nkhaus ntawm Li / SCE / Li pawg ua haujlwm ntawm qhov ceev tam sim no ntawm 0.1, 0.2, 0.5, thiab 0.1 mA / cm2.(H) 1st, 10th, 125th, thiab kawg polarization ntawm Li/SCE/Li pawg stressed ntawm 0.1 mA/cm2, qhia hauv (G).Rau (G) thiab (H), SCE muaj qhov conductivity ntawm 0. 34 mS / cm, thiab thickness ntawm SCE pellet yog 0.152 cm.

A 100-nm LiMn2O4 (LMO) nyias-zaj duab xis tau siv los ua tus qauv zoo electrode los kuaj ob qho tib si kev ruaj ntseg ntawm nano-SCE thiab cov khoom siv electrode thaum tshem tawm cov teeb meem cuam tshuam hauv cov khoom sib xyaw electrodes (37).Qhov kev ua tau zoo ntawm cov yeeb yaj kiab nyias nyias / SCE pawg ua kom pom kev ruaj ntseg ntawm kev sib tshuam ntawm cov electrode thiab electrolyte.Nyob rau hauv cov qauv no nyias-zaj duab xis teeb, tsuas yog ib zaug xwb, zoo-txhais, thiab kev sib txuas lus sib txuas yog tam sim no ntawm electrolyte thiab electrode, piv txwv li, nws yog ib qho zoo tshaj plaws platform los kawm cov electrochemistry ntawm electrolyte / electrode interface yam tsis muaj teeb meem ntawm kev hloov pauv. , thiab lwm yam nyob rau hauv qhov kev sim no, tus nqi kev ua tau zoo tsis txwv los ntawm Li-foil txee electrode, raws li qhov ceev tam sim no (6 μA / cm2 rau 1C) yog qis dua ntawm qhov chaw ruaj khov anodic tam sim no toj siab rau lithium ib nrab- cell (0.03 mA / cm2).Reproducible thiab ruaj khov them / tawm nkhaus yog tau rau qhov txiav tawm voltage ntawm 4.3 V rau C-tus nqi ntawm 1 thiab 20C rau ntau tshaj 20 cycles (Fig. 6B).LMO tsis ruaj khov hauv cov kua electrolyte rau LiB.Piv txwv li, 50% muaj peev xwm txo tau raug pom ntawm 100-nm LMO zaj duab xis them-tso tawm rau 10 lub voj voog hauv LiClO4 / propylene carbonate electrolyte ntawm 1C (37).Peb cov txiaj ntsig tau pom tias nano-SCE tau tshaj LMO ntau dua li cov kua electrolyte.

Txhawm rau ua kom pom kev sib koom ua ke ntawm nano-SCE, peb kuj tau tsim ib nrab ntawm tes nrog Li4Ti5O12 (LTO) thiab LiFePO4 (LFP) hmoov electrodes.Cov tshuaj precursor tau poob-casted rau hauv lub xov tooj ntawm tes kom impregnate cov ntxeem tau electrodes thiab sab laug rau ntxiv gelation ua ntej lawv qhuav thiab nqus-annealed zoo ib yam li nano-SCE pellets.Cov hlwb qhia cov yam ntxwv lithiation/delithiation ntawm cov electrodes coj (Fig. 6C).Qhov qis qis tshaj tam sim no rau LFP dua li LTO yog vim qhov sib txawv ntawm txheej txheej.Tus nqi kev ua tau zoo thaum lub sij hawm them nqi / kev ntsuas tawm tam sim no raug txwv los ntawm Li-foil counter electrode nias ntawm nano-SCE txheej tsim nyob rau sab saum toj ntawm 30- txog 40-μm-thick electrode coatings (Fig. 6, D thiab E).Lub LTO / nano-SCE / Li cell mus txog nws qhov siab tshaj plaws ntawm 160 mA·hour / g tsuas yog qis C-tus nqi ntawm 0.02C (Fig. 6D).Lub peev xwm nkag tau poob sai nrog C-tus nqi nrog tsawg dua 10% rau C-tus nqi loj dua 0.1C.Ib yam li ntawd, LFP / SCE / Li cell mus txog nws lub peev xwm siab tshaj plaws ntawm 140 mA·hour / g ntawm 0.01C (Fig. 6E).Daim duab 6F qhia qhov kev ua tau zoo rau tag nrho 30 lub voj voog, ua kom pom kev ruaj khov ntawm tes.Cov kev sim no qhia txog kev ua haujlwm ntawm nano-SCE li Li-ion electrolyte thiab qhov ua tau rau kev koom ua ke hauv Li-ion hlwb.

