silika gel olimba nanocomposite electrolytes ndi interfacial conductivity kukwezedwa kupitirira chochuluka Li-ion madutsidwe wa ionic madzi electrolyte filler

Kusintha kwa mabatire a Li-ion a state-state kumathandizira kupita patsogolo kwa mphamvu zamagetsi za 1000 W·hour/lita ndi kupitirira.Zophatikizika za mesoporous oxide matrix odzazidwa ndi ma electrolyte osavolatile a ionic liquid electrolyte adawunikidwa ngati njira yolimba ya electrolyte.Komabe, kutsekeka kosavuta kwa mayankho a electrolyte mkati mwa ma pores amtundu wa nanometer kumabweretsa kutsika kwa ma ion conductivity pamene mamasukidwe akayendedwe akuwonjezeka.Apa, tikuwonetsa kuti Li-ion conductivity ya nanocomposites yokhala ndi mesoporous silica monolith yokhala ndi ma ionic liquid electrolyte filler imatha kukhala yokwera kangapo kuposa ya ionic yamadzimadzi yamadzimadzi electrolyte poyambitsa gawo la ayezi.Kutsatsa kwamphamvu ndikuyitanitsa mamolekyu amadzi a ionic kumapangitsa kuti asasunthike komanso olimba ngati gawo la ayezi wolumikizana.The dipole pamwamba pa adsorbate mesophase wosanjikiza kumabweretsa kuthetsedwa kwa ma Li + ions kuti apititse patsogolo conduction.Mfundo yowonetseredwa yopititsa patsogolo ma ion conduction ingagwiritsidwe ntchito pamakina osiyanasiyana a ion.

Ma electrolyte olimba akuyembekezeka kupereka chilimbikitso chotsatira kuti mabatire a Li-ion apitirire denga logwira ntchito la 800 W·hour/lita kapena 300 W·hour/kg zoyikidwa pa cathode ndi anode chemistries zomwe zilipo pakali pano.Kuwonjezeka koyembekezeka kwa kachulukidwe ka mphamvu zamabatire amtundu wokhazikika kumachokera ku zopereka zingapo, zonse zimayang'ana kukulitsa kuchuluka kwazinthu zogwira ntchito muselo.Chodziwika kwambiri ndikuyambitsa zitsulo za lithiamu kuti zisinthe graphite ndi graphite / silicon ngati anode.Lifiyamu chitsulo choyera chimakhala ndi mphamvu zambiri zomwe zingatheke ndipo zimafuna malo ochepa kwambiri.Komabe, nkhani zambiri zikufunikabe kuthetsedwa, monga zomwe sizingasinthe (ndipo kugwiritsa ntchito) kwa lithiamu zitsulo, mapangidwe a dendrite, kuwonjezeka kwa kachulukidwe kamakono kamakono a lifiyamu a planar poyerekeza ndi porous graphite (silicon) electrodes, ndipo, koma osachepera, "kutayika" kwa lithiamu panthawi yotulutsa (deplating) ndipo motero kutaya kukhudzana ndi electrolyte yolimba.Kapangidwe ka makina olimba a ma electrolyte olimba a ceramic alibe kutsata, ndipo kukakamizidwa kwambiri kumafunika kukanikiza lithiamu mwamphamvu motsutsana ndi gawo lolimba la electrolyte.Kupanikizika kwapadera kumatsitsa malo owoneka bwino kwambiri, zomwe zimapangitsa kuti ma dendrite apangidwe komanso ma depositi a spongy.Ma polima electrolyte amayenderana kwambiri ndi makina koma samawonetsa ma ionic conductivity yokwanira kutentha kutentha.Zinthu zatsopano zosangalatsa kwambiri pankhaniyi ndi ma electrolyte a silika a gel, omwe amatchedwanso "ionogels," pomwe ionic liquid electrolyte (ILE) imakhala mu nanoporous silica matrix (1).Kuchuluka kwambiri kwa matrix a silika (70 mpaka 90%) kumapangitsa kuti zida za nanocomposite electrolyte izi zikhale ngati gel ndipo motero zimawapangitsa kuti azigwirizana ndi ma electrolyte a polima.Ma gels a silika awa nthawi zina amawonetsedwa ngati ma electrolyte olimba osakanizidwa, chifukwa amakhala ndi madzi.Komabe, kwa silika nanocomposites, monga momwe zafotokozedwera mu pepalali, ma electrolyte a ionic "amadzimadzi" amakhala olimba ngati atsekeredwa mu makumi a njira zazikuluzikulu za nanometer powonjezera kukhuthala komanso kutengera pakhoma la silika lomwe limatsekereza khoma. njira.Ngati silika masanjidwewo akadangokhala ngati porous separator, ndiye kuwonjezeka mamasukidwe akayendedwe kwa wotsekeredwa madzi electrolyte kungachititse kuti kuchepa ayoni madutsidwe.M'malo mwake, kuyanjana pakati pa mamolekyu a ILE ndi khoma la silika pore kumapangitsa kuti katundu wa nanocomposite akhale wosiyana ndi kuchuluka kwa zigawo zake.Kumangirira kwa zakumwa za ayoni pa ma oxides ndi mapangidwe a masophase zigawo zolimba mpaka ma nanometer ochepa mu makulidwe awonetsedwa pa malo olinganiza ndi ma atomiki amphamvu ya microscopy (2).Kusankhidwa kosankhidwa kwa ma anion amadzimadzi a ionic ndi ma cations pamalo a oxide amatha kupititsa patsogolo kuwongolera kwa Li + panjira izi.Zachidziwikire, kuwongolera komwe kumayenderana ndi oxide kuyenera kubweza kapena kupitilira kutsika kwamayendedwe kudzera mu ILE yomwe ili pakatikati pa pores.Chifukwa chake, kukula kwakung'ono kwa pore ndi kuchuluka kwapamwamba kwa voliyumu kumafunidwa.Pakadali pano, ma ionogel okhala ndi ma ion conductivities akuyandikira a ILE omwe awonetsedwa ndi kukhathamiritsa kwa mawonekedwe a mesoporous (3).Izi zikutanthauza kuti kuwongolera mawonekedwe kunalipo kale koma osati kupitilira kuchuluka kwa ma conductivity.