Kev ruaj ntseg lossis cyclability ntawm nano-SCE tau sim siv Li / SCE / Li symmetric pawg.Nws tau cycled rau ntau tshaj 120 lub voj voog ntawm qhov ceev tam sim no ntawm 0.1 mA / cm2 rau 0.5 teev (Fig. 6G) yam tsis muaj teeb meem lossis kev tsim dendrite (Fig. 6H).Lub polarization voltage tau me dua lub sijhawm, qhia txog kev txhim kho kev sib cuag.Ntxiv mus, lub xovtooj ntawm tes tau ntxhov siab txog tam sim no qhov ceev ntawm 0.5 mA / cm2, tsis muaj kev tsim cov lithium dendrites lossis cov cim qhia ntawm kev puas tsuaj ntawm nano-SCE lossis qhov cuam tshuam (Daim duab 6G).Metallic lithium paub tias tsim cov txheej txheem tiv thaiv kev tiv thaiv lossis SEI ntawm nws qhov chaw hauv BMP-TFSI-based ILEs (27).Cov tshuaj tiv thaiv no kuj tshwm sim ntawm lithium / nano-SCE interface;Raws li tau tham hauv daim duab 6A, SEI tuaj yeem loj hlob me ntsis hauv qhov pores, piav qhia txog SEI siab dua rau nano-SCE dua li ILE (saib saum toj).Pov thawj rau ib txheej SEI tau txais los ntawm IR spectra (daim duab S9).Zoo ib yam li SEI txheej hauv classical LiB, uas tshuaj xyuas cov graphite electrode los ntawm cov kua electrolyte kom tsis txhob muaj cov tshuaj tiv thaiv ntxiv, peb ntseeg tias SEI ntawm no kuj tiv thaiv cov dej khov txheej los ntawm cov tshuaj tiv thaiv ntxiv los ntawm cov hlau lithium anode.Impedance spectra ua ntej thiab tom qab polarization ntawm Li / nano-SCE (x = 1.5) rau 10 teev tsis pom muaj kev hloov pauv ntawm cov electrolyte tsis kam.Kev ntsuas kev caij tsheb kauj vab ntev yuav xav tau kom tshem tawm qeeb ziab ntawm nano-SCE los ntawm lithium hlau, tab sis cov txiaj ntsig no tau qhia nws lub peev xwm rau kev ua tau zoo ntawm SCE hauv lithium hlau-raws li cov roj teeb hauv lub xeev.Txawm li cas los xij, cov txheej txheem interphase tuaj yeem raug txiav txim siab los txhim kho lub interface impedance tag nrho.

Peb tau pom tias ion conduction nce qib ntawm silica interfaces tuaj yeem ua tiav los ntawm kev qhia txog txheej txheej dej chemisorbed ntawm OH-txiav silica nto.Lub TFSI anions chemisorb ntawm cov dej no ua haujlwm txheej los ntawm hydrogen bonding nrog symmetric O═S═O pab pawg.Cov dej saum npoo txheej yog immobile thiab li no kuj pins cov adsorbed TFSI txheej rau saum npoo.Qhov loj BMP cations koom nrog TFSI monolayer, yog li qhia txog kev txiav txim siab molecular ntawm TFSI-BMP ntawm qhov chaw.Peb ntseeg hais tias qeeb gelation nyob rau hauv ib puag ncig aqueous thiab qeeb ziab pab hauv kev sib koom ua ke ntawm cov dej ua haujlwm thiab txheej txheej txheej ntawm cov organic ions saum nws.Raws li thawj TFSI anion txheej koom ib feem ntawm nws cov nqi tsis zoo nrog hydroxylated silica, BMP cation txheej nyob rau sab saum toj yuav nrhiav kev koom tes nrog lwm TFSI anion, uas ntau BMP tuaj yeem faib lawv cov nqi them tsis tau them nrog ib TFSI (tej zaum peb mus rau ib yam li hauv ratio of IL to Li-TFSI in the ILE).Raws li Li-TFSI ntsev molecules muaj txoj hauv kev ze tshaj plaws, Li + ions yuav cuam tshuam thiab raug teeb tsa kom nrawm nrawm nrawm ntawm txheej txheej txheej no.Rau kev txhim kho kev ua tau zoo, cov kab dawb Li + no xav tau tsawg kawg ib qho ntxiv ionic kua txheej kom txav mus los.Vim li no, nano-SCE nrog tus nqi qis x ntawm 0.5 pom tias tsis muaj kev txhim kho conductivity, raws li ILE ntim / silica nto cheeb tsam txaus rau tsuas yog ib qho kaw monolayer.

Nws tau pom ntxiv tias cov khoom zoo li cov dej los yog cov dej khov txheej tsis yog electrochemically active.Lub sijhawm no, peb tsis tuaj yeem cais tawm tias cov dej khov hauv kev sib cuag ncaj qha nrog cov electrode nto tsis hnov ​​​​tsw.Txawm li cas los xij, peb tau pom tias qhov tawm ntawm cov dej saum npoo av qeeb thiab yog li kinetically negligible rau kev kuaj pom.Peb paub tias cov dej paug, txawm tias me me, yuav ib txwm muaj kev txhawj xeeb, thiab tsuas yog kev ntsuas lub neej ntev tuaj yeem muab cov lus teb meej txog seb cov dej puas txaus.Txawm li cas los xij, lwm cov khaubncaws sab nraud povtseg uas ua haujlwm zoo sib xws lossis loj dua tuaj yeem tsim tau tam sim no.Hauv qhov no, pab pawg ntawm Li twb tau qhia txog lub peev xwm ntawm glycidyloxypropyl txheej raws li pab pawg ua haujlwm (18).Cov dej khov nab kuab yog ib txwm nyob rau silica thiab yog li tsim nyog los kawm txog cov txiaj ntsig ntawm kev ua haujlwm saum npoo ntawm ion conduction kev txhawb nqa, raws li tau ua tiav ntawm no.Tsis tas li ntawd, cov txheej txheem mesophase thiab nws cov dipole yuav nyob ntawm cov oxide thiab ntawm cov adsorbed organic molecules thiab yog li tuaj yeem hloov kho los ntawm ob qho tib si.Hauv chav kuaj, peb twb tau pom qhov sib txawv loj hauv ion conduction nce qib rau cov kua ionic sib txawv.Tsis tas li ntawd, lub hauv paus ntsiab lus qhia yog generic rau ion conduction thiab yog li no yuav siv tau rau txawv ion systems haum, piv txwv li, rau sodium, magnesium, calcium, los yog txhuas ion roj teeb.Hauv kev xaus, nanocomposite electrolyte nrog kev sib txuas lus qhia ntawm no yog lub tswv yim es tsis yog ib qho khoom siv, uas tuaj yeem txuas ntxiv (nano) engineering rau cov khoom xav tau ntawm ion conduction, thauj tus naj npawb, electrochemical qhov rai, kev nyab xeeb, thiab tus nqi rau lub neej yav tom ntej roj teeb cell tiam. .