Kukonzekera kwa ma ionogel kumayambira pakusakaniza kwamadzimadzi kofanana, komwe ILE imawonjezeredwa ku sol-gel precursor yankho la kaphatikizidwe ka oxide matrix (4, 5).Munjira iyi, ILE ndi matrix zimapanga kompositi mwanjira ya "in situ": Zotsogola mu yankho zimachita kupanga matrix oksidi mozungulira template yamadzi a ionic, ndikuyiyika munjirayo.Pazifukwa zina zophatikizira, ILE-SCE yokonzeka (yolimba yopangidwa ndi electrolyte) imatha kukhala ngati monolith yokhala ndi ILE yophatikizidwa ndi netiweki ya mesoporous inorganic oxide network.Pakadali pano, ma ILE-SCEs ambiri a silica akonzedwa motere, ngakhale zitsanzo zapangidwanso ndi alumina (6), titania (7), komanso tin oxide (8).Ambiri akuti sol-gel osakaniza formulations muli ILE, ndi alkyl-silicate monga tetraethyl orthosilicate (TEOS) monga silica kalambulabwalo, ndi formic acid monga reagent ndi zosungunulira (9, 10).Malinga ndi njira yomwe ikufunsidwa (11) ya ndondomeko ya sol-gel, silika imapangidwa makamaka ndi zomwe zimachitika pakati pa TEOS ndi formic acid, ngakhale kuti madzi amapangidwa panthawi ya sol-gel.Kupatula izi zosakaniza za "nonaqueous" za "nonaqueous", amadzimadzi sol-gel osakaniza ndi HCl monga chothandizira ndi H2O monga reagent (kuphatikiza zosungunulira organic) zafotokozedwanso, komabe mu nkhani iyi ya kaphatikizidwe wa silica composite ndi Ionic madzi okha (12-15).

Nthawi zambiri, ma ionogel amawonetsa ma ion conductivity otsika kuposa a ILE reference.M'badwo woyamba wa ma ionogel anali ndi kutentha kwachipinda nthawi zambiri amakhala pafupifupi 30 mpaka 50% ya kuchuluka kwa mtengo wa ILE, ngakhale zitsanzo zina zofikira 80% zanenedwapo (9, 10, 16, 17).Zotsatira za zomwe zili mu ILE ndi zotsatira za pore morphology pa ionogel conductivity zafufuzidwa kale mwatsatanetsatane (3);komabe, palibe kafukufuku wokhazikika wa zotsatira zowonjezera mawonekedwe omwe amadziwika.Wu et al.(18) posachedwapa adanenanso za in situ functionalized ionogel, yomwe idaperekanso kupititsa patsogolo kuyerekeza ndi kuchuluka kwa ILE.Kupititsa patsogoloku kudachitika chifukwa cha kuyanjana pakati pa anion ndi gulu logwira ntchito la 3-glycidyloxypropyl pamtunda wa silica.Kupeza uku kumathandizira lingaliro loti magwiridwe antchito apamwamba amathanso kupititsa patsogolo kukweza kwa mawonekedwe.

Mu ntchito iyi, timasonyeza mu situ mapangidwe olimba ayezi madzi wosanjikiza pa silika ndi mwatsatanetsatane limagwirira interfacial Li-ion conduction ndi kuchuluka dipole kucheza pakati pa pamwamba ayezi zinchito wosanjikiza ndi adsorbed ayoni madzi mesophase wosanjikiza.Kuphatikizika kwa malo okwera amkati ndi madzi oundana oundana, ma electrolyte olimba a nanocomposite (nano-SCE) okhala ndi 200% apamwamba a Li-ion conductivity kuposa kuchuluka kwa ILE komwe kunapezedwa.Matrix a silica akuwonetsedwa kuti ali ndi mawonekedwe enieni a monolithic mesoporous okhala ndi ma pore voliyumu ndi malo oyambira mpaka 90% ndi 1400 m2/g, motero amapereka ma ratioti apamwamba kwambiri amtundu wa voliyumu omwe amalola thandizo lalikulu la kuwongolera ma conduction panjira izi.Ndi wokometsedwa functionalization wa silika pamwamba pamodzi ndi maximizing pamwamba-to-voliyumu chiŵerengero, nano-SCE ndi ion conductivities bwino kuposa 10 mS/cm akhoza mwina injiniya motero ndi wokongola mabatire lalikulu mphamvu kwa ntchito galimoto.

Cholinga cha pepala lathu ndi pamakina opititsa patsogolo mawonekedwe a mawonekedwe popanga masophase layer ndi umboni wochokera ku Raman, Fourier transform infrared (FTIR), ndi nuclear magnetic resonance (NMR) spectroscopy.Kukhazikika kwa mawonekedwe azinthu zathu za nano-SCE pamagetsi apamwamba amawonetsedwa pogwiritsa ntchito ma elekitirodi a lithiamu manganese oxide (LMO) afilimu.Mwanjira iyi, kuyang'ana kumapitilira pazinthuzo m'malo molumikizana ndi ma elekitirodi ndi nkhani za msonkhano wama cell.Mofananamo, zenera la electrochemical ndi kukhazikika kwazitsulo za lithiamu zimadziwika bwino.Kugwira ntchito ndi kuphatikizika kwa nano-SCE yathu kumawonetsedwa kudzera mu kuyesa kwa ma lithiamu iron phosphate (LFP) ndi lithiamu titanate (LTO) maselo.Kukhazikika kwa electrolyte yathu ndi kusagwira ntchito kwa electrochemical kwa madzi oundana kunawonetsedwa kudzera panjinga yayitali yama cell a Li-SCE-Li.Kukhathamiritsa kwa kachulukidwe kamphamvu, magwiridwe antchito, komanso kuyendetsa njinga zama cell osonkhanitsidwa kwathunthu ndizomwe zimayang'ana pamapepala otsatila (19, 20).