Nano-SCE tau npaj siv txoj kev sol-gel.Lithium bis (trifluoromethylsulfonyl) imide Li-TFSI;Sigma-Aldrich;99.95%), 0.5 ml ntawm deionized H2O, 0.5 ml ntawm TEOS (Sigma-Aldrich; 99.0%), 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide (BMP-TFSI; Sigma-Aldrich; 98.5%), thiab ml ntawm PGME tau muab sib xyaw rau hauv lub khob vial.Cov molar ratio, x, nruab nrab ntawm [BMP][TFSI] thiab TEOS nyob rau hauv qhov sib tov yog varied ntawm 0.25 thiab 2. Lub molar ratio ntawm Li [TFSI] thiab [BMP][TFSI] yog tsau ntawm 0.33: 1.Tus nqi ntawm Li[TFSI] thiab [BMP][TFSI] tau txiav txim los ntawm cov piv txwv no.Piv txwv li, thaum x = 1, qhov ntxiv [BMP][TFSI] thiab Li[TFSI] hauv cov tshuaj yog 0.97 thiab 0.22 g, feem.Cov sib tov tau shaken rau 1 min los tsim cov tshuaj monophasic.Cov kev daws teeb meem no tau muab khaws cia rau hauv cov vials kaw yam tsis tau nplawm los ua cov gels hauv qhov ntsuas kub- thiab cov av noo-tswj chamber (SH-641, ESPEC Corp.) nrog rau qhov kub thiab txias thiab RH% ntawm 25 ° C thiab 50%, feem.Nyob ntawm qhov x, qhov sib tov coj, qhov nruab nrab, 5 mus rau 9 hnub los tsim cov gel ntshiab.Tom qab gelation, cov vials nrog 2.4- mus rau 7.4-ml gel yog thawj zaug qhuav ntawm 40 ° C rau plaub hnub tag nrho ntawm qhov txo qis me ntsis (80 kPa) thiab tom qab ntawd txav mus rau hauv qhov cub nqus rau 72 teev ntawm 25 ° C.Raws li cov dej noo ntxiv tau raug tshem tawm, lub tshuab nqus tsev maj mam txo los ntawm qhov pib siab ntawm 50 Pa mus rau qhov kawg siab tas li ntawm 5 Pa tom qab li 1 hnub.Vim tias muaj dej ntau thiab PGME uas yuav tsum tau muab tshem tawm, qhov tshwm sim ntawm SCE pellets tau poob qis los ntawm 20% (x = 0.5) mus rau ~ 50% (x = 2) ntawm thawj gel ntim.Qhov hnyav ntawm cov gels tshwm sim tau ntsuas nrog qhov sib npaug semimicro (SM 1245Di-C, VWR).

TGA tau ua tiav ntawm Q5000 IR (TA Instruments, New Castle, DE, USA) hauv qab nitrogen.Thaum lub sij hawm ntsuas, cov qauv tau rhuab mus rau 700 ° C ntawm qhov cua kub ntawm 2 ° C / min.FTIR spectrometry tau ua tiav siv Bruker Vertex 70 hauv yoj tus lej txij li 4000 txog 400 cm-1 hauv kev sib kis.Nws pycnometry tau ua tiav siv Micromeritics AccuPyc II 1340.

Txhawm rau ntsuas cov ionic conductivity, ib qho me me ntawm SCE tau muab los ntawm leej niam lub raj mis hauv lub thawv hnab looj tes Ar-filled (0.1-ppm H2O thiab 0.1-ppm O2).Kwv yees li ntawm 23 μl ntawm SCE tau ntim rau hauv ib lub nplhaib polytetrafluoroethylene (PTFE) nrog 4.34-mm puab txoj kab uas hla thiab 1.57-mm qhov siab, tsim ib pellet.Lub pellet nyob rau hauv lub nplhaib yog ces sandwiched ntawm ob stainless hlau (SS) disks (0.2 hli tuab; MTI).Kev ntsuas impedance tau ua tiav siv PGSTAT302 (Metrohm), nrog rau AC amplitude ntawm 5 mV nyob rau hauv ntau zaus ntawm 1 MHz txog 1 Hz.Lub ion conductivity (σi) tau txiav txim siab los ntawm kev cuam tshuam nrog cov axis tiag tiag hauv Nyquist cov phiaj xwm.Tom qab kev ntsuas kev ntsuas, cov nano-SCE pellet tau tso cai kom qhuav tawm hauv lub hnab looj tes ntxiv.Rau qhov ntsuas kub ntawm qhov ntsuas kub, SS / SCE / SS pawg tau kaw hauv ib lub xov tooj ntawm tes.Tom qab sealing, cov conductivity tseem nyob twj ywm rau ob peb hnub (saib daim duab S3).Qhov kub ntawm lub xov tooj ntawm tes yog tswj nrog lub tsho thermal nrog lub thermal da dej siv H2O / ethylene glycol ua haujlwm nruab nrab.Cov hlwb tau ua ntej txias kom txog -15 ° C thiab tom qab ntawd maj mam ua kom sov mus rau 60 ° C.