Kukwezeleza kwa ma ion conductivity m'magawo awiri ophatikizika kwadziwika kwa zaka pafupifupi 90 (21).Mwachitsanzo, mpaka madongosolo anayi a kuwonjezeka kwa ayoni madutsidwe wasonyezedwa kwa nsanganizo zosavuta lifiyamu mchere monga lithiamu ayodini ndi mesoporous okusayidi particles monga silika kapena aluminiyamu poyerekeza ndi ion conductivity wa koyera lithiamu mchere electrolyte (22).Ma ion omwe ali mu ma SCE awa amatha kufalikira mwachangu motsatira magetsi a Li ion-depleted (kapena olemera) omwe amapangidwa pa mawonekedwe a oxide/electrolyte.Tsoka ilo, ma ion conductivity omwe amapezeka m'zigawo ziwiri zosavuta za inorganic solid-solid composites (1) sanadutse 1-mS/cm2 polowera mtunda wofunikira kuti atseke mtunda wa ma micrometer mazana angapo pakati pa mbale zotolera zomwe zilipo mu batire ya Li-ion. .Lingaliro la heterogeneous doping yokhala ndi oxide matrix kuti apange ma ionic conductivity adawunikiridwanso pa ma polymer electrolyte (23) ndi ma ILEs (24), omwe ali ndi ma ionic apamwamba kwambiri poyambira.Kuphatikiza apo, mamolekyu olemera (stereo) chemistry ya gawo lachitatu amatsegula njira zowonjezera za ion conduction, monga (di) mamolekyu ngati ma polar solvent atha kutenga nawo gawo pakupanga gawo lamagetsi lawiri.Ngakhale solvating zochita za magulu etere mu polyethylene okusayidi polima electrolytes amapereka olimba boma ayoni conductivities wa ~ 10−6 S/cm kwa LiClO4 ~ 10−5 S/cm kwa LiN(SO2CF3)2, nsanganizo awo ndi silika, aluminiyamu. , kapena titania nanoparticles angaperekedi kuwonjezereka kwa 10 muyeso wa ma ion conductivity (25), mwatsoka, akadali pansi pa chipinda cha kutentha kwa 1 mS/cm.ILE solutions ndi zosakaniza za Li-salt solute ndi ionic liquid zosungunulira, zomwe zimatha kukhala ndi ma intrinsic ionic conductivities pakati pa 0.1 ndi 10 mS/cm (26, 27).Kuyesera kangapo kumapangitsa kuti ma ion conductivity apangidwe mwa kusakaniza kapena kusakaniza ndi oxide nanoparticles kapena kutsekereza ILE mu mesoporous microparticles (9, 16, 28, 29).Komabe, mpaka pano, palibe kuwongola kwa ion conductivity wakhala anaona kwa chigawo chimodzi Li-mchere / ionic madzi / okusayidi nsanganizo (mkuyu. S1).Ngakhale kugwiritsa ntchito ma mesoporous silica microparticles kumapangitsa kuti pakhale kusinthika kwakukulu poyerekeza ndi zophatikizika ndi ma nanoparticles olimba, malo ophatikizika ndi mawonekedwe a ion conduction sikokwanira kupitilira kuchuluka kwa ILE conductivity.

Mesoporous silica ndi chinthu chodziwika bwino chomwe chimagwiritsidwa ntchito pothandizira.Amapangidwa ndi hydrothermal kapena yosavuta sol-gel synthesis.Njira za Hydrothermal nthawi zambiri zimatsogolera ku ufa wa mesoporous, koma ndikuwongolera mosamalitsa kutentha kwa chipinda cha sol-gel, magalasi akuluakulu opangidwa ndi magalasi kapena ma aerogel apangidwanso.Silika masanjidwewo amapangidwa kudzera hydrolysis ndi condensation zochita za tetra-alkyl orthosilicates (30).Chofunikira pakuwongolera kapangidwe ka pore ndikugwiritsa ntchito ma templates, mwachitsanzo, micelle yamtundu wa surfactant, pomwe matrix a silika amapangidwira.Madzi a ayoni akawonjezeredwa ngati molekyulu yoyeserera, matrix a hydrated silica amalumikizana ndi madzi a ionic, kupanga gel, ndipo atatha kuchiritsa ndi kuyanika, madzi a ayoni amatsekeredwa mkati mwa matrix olimba a nanoporous silika (13).Mchere wa lithiamu ukawonjezedwa ngati gawo lachitatu, ILE yomwe ili mu silika matrix imapanga silika gel electrolyte, yomwe imatchedwanso ionogel (24).Komabe, mpaka pano, izi silika gel osakaniza electrolyte kusonyeza conductivities kuyandikira kwa chochuluka ILE koma osapitirira izo, kupatula pa nthawi imodzi pamene silika anali mankhwala functionalized (onani Mau Oyamba) (18).

Pano, tikuwonetsa, kukwezedwa mwadongosolo kwa Li-ion conductivity ya nanocomposite bwino kuposa ya ILE yoyera.Chitsanzo cha 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP-TFSI) imagwiritsidwa ntchito pano.Zimaganiziridwa kuti kutengeka kwa mamolekyu a ionic amadzimadzi pamtunda wa silika wa OH kumalimbikitsidwa ndi kukhalapo kwa madzi oundana a madzi oundana.Kulumikizana kwamphamvu kwa haidrojeni pakati pa madzi oundana ndi TFSI− anion kumapangitsa kuyitanitsa kwamadzi kwamadzi a ionic, ofanana ndi madera olamulidwa omwe amangopanga zakumwa za ayoni (31).Kusiyana kwakukulu ndi madera opangidwa mwachisawawa muzambiri za ILE ndikuti madzi oundana amakhala ngati gawo logwira ntchito lomwe (i) limapangitsa kuyitanitsa kwa mamolekyulu pamtunda wa oxide ndi (ii) kumayambitsa ma H-bonding amphamvu kuti apangitse dipoles kuti amasule Li + yaulere. kwa kupititsa patsogolo.Pafupi ndi kuwonjezeka kwa ndende ya Li + yaulere, tiwonetsa kuti mphamvu yoyambitsa kufalikira ndi yotsika pamodzi ndi mawonekedwe ophatikizika ndi adsorbed ILE wosanjikiza ndi madzi oundana.

Madzi ochepa a monolayers-thick-thick surface pa silika ndi wosanjikiza ngati wolimba, chifukwa amamangiriridwa kwambiri ndi magulu a silanol kupyolera mu H-milatho ndipo motero amatchedwanso ayezi (32).Kachulukidwe ake ndi makulidwe (akuyerekeza atatu mpaka anayi monolayers, ndi ~ 0.25 nm pa ayezi monolayer) ali mu thermodynamic equilibrium ndi pang'ono madzi kuthamanga [chibale chinyezi (RH)] mu chilengedwe (mkuyu. S2).Timasonyeza kuti ma ion conductivity amawonjezeka ndi makulidwe a madzi oundana monga kugwirizana kwa haidrojeni ndi zigawo za adsorbed ionic kumawonjezeka.Madzi oundana amakhala okhazikika mofanana ndi madzi a kristalo mumagulu a mankhwala.Izi ndizosiyana kwambiri ndi ma electrolyte amadzimadzi ochuluka kwambiri kapena otchedwa madzi osakaniza mchere, pomwe zenera la electrochemical limakulitsidwa kwambiri koma, pamapeto pake, madzi akadali amphamvu kwambiri (33).

Mosiyana ndi maphikidwe amtundu wa formic acid-catalyzed ionogel, tidagwiritsa ntchito pH 5 yosakaniza ndi madzi ochulukirapo ndi PGME (1-methoxy-2-propanol) yowonjezeredwa ku kalambulabwalo wa TEOS wokhala ndi mchere wa Li-TFSI ndi madzi aionic a BMP-TFSI.Pa pH iyi, machitidwe a hydrolysis amachedwa, pomwe ma condensation ndi abwino (30).The Li ions amakhulupirira kuti amachita ngati chothandizira kuti hydrolysis reaction, monga palibe gelation inachitika popanda lithiamu mchere pamene onse anali ndi pH yofanana 5. The molar chiŵerengero cha madzi ionic kwa TEOS (ndipo motero silica moieties) ndi ikuwonetsedwa ngati mtengo wa x ndipo inali yosiyana pakati pa 0.25 ndi 2. Chiŵerengero cha molar cha BMP-TFSI ku Li-TFSI chinasungidwa pa 3 (chofanana ndi 1 M Li-ion solution).Kuyanika pang'onopang'ono kunali kofunikira kuti musunge kukhulupirika kwa kapangidwe ka monolith (onani Zida ndi Njira).Chithunzi 1A chikuwonetsa chithunzi cha pellet monolithic chopezedwa pambuyo poyanika vacuum.Kuwumitsa vacuum kwa maola 72 kunali kokwanira kuchotsa chinyontho chonse mpaka pomwe madzi onse aulere adachotsedwa pomwe madzi oundana a adsorbed adakhalabe osasunthika, monga zatsimikiziridwa ndi FTIR.Palibe kugwedezeka kwa madzi aulere omwe adapezeka pa 1635 cm-1 muzotsatira zilizonse pambuyo pa gawo lowumitsa vacuum (mkuyu 2).Poyerekeza, mawonekedwe a FTIR a chitsanzo cha nano-SCE (x = 1.5) chosungidwa kwa sabata limodzi mu bokosi la glove la N2 pa 60% RH ikuwonetsedwa.Pankhaniyi, nsonga yamadzi yaulere yaulere ikuwonekera.Zitsanzo zonse, kumbali ina, zidawonetsa chizindikiro chomveka bwino cha ntchito ya silanol (Si─OH kupinda pakati pa 950 ndi 980 cm−1) ndi madzi oundana adsorbed (O─H kutambasula pa ~ 3540 cm−1) magulu a ─OH opangidwa ndi H-bonding (zambiri pansipa).Mbalezo zinali zolemera musanayambe komanso pambuyo poyanika kuti muyese madzi osungidwa mu nano-SCE (tebulo S1).Pambuyo pake, tiwerengera kuchuluka kwa ma monolayers ofanana a zigawo za ayezi kuchokera pa kulemera kowonjezera.Ma pellets owumitsidwa ndi vacuum adabweretsedwa m'bokosi la magolovu [<0.1-ppm (gawo pa miliyoni) H2O] ndikusungidwa m'mabotolo otsekedwa kuti asunge madzi oyambira.Voliyumu yaying'ono idatengedwa kuchokera pa pellet kuti iwonetsedwenso.

(A) Chithunzi cha ma pellets awiri a nano-SCE (kumanzere) opangidwa mu vial;pambuyo pa gelation, pellet yowonekera imapezeka.Zindikirani kuti pellet imawonekera bwino ndipo idapatsidwa mtundu wabuluu kuti uwoneke.ILE ikachotsedwa, pellet yoyera yoyera imakhalabe ya matrix owopsa kwambiri a silica (kumanja).(B) Kujambula ma electron microscopy (SEM) chithunzi cha matrix a SiO2 chomwe chimatsalira pambuyo pochotsa ILE.(C) Mawonekedwe a chithunzi chowonetsedwa mu (B) chosonyeza mawonekedwe a masoporous a matrix okhala ndi macropores.(D) Chithunzi cha Transmission electron microscopy (TEM) chosonyeza kulongedza wandiweyani wa 7- mpaka 10-nm silica nanoparticles monga zomangira za porous matrix material.(E) Kukhazikika kwa kapangidwe ka matrix komwe kumapangidwira magawo osiyanasiyana a molar a ILE molingana ndi SiO2 (x mtengo).Mzere wodutsa umapereka porosity yamalingaliro yomwe imatsimikiziridwa kuchokera kugawo la ILE ndi silika.Zitsanzo zotsukidwa ndi acetone (mabwalo akuda) zidawumitsidwa mumlengalenga, zomwe zimapangitsa kugwa pang'ono kwa kapangidwe ka x> 0.5.Supercritical CO2 kuyanika kwa ethanol-rinsed nano-SCE (mabwalo obiriwira) kumalepheretsa kugwa mpaka x = 2 pakuchotsa pang'onopang'ono kwa CO2 (bwalo lotseguka).BET, Brunauer-Emmett-Teller.Chithunzi chojambula: Fred Loosen, imec;Akihiko Sagara, Panasonic.