Los ntawm txhua tus nano-SCE pellet, kwv yees li 23 μl tau coj mus rau hauv lub nplhaib (4.34-mm puab txoj kab uas hla thiab 1.57-mm qhov siab) rau kev ntsuas hluav taws xob ncaj qha rau hauv lub hnab looj tes N2-filled nrog tswj cov av noo.Lub nplhaib nrog SCE tau muab tso rau ntawm ob lub SS disks (0.2 hli tuab; MTI).Kev ntsuas impedance tau ua tiav siv PGSTAT302 (Metrohm) nrog AC amplitude ntawm 5 mV thiab zaus ntawm 1 MHz txog 1 Hz tswj los ntawm Nova software.Cov qauv raug khaws cia ntawm txhua tus nqi RH% rau 48 teev ua ntej qhov kev ntsuas tau raug saib xyuas kom txog thaum muaj kev ruaj khov.Lub stabilized ionic conductivity rau ib tug muab RH% tus nqi (σi) tau txiav txim los ntawm lub high-frequency intercept nrog lub tiag tiag axis nyob rau hauv Nyquist plots.

Tag nrho cov kev ntsuas hluav taws xob thiab cov qauv kev npaj tau ua tiav hauv lub thawv ntim hnab looj tes argon (PureLab, PL-HE-4GB-1800; <1-ppm O2 thiab H2O qib) rau siab rau electrochemical characterizations.

Lub morphology ntawm cov pellet nrog thiab tsis muaj Li [BMP][TFSI] ILE tau kuaj xyuas nrog SEM siv Thermo Fisher Scientific Apreo cov cuab yeej ntawm 1.5 txog 2.0 kV uas ua haujlwm nyob rau hauv ib qho kev ntsuas dual-ntaus hom siv T1 thiab T2 ntes nyob rau hauv parallel rau nyob-duab hloov kho, thiab T2 ntes tau siv los sau cov duab SEM;tus qauv tau tsau rau ntawm carbon conductive daim kab xev.TEM tau ua tiav siv Tecnai ua haujlwm ntawm 300 kV.

Lub ILE raug tshem tawm ntawm SCE pellet nyob rau hauv ob txoj kev sib txawv.Ib qho kev xaiv kom tau txais cov silica ntxeem tau yog ua los ntawm immersing SCE hauv acetone rau 12 teev kom rho tawm Li[BMP][TFSI] ILE.Qhov dej yaug no rov ua dua peb zaug.Lwm qhov kev xaiv yog los ntawm soaking SCE hauv ethanol.Hauv qhov no, ethanol raug tshem tawm los ntawm kev siv lub tshuab ua kua CO2 tseem ceeb.

Ob lub cuab yeej sib txawv tau siv rau kev ziab khaub ncaws supercritical, uas yog, Automegasamdri-916B, Tousimis (txoj kev 1) thiab cov cuab yeej tsim los ntawm JASCO Corporation (txoj kev 2).Thaum siv cov cuab yeej thawj zaug, qhov kev ziab kom qhuav pib nrog qhov kub thiab txias mus txog 8 ° C.Tom qab ntawd, CO2 tau purged los ntawm lub chamber, nce siab mus rau 5.5 MPa.Hauv cov kauj ruam hauv qab no, CO2 tau ua kom sov rau 41 ° C, nce siab mus rau 10 MPa, thiab khaws cia li li 5 feeb.Txhawm rau txiav txim siab, hauv cov kauj ruam los ntshav, lub siab tau qis dua ib lub sijhawm ntawm 10 min.Thaum siv cov cuab yeej tsim kev cai, ib ntu zoo sib xws tau ua raws.Txawm li cas los xij, lub sij hawm thiab cov kev ntxhov siab sib txawv heev.Tom qab cov kauj ruam purging, lub siab tau nce mus rau 12 MPa ntawm qhov kub ntawm 70 ° C thiab tseem nyob li 5 mus rau 6 teev.Tom qab ntawd, lub siab tau txo qis hauv ntu ntawm 12 mus rau 7 MPa, 7 mus rau 3 MPa, thiab 3 mus rau 0 MPa nyob rau lub sijhawm ncua ntawm 10, 60, thiab 10 min, feem.

Nitrogen physisorption isotherms tau ntsuas ntawm T = 77 K siv Micromeritics 3Flex nto tus yam ntxwv ntsuas ntsuas.Tom qab ntawd cov silica porous tau tawm mus rau 8 teev ntawm 100 ° C hauv qab 0.1-mbar nqus tsev.Cov silica ntxeem tau los ntawm supercritical drying yog outgassed rau 18 teev ntawm 120 ° C nyob rau hauv ib tug 0.1-mbar nqus tsev vacuum.Tom qab ntawd, nitrogen physisorption isotherms raug ntsuas ntawm T = 77 K siv Micromeritics TriStar 3000 automated gas adsorption analyzer.

Kev ntsuas PFG-NMR tau ua tiav siv JEOL JNM-ECX400.Cov txheej txheem txhawb nqa ncha mem tes yog siv rau kev ntsuas diffusion.Lub normalized ncha teeb liab attenuation, E, yog piav nyob rau hauv kab zauv (38)E = exp(−γ2g2δ2D(Δ−δ/3))(1) qhov twg g yog lub zog ntawm lub gradient mem tes, δ yog lub sij hawm ntawm lub gradient. mem tes, ∆ yog lub caij nyoog ntawm cov npoo ntawm cov gradient pulses, γ yog qhov sib nqus magnetogyric, thiab D yog tus kheej diffusion coefficient ntawm cov molecules.Tus kheej-diffusion coefficients tau kwv yees los ntawm kev ua kom haum cov ncha teeb liab uas tau txais los ntawm kev hloov ∆ nrog Eq.1. 7Li raug xaiv los txiav txim qhov sib txawv ntawm cov lithium ion.Txhua qhov ntsuas tau ua tiav ntawm 30 ° C.

Lub Raman spectroscopy teeb yog ib lub tsev tsim siv lub argon ion muaj peev xwm raug kho rau 458-nm laser excitation teeb uas tau ua ke rau hauv ib qho inverted Olympus IX71 microscope, thiab lub teeb rov qab tawg tau dhau los ntawm TriVista triple spectrometer teeb (Princeton Instruments ), uas tau siv los cuam tshuam cov teeb liab kho qhov muag uas tau kuaj pom siv cov kua nitrogen-cooled charge-coupled device koob yees duab.Muab qhov siab ntawm qhov muag pom ntawm cov wavelengths no, lub zog laser kuj tau siv kom tsis txhob muaj cua sov laser (<100 W·cm−2).

DFT hauv av-xeev geometry optimization thiab analytical zaus xam siv cov nrov B3LYP hybrid haumxeeb thiab 6-311++ G ** lub hauv paus teeb, nrog Grimme lub atom-pairwise dispersion kho (39) nrog lub Becke-Johnson damping scheme (D3BJ), raws li siv hauv ORCA 3.0.3 (40).Raman spectra tau simulated siv ORCA, thiab qhov pom ntawm cov khoom molecular tau ua tiav siv Avogadro software pob (41) nrog ORCA-txhawb hloov tshiab.