(A) Mawonekedwe a IR a nano-SCE monga zouma mu vacuum (wakuda) ndipo kenako zowuma mu bokosi la glove ndi 0.0005% RH kwa masiku 9 (buluu) ndikuwonekera kwa 30% RH kwa masiku 4 (wofiira) ndi 60 % RH kwa masiku 8 (wobiriwira), motsatana.kapena, mayunitsi osagwirizana.(B) Cyclic voltammograms ya stack ya Li/SCE/TiN yokhala ndi ma x 1.0 (blue), 1.5 (green), ndi 2.0 (red) ndi ILE reference (yakuda);chithunzichi chikuwonetsa zomwe zikuchitika mu sikelo ya logarithmic.(C) Cyclic voltammograms ya Li/SCE (x = 2)/40-nm TiO2 stack (yofiira), ILE (madontho akuda), ndi ILE spiked ndi 5 kulemera % (wt %) H2O (dash-dotted blue line);mu (B) ndi (C), miyeso ya ILE ndi ILE yokhala ndi H2O idapangidwa mukusintha ma elekitirodi atatu ndi TiN ngati electrode yogwira ntchito ndi Li monga maelekitirodi owerengera ndi mareferensi.SCE idawumitsidwa kwa masiku awiri mubokosi la magolovu mutatha kuyanika.

The ionic conductivity (σi) wathu vacuum-annealed nano-SCE anawonjezeka ndi voliyumu gawo la ILE (x mtengo) monga tinthu composites (mkuyu. S1).Komabe, pankhaniyi, ma ionic conductivity adaposa ILE yoyera yokhayokha kuposa 200% pamitengo yapamwamba kwambiri ya x (mkuyu 3).Kuphatikiza apo, kudalira kwa kutentha kwa nano-SCE yokhala ndi ma ion conductivity opititsa patsogolo kunawonetsa khalidwe losiyana ndi la ILE yoyera: Pamene Li-TFSI mu BMP-TFSI ILE ikuwonetsa kusintha kowonekera kwa conductivity ndi activation mphamvu (kutsetsereka) kuzungulira kusungunuka. mfundo ya osakaniza pa 29 ° C, nano-SCE ndi kumatheka madutsidwe satero.M'malo mwake, zikuwonetsa kusinthasintha kosalekeza kwa σi ndi kutentha, kusonyeza kuti mtundu wosadziwika wa gawo kapena mesophase umapangidwa, womwe ndiye umayambitsa kukhathamiritsa kopitilira muyeso.Komanso, otsetsereka ang'onoang'ono motero kuchepetsa kutsegula mphamvu kwa mayamwidwe kwa nano-SCE poyerekeza ILE zimasonyeza zinthu zosiyanasiyana katundu (mkuyu. S3).Zikuganiziridwa kuti kuyanjana kwakukulu pakati pa mamolekyu a ionic amadzimadzi ndi madzi oundana olimba pa scaffold ya silika ndizomwe zimayambitsa machitidwe a mesophase, monga tidzakambitsirana ndi chitsanzo chomwe chili pansipa.

(A) Kutentha kwa kutentha kwa nano-SCEs zouma kwa masiku 8 mu bokosi la glove (GB) yokhala ndi ma x 2 (mabwalo akuda), 1.75 (mabwalo alalanje), 1.5 (makona atatu abuluu), ndi 1.0 (makona atatu obiriwira ) ndi zolemba za ILE (mabwalo otseguka).(B) Mayendedwe a nano-SCEs amawumitsidwanso mu GB kwa masiku 0 (mabwalo obiriwira), masiku 10 (makona atatu akuda), ndi masiku 138 (makona atatu abuluu).(C) Conductivity motsutsana ndi muzu wa square wa kuyanika nthawi ya nano-SCE yokhala ndi ma x ma 2 (mabwalo akuda), 1.5 (makona atatu abuluu), 1.0 (makona atatu obiriwira), ndi 0.5 (madiamondi abulauni).(D) Mayendedwe a nano-SCE okhala ndi x = 2 (mabwalo akuda), 1.5 (makona atatu abuluu), ndi 1.0 (makona atatu obiriwira) owonekera muchipinda chonyowa chodzaza ndi N2.

Mphepete mwa argon mu bokosi la glove muli madzi osachepera 0.1 ppm, omwe amafanana ndi 0.0005% RH, kuthamanga kwa madzi pang'ono kwa 0.01 Pa, kapena mame -88 ° C.Monga kuchuluka kwa zigawo za madzi otsekemera pa silanol-terminated silica ndi zofanana ndi kuthamanga pang'ono kwa madzi (mkuyu.Chithunzi 3C chikuwonetsa kusintha kwa madulidwe a 23 μl a nano-SCE ngati ntchito yanthawi yokhala mubokosi la magolovu.The ion conductivity imachepa ndi kuyanika mpaka imakhuta pamtengo wolingana ndi silika pamwamba pamlingo wofanana ndi kuthamanga kwapang'ono kwamadzi kwa 0.01 Pa mu bokosi la glove.Ngakhale pansi pawuma wouma kwambiri wa bokosi la glove, osachepera pang'ono adsorbed madzi pa silanol alipo, monga Raman spectroscopy akadali anasonyeza chizindikiro pa 3524 cm−1, amene ali enieni monolayer woyamba wa madzi adsorbed pa silanol. (Mkuyu 4B).Mawonekedwe a ion pansi pamikhalidwe yodzaza anali otsika kwambiri a ILE yamunthu nthawi zonse.Chifukwa chake, kuwongolerako sikukwanira kulipira kutayika kwa ma ionic conductivity ya ILE yotsekeka pakatikati pa pore.

(A) IR spectra ya nano-SCE yokhala ndi mtengo wa x wa 1.5 (wofiira), ILE reference (yakuda), ndi SiO2 (buluu), kusonyeza kuti gulu la O═S═O (1231 cm−1) likukhudzidwa ndi kugwirizana ndi OH-magulu pa silika pamwamba.(B) Mawonekedwe a Raman a nano-SCE okhala ndi ma x a 2 (wakuda), 1.5 (ofiira), ndi 0.5 (buluu), akuwonetsa kupezeka kwa madzi oundana omangika pa silanol-terminated silica ngakhale nano-SCE pafupi ndi machulukitsidwe (0.0005 % RH) mu bokosi la glove (masiku 30).(C) Chitsanzo chokonzekera cholumikizirana mu nano-SCE ndi dissociation Li-TFSI mu Li + yaulere monga TFSI-anion imagawana gawo la ndalama zake zoipa ndi adsorbed ice-TFSI-BMP wosanjikiza;mitunduyo imayimira zinthu zosiyanasiyana zofiirira (silicon), zofiira (lithiamu), chikasu chakuda (sulfure), lalanje (oxygen), buluu (nayitrogeni), woyera (hydrogen), ndi wobiriwira (fluorine).Mizere yofiirira imayimira mgwirizano wa haidrojeni pakati pa gulu la O═S la TFSI anion ndi OH-magulu a hydroxylated silica surface.Ma Li + ions omasulidwa ndi dipole pamwamba pa wosanjikiza adsorbed amatha kusuntha kudzera m'magawo otsatizana a mafoni kapena ophatikizika amadzimadzi a ionic pamwamba pa magawo a mawonekedwe.Dziwani kuti kutengera mphamvu ya ma hydrogen bond ndi mtengo wofananira pa silika, wosanjikiza angapo adsorbed angapangidwenso.Mawonekedwe athunthu akuwonetsedwa mkuyu.S8.

Chochititsa chidwi ndi mgwirizano wa mzere ndi muzu wapakati wa nthawi yowumitsa monga momwe tawonetsera mkuyu 3C, kusonyeza kuti kusintha kwa conductivity kumagwirizana mwachindunji ndi kusintha kwa madzi oundana a adsorbed pa silika ndi kuti kuchotsedwa kwa madzi apamtunda ndi kufalikira kochepa.Zindikirani kuti "kuyanika" kumangochitika pamalo otseguka pomwe RH imakhala yotsika kuposa ya ayezi wolingana.Ma conductivity sanasinthe chodziwika, mwachitsanzo, m'maselo otsekedwa omwe amagwiritsidwa ntchito poyezera kutentha.

Kudalira kwa kutentha kwa nano-SCE kunayesedwa nthawi zosiyanasiyana za kuyanika mu bokosi la glove.Pamene conductivity ya nano-SCE yowuma inayandikira ya ILE, mbiri yopitirira σi motsutsana ndi 1 / T ya mesophase conductivity pang'onopang'ono inasintha kukhala mbiri ya ILE, ndikuwululanso dontho lozungulira malo ake osungunuka (mkuyu. S3).Kuwona uku kumathandiziranso lingaliro loti madzi oundana amakhala ngati gawo lothandizira kulumikizana ndi ILE, zomwe zimapangitsa machitidwe a mesophase mu nano-SCE.Chifukwa chake, gawo logwira ntchito likachotsedwa, ILE imangokhala yotsekeredwa mu membrane ya mesoporous oxide.

Miyezo ya zenera lokhazikika la electrochemical imatsimikizira kuti madzi oundana mu nano-SCE ndi okhazikika, popeza palibe nsonga zochepetsera madzi kapena oxidization zomwe zinawonedwa pa inert TiN electrode (mkuyu 2) kapena pa TiO2 yopyapyala-filimu electrode, yomwe imachita mosiyana. monga electro-chothandizira kuchepetsa madzi.M'malo mwake, mphamvu ya electrochemical ya nano-SCE ndi yofanana kwambiri ndi ya ILE ndipo motero imachepetsedwa ndi okosijeni wa TFSI- pa electrode potentials> 4.3 V ndi kuchepetsa TFSI- ndi BMP + pa kuthekera <1 V motsutsana ndi Li +/Li (33).Poyerekeza, voltammogram ikuwonetsedwa kwa ILE yokhala ndi 5 kulemera % (wt%) madzi owonjezera (zofanana ndi za nano-SCE; onani tebulo S1).Pankhaniyi, nthambi ya cathodic yochepetsera madzi imayesedwa mwamsanga potsatira Li-intercalation nsonga ya anatase pa 1.5 V motsutsana ndi Li +/Li.

Kukhazikika kwamafuta ndi (electro) kwa nano-SCE kumatsimikiziridwa ndi ILE filler.Kusanthula kwa Thermogravimetric (TGA) kunawonetsa kukhazikika kwa kutentha kwa SCE ndi ILE mpaka 320 ° C, mosasamala kanthu za chiwerengero cha ILE-to-silica (mkuyu S4).Pamwamba pa kutenthaku, Li-TFSI ndi BMP-TFSI zimawola kotheratu ku zigawo zosasunthika, ndipo matrix a silica okha amakhala mozungulira 450 ° C.Kuchuluka kwachulukidwe kotsalira pambuyo pakuwola kwamafuta kumagwirizana bwino kwambiri ndi gawo la silica mu SCE.

The nano-SCE sanasonyeze bwino microstructure mu kupanga sikani elekitironi maikulosikopu (SEM) kupatula pa yosalala pamwamba ndi zina silika yamawangamawanga peeking kunja (mkuyu. S5).Kuchulukana kwapadera kwa SCE kunatsimikiziridwa ndi helium pycnometer ndipo inali pafupi 1.5 g/cm3 pamitengo yonse ya x (tebulo S1).Matrix onse a silika adawululidwa ndi kutulutsa kotopetsa kwa ILE mu zosungunulira (onani Zida ndi Njira).Mwa kuyanika mosamala pamalo ovuta kwambiri a CO2, ma airgel monoliths osasunthika atha kupezeka ngati omwe akuwonetsedwa mkuyu 1A.Kuyang'ana kwa SEM kukuwonetsa scaffold ya silika ya mesoporous yokhala ndi 10- mpaka 30-nm pore diameter, yomwe imakutidwa ndi ma macropores akuluakulu a 100 mpaka 150 nm, monga tikuwonera mkuyu 1 (B ndi C).Mkulu-kusamvana kufala elekitironi maikulosikopu (TEM) (mkuyu. 1D) patsogolo poyera ndi microstructure wopangidwa ndi odzaza kwambiri silika nanoparticles.Avereji ya tinthu tating'onoting'ono tinthu tating'onoting'ono tomwe timatulutsa timayambira 7 mpaka 14 nm pamitengo ya x pakati pa 0.5 ndi 1.5.