Tag nrho cov kev ntsuas hluav taws xob thiab cov qauv kev npaj tau ua tiav hauv lub thawv ntim hnab looj tes argon (PureLab, PL-HE-4GB-1800; <1-ppm O2 thiab H2O qib) rau siab rau electrochemical characterizations.SCE pellet tau muab tso rau ntawm Li ribbon (Sigma-Aldrich; 99.9%) txhawb nqa ntawm lub phaj tooj liab raws li lub txee electrode thiab ob lub punched Li disks (5-mm txoj kab uas hla) tau muab tso rau sab saum toj ntawm SCE pellet rau siv thiab ua haujlwm. electrodes.Kev teeb tsa yog qhia hauv daim duab.S7.Kub pins tau siv rau kev hu rau lithium siv thiab ua haujlwm electrodes.Cyclic voltammetry thiab impedance ntsuas tau ua tiav siv PGSTAT302 (Metrohm) tswj los ntawm Nova software.Cyclic voltammetry tau ua tiav nrog qhov ntsuas ntsuas ntawm 20 mV / s.Kev ntsuas impedance tau ua tiav nrog AC amplitude ntawm 5 mV thiab zaus ntawm 1 MHz txog 0.1 Hz.

Ib qho 40-nm anatase TiO2 nyias-film electrode tau tso los ntawm atomic txheej deposition (ALD) ntawm 300-mm silicon wafer nrog 40-nm TiN underlayer kuj tso los ntawm ALD.Nws yog ib qho kev sim electrode zoo heev rau kev ua qauv qhia ntawm Li-ion conductivity los ntawm cov electrolytes, vim TiO2 tsis raug kev txom nyem los ntawm cov tshuaj degradation los yog mechanical stress (tsis muaj qhov tseem ceeb hloov pauv) thaum caij tsheb kauj vab.Txhawm rau ntsuas Li / SCE / TiO2 cell, ILE-SCEs tau ntim rau hauv lub nplhaib PTFE nrog txoj kab uas hla ntawm 4.3 hli thiab thickness ntawm 0.15 cm;Tom qab ntawd, lub nplhaib tau sib cais ntawm Li ntawv ci thiab TiO2 zaj duab xis.

Nano-SCE/thin-film electrode ib nrab pawg, nrog rau LMO electrode, tau fabricated los ntawm synthesizing nano-SCE zaj duab xis ntawm electrodes.Tag nrho 150 μl ntawm x = 1.5 tov, muaj hnub nyoog 2 hnub, tau poob-casted nyob rau hauv lub iav nplhaib (inch, 1.3 hli) mounted rau ntawm electrolyte films.Tom qab ntawd lub nplhaib raug kaw nrog parafilm, thiab cov tshuaj tau khaws cia rau hauv lub thawv kaw rau gel rau 4 hnub.Cov tsim gel / electrode pawg xws li tau qhuav los ua nano-SCE / electrode stacks.Lub thickness ntawm nano-SCE, txiav txim siab siv lub micrometer, yog 300 μm.Thaum kawg, ib daim ntawv lithium (1.75 hli tuab, 99.9%; Sigma-Aldrich) tau nias ntawm nano-SCE / electrode pawg ua cov anode.Lub 100-nm LiMn2O4 (LMO) nyias-zaj duab xis electrode tau tso los ntawm xov tooj cua zaus sputtering nyob rau hauv Ar ntws ntawm silicon wafer coated nrog 80-nm Pt (DC sputtering) / 10-nm TiN (ALD) underlayers.Cov pawg no tau muab tso rau 20 feeb ntawm 800 ° C hauv cov pa oxygen.

LiFePO4 (LFP) electrode films tau npaj los ntawm cov hniav txheej.Ua ntej, cov pa roj carbon dub thiab LFP (2 mus rau 3 μm) tau ntxiv rau cov tshuaj aqueous uas muaj carboxymethylcellulose (CMC) los ua ib qho kev sib xyaw uas tom qab homogenized siv lub ntiaj teb sib tov.Tom qab ntawd, cov khoom lag luam homogenized tau tov nrog dej deionized thiab fluorinated acrylic latex (JSR, TRD202A) hauv lub tshuab nqus tsev tov khoom los tsim cov slurry rau electrode txheej.Cov slurry npaj tau cam khwb cia rau ntawm aluminium foils rau deposit electrode films siv ib tug hniav coater.Cov electrodes li-coated ntub dej tam sim ntawd tau muab tso rau hauv qhov cub atmospheric nrog cua nyob ntawm 70 ° C rau 10 min thiab tau qhuav ntxiv ntawm 140 ° C rau 4 xuab moos hauv lub tshuab nqus tsev.Cov yeeb yaj kiab qhuav electrode muaj 91 wt% LiFePO4, 3 wt% carbon dub, 2 wt% CMC, thiab 4 wt% TRD202A.Zaj duab xis thickness yog 30 μm (txiav txim siab siv lub micrometer thiab scanning electron microscope).