Malo enieni a pamwamba [Brunauer-Emmett-Teller (BET)], porosity, kukula kwa pore, ndi kukula kwa pore kunatsimikiziridwa ndi N2 adsorption / desorption miyeso (tebulo S1 ndi mkuyu. S6).Kugwa pang'ono kwa kapangidwe kake ndi kuchotsedwa kosakwanira kwa adsorbed ILE kumatha kuyimira molakwika manambala.Kusamala m'zigawo za madzi ayoni ndi kuyanika pang'onopang'ono ntchito supercritical CO2 anapereka Komabe, odalirika zotsatira pafupi ndi porosity kuyembekezera masamu kuchokera voliyumu kachigawo ILE kuti silika (mkuyu. 1).BET pamwamba dera ranges pakati 800 ndi 1000 m2/g.Kukula kwa pore komwe kumachokera kumalo otsetsereka a isotherm kunali pakati pa 7 ndi 16 nm.Kuonjezera apo, kachigawo kakang'ono ka ma pores akuluakulu mpaka pafupifupi 200 nm adayesedwa (mkuyu. S6), malinga ndi kuwonetsetsa kwa SEM.Kutalika kwa pore kumayenderana bwino kwambiri ndi kuwirikiza kofanana kwa ILE wosanjikiza wotengedwa kuchokera ku gawo la voliyumu ya ILE ndi BET pamwamba, kutanthauza kuti masopores amadzazidwa kwathunthu ndi ILE.

Malo omwe adanenedwa a BET ndi a mesopores ndi macropores okha.Kwa matrix otsukidwa acetone, ma micropores (~ 0.6 nm) adayesedwanso.The ma micropores amapezeka pakati pa munthu silika nanoparticles kupanga dongosolo monga mmene TEM chifaniziro cha Mkuyu 1D.Malo owonjezera ochulukirapo pakati pa 650 (x = 0.5) ndi 360 m2 / g (x = 1.5) akuyerekezedwa (tebulo S1).

Mawonekedwe a FTIR ndi Raman amawonetsa umboni womveka bwino wamagulu a silanol okhala ndi mamolekyu amadzi owundana amadzi owundana pamtunda wapamwamba kwambiri wa silika wokhala ndi malo ogwira mtima kwambiri opitilira 1400 m2/g poganizira ma micropores, mesopores, ndi macropores.Pakati pa ziro ndi ma monolayers atatu amadzi amawerengedwa kuchokera kumadzi ochulukirapo mu nano-SCE ya x <1.75.Pakuti planar silika, woyamba monolayers atatu adsorbed madzi ndithudi amaonedwa osasunthika ndi olimba ngati chifukwa cha amphamvu hydrogen kugwirizana kwa OH-zinatha pamwamba (32) (onani mkuyu. S2).Kutambasula kwa O─H komwe kumalumikizidwa ndi silanol hydrogen yolumikizidwa ndi madzi oundana kumapezeka pa 3540 cm−1 mu mawonekedwe a FTIR.Ma nano-SCE onse amawonetsa, nsonga yodziwika bwino pa 3540 cm−1 ya madzi oundana pambuyo poyanika vacuum komanso mutatha kuyanika mu bokosi la glove (mkuyu 2).Ngakhale kuti agwirizane nano-SCE pa 0.0005% RH (magulovu bokosi), Raman spectroscopy akadali anasonyeza pamaso osachepera tsankho monolayer (mkuyu. 4B).Monolayer wachinayi pa silika wa planar amakhulupirira kuti ndi wosanjikiza, kutanthauza kuti akadali adsorbed ndi zoletsedwa koma akhoza kuyenda.Kuyambira gawo lachisanu kupita mtsogolo, madziwo amakhala oyenda komanso ngati madzi.Madzi ngati amadzimadzi aziwoneka pamafunde apamwamba kwambiri mu sipekitiramu ya FTIR chifukwa cha kutsika kwa H-bonding m'madzi amadzimadzi.Kwa nano-SCE yowonekera ku 60% RH, 3540-cm−1peak ikuwonetsadi kugwedezeka kwina kosinthidwa kupita ku manambala okwera chifukwa chamadzi owonjezera amadzimadzi.Chochititsa chidwi pankhaniyi ndi kuyesa kumene chitsanzocho chinawonekera ku 30% RH, popeza palibe madzi amadzimadzi omwe akuyembekezerabe pa silika pa chinyezi ichi (mkuyu. S2).Pachitsanzo ichi, nsonga ya 3540 cm−1 yokha yamadzi a ayezi imawoneka mu FTIR.Kuphatikiza apo, palibe nsonga yamadzi yaulere yomwe idapezeka pa 1635 cm−1 ngakhale patatha masiku 4 pa 30% RH.Izi zikutanthauza kuti madzi samatengedwa ndi hygroscopic Li-TFSI kusungunuka mu hydrophobic BMP-TFSI kamodzi nano-SCE zouma ndi vacuum mankhwala.Chifukwa chake, madzi aliwonse owonjezera mu SCE adzakhala adsorbed pamtunda wa silika wa OH.Chifukwa chake, ponena za silika ya planar, matrix a silika a SCE ali ofanana ndi kuthamanga pang'ono kwa madzi m'chilengedwe.