Li4Ti5O12 (LTO) electrode films tau ua rau ntawm tooj liab foils tib yam.Cov muaj pes tsawg leeg ntawm qhuav electrodes yog 85 wt% Li4Ti5O12, 5 wt% carbon dub, 5 wt% CMC, thiab 5 wt% fluorinated acrylic latex (TRD2001A).Zaj duab xis thickness yog 40 μm.

Kev daws ntawm SCE tau poob-casted ntawm particle-based LFP thiab LTO electrode zaj duab xis.Ua ntej, 100 μl ntawm x = 1.5 tov, hnub nyoog 2 hnub, tau poob-casted rau ntawm ib tug electrode zaj duab xis, nrog ib txoj kab uas hla ntawm 15 hli, muab tso rau hauv ib lub npib cell (#2032, MTI).Tom qab lub impregnated SCE tau gelled, zaj duab xis tau qhuav ntawm 25 ° C rau 72 teev nyob rau hauv lub tshuab nqus tsev qhov cub (<5 × 10−2 mbar) los ua cov nano-SCE thiab electrode pawg.Nano-SCE thickness yog 380 μm.Thaum kawg, ib daim ntawv lithium tau nias rau ntawm SCE / electrode stacks raws li cov anode, thiab cov npib cell raug kaw.Kev ntsuas electrochemical tau ua tiav siv Solartron 1470E potentiostat ntawm chav tsev kub.

Cov ntaub ntawv ntxiv rau tsab xov xwm no muaj nyob ntawm http://advances.sciencemag.org/cgi/content/full/6/2/eaav3400/DC1

Tab S1.Cov yam ntxwv ntawm silica matrix nyob rau hauv nano-SCE rau nce molar feem ntawm ionic kua rau silica (x tus nqi) txiav txim los ntawm N2 adsorption / desorption los yog BET ntsuas thiab TEM soj ntsuam.

Qhov no yog ib tsab xov xwm qhib tau muab faib raws li cov ntsiab lus ntawm Creative Commons Attribution-NonCommercial daim ntawv tso cai, uas tso cai rau siv, faib, thiab luam tawm nyob rau hauv ib qho nruab nrab, tsuav yog qhov tshwm sim ntawm kev siv tsis yog rau kev lag luam kom zoo dua thiab muab cov haujlwm qub kom zoo. hais.

CEEB TOOM: Peb tsuas yog thov koj qhov chaw nyob email kom tus neeg uas koj tab tom qhia nplooj ntawv kom paub tias koj xav kom lawv pom nws, thiab nws tsis yog ntawv xa tuaj.Peb tsis ntes ib qho email chaw nyob.

Lo lus nug no yog rau kev sim seb koj puas yog tib neeg tuaj xyuas thiab tiv thaiv kev xa tawm tsis siv neeg spam.

Los ntawm Xubin Chen, Brecht Put, Akihiko Sagara, Knut Gandrud, Mitsuhiro Murata, Julian A. Steele, Hiroki Yabe, Thomas Hantschel, Maarten Roeffaers, Morio Tomiyama, Hidekazu Arase, Yukihiro Kaneko, Mikinari Shimada, Maarten Mees, Philippe

Los ntawm Xubin Chen, Brecht Put, Akihiko Sagara, Knut Gandrud, Mitsuhiro Murata, Julian A. Steele, Hiroki Yabe, Thomas Hantschel, Maarten Roeffaers, Morio Tomiyama, Hidekazu Arase, Yukihiro Kaneko, Mikinari Shimada, Maarten Mees, Philippe

© 2020 American Association rau Advancement of Science.Txhua txoj cai.AAAS yog ib tug khub ntawm HINARI, AGORA, OARE, CHORUS, CLOCKSS, CrossRef thiab COUNTER.Science Advances ISSN 2375-2548.