Kuti muyese lingaliro ili mowonjezereka, ion conductivity ya nano-SCE (x = 1, 1.5, ndi 2) inayesedwa pa% RH yosiyana;zitsanzo anali poyera kuti ankalamulira osakaniza youma ndi wothira mpweya N2 mu bokosi magolovesi kwa 2 masiku kulola adsorbed madzi Kuphunzira kufika mgwirizano (mkuyu. 3D).Pazigawo za ~ 0% RH, ma conductivity a nano-SCE yofanana mu bokosi la glove adatengedwa.Chodabwitsa n'chakuti, maonekedwe a ion motsutsana ndi RH (%) adatsata khalidwe loyembekezeka la madzi adsorption pa planar silica (mkuyu S2).Pakati pa 0 ndi 30% RH, ma conductivity akuwonjezeka ndi kuwonjezeka kwa RH.monga kuyembekezera kuwonjezeka kwa adsorbed ayezi wosanjikiza kachulukidwe ndi makulidwe (zogwirizana ndi chimodzi kapena atatu zigawo za ayezi pa planar silica).Dziwani kuti FTIR inasonyeza kuti palibe madzi aulere omwe analipo mu nano-SCE kwa masiku angapo pa 30% RH.Kusintha kumawoneka mozungulira 50% RH, yolingana ndi mikhalidwe yomwe madzi osinthika adsorbed amayembekezeredwa pa pulani ya silika.Pamapeto pake, kuwonjezereka kwapadera kwa ma ion conductivity kumapezeka ku 60% ndi chinyezi chapamwamba kumene, mofanana ndi silika ya planar, tsopano, komanso madzi osakanikirana amadzimadzi amatha kupangidwa pakati pa silika ndi ILE yophatikizidwa.Ndi FTIR, madzi amadzimadzi amadzimadzi pamadzi oundana tsopano akudziwika ndi kusintha kwa silanol / ayezi / madzi kugwedezeka kwapamwamba kupita ku mphamvu zapamwamba (mkuyu 2A).Kusintha komwe kumawonedwa mu conductivity ndikosinthika;motero, nano-SCE imatha kukhala ngati sensa ya chinyezi ndi Li-ion electrolyte.Kuchokera mkuyu 3D, ion conductivity ya nano-SCE mwamsanga pambuyo vacuum anneal limafanana ndi equilibrium hydrated silica ya ~ 10% RH.The ma ion conductivity kuti machulukitsidwe m'zipinda zowuma (~ 0.5% RH) angakhale pafupi 0.6 mS/cm (kwa x = 2).Kuyesera uku kukuwonetsa momveka bwino momwe madzi amachitira pamayendedwe a ion.Kwa RH> 60%, ma ion conductivity apamwamba amatha kufotokozedwa ndi kufalikira kwachangu kwa Li+ wosungunulidwa kudzera pamadzi ngati madzi.Komabe, ngati pali madzi oundana olimba, kufalikira kwa Li + ion kudzakhala kufalikira kwamtundu wokhazikika ndipo motero pang'onopang'ono kusiyana ndi madzi a ionic omwe.M'malo mwake, kupititsa patsogoloku kumatheka chifukwa cha kuwonjezereka kwa ma anions organic ndi ma cations a Li-mchere ndi ma ionic madzi mamolekyu, monga momwe zafotokozedwera mu chitsanzo pansipa.

Ife akamufunsirire chitsanzo kumene ayoni madzi mamolekyu ndi adsorbed pa silika pamwamba kudzera H-milatho ndi immobile ayezi wosanjikiza pa magulu silanol (mkuyu. 4).The intrinsic chikhalidwe cha hydrolysis condensation anachita amapereka apamwamba silanol kachulukidwe (4 × 1014 kuti 8 × 1014 cm−2, amene amafanana bwino ndi kachulukidwe wa monolayer umodzi wa ayezi ndi ~ 8 × 1014 madzi mamolekyu pa cm2) (34).Umboni wa kuyanjana kwa mamolekyu pakati pa ma atomu a O a ma anion a TFSI ndi silika waperekedwa ndi FTIR, yomwe ikuwonetsa kuwirikiza kawiri kwa nsonga ya O═S═O pa nano-SCE yonse poyerekeza ndi ILE reference (Mkuyu 4A; mawonekedwe athunthu. mkuyu S8).Kusintha kwa nsonga yowonjezera ndi pafupifupi −5 cm−1 kuchokera ku 1231 cm−1 kumasonyeza kugwirizana kwa magulu a O═S═O osachepera gawo la anions a TFSI.Choncho, H-kugwirizana kwa TFSI anions pa madzi oundana amaganiziridwa.Pambuyo pake, ma cations akulu a hydrophobic BMP amalumikizana ndi wosanjikiza woyamba wa TFSI, kumaliza gawo loyamba la ma adsorbed a mamolekyu amadzi a ionic.Pankhani ya ayezi, mamolekyu a BMP-TFSI amaganiziridwa kuti ndi osasunthika, motero amakulitsa mawonekedwe oundana ngati ayezi pamtunda wa silika.Monga TFSI anion ili ndi gulu la symmetric O═S═O, atomu imodzi ya okosijeni imatha kuyanjana ndi hydroxylated silica pamwamba pomwe ina imapanga mfundo zomata za ma cations a BMP.TFSI anion ilinso ndi magulu awiri a O═S═O, kutsimikizira kutsatsa kolimba komanso kuyitanitsa kolimba kwa anion monolayer.Adsorption ndiyothandiza kwambiri ngati pali ayezi wandiweyani wokhala ndi kachulukidwe kakang'ono kwambiri ka magulu a OH ngati malo omatira.Pamaso pa magulu a silanol okha, kutsatsa sikungakhale kokwanira kuti apange wosanjikiza wosalekeza wa adsorbate.Kuphatikiza apo, kuchulukirachulukira kwa ma ice monolayers kumadziwika kuti kumawonjezera mphamvu ya hydrogen bond (35).Dziwani kuti kuyanjana kwa mamolekyu pakati pa BMP cation ndi TFSI monolayer yolamulidwa idzakhala yosiyana ndi yamadzimadzi a ionic pomwe TFSI anion ili ndi ufulu wozungulira ndipo palibe polarization kuchokera pansi.Mlandu wa cation yayikulu ya BMP imagawidwa pa maatomu ambiri ndikuyika ma bond amkati komanso kulumikizana kwa ma cell ndi chilengedwe chake chamankhwala komanso, makamaka, adsorbed TFSI anion.Kugwirizana kwa H pakati pa O-gulu la TFSI anion ndi OH-kutha kwa ayezi tsopano kumayambitsa dipole pamwamba pa wosanjikiza woyamba, ndikupangitsa kuyitanitsa kwa ma cell mwa mayanjano.Amakhulupirira kuti pakadali pano, mamolekyu ang'onoang'ono a Li-TFSI amatsitsa gawo la molekyulu pomwe TFSI anion tsopano imalipiritsa ndalama zotsalira za dipolar zamtundu umodzi kapena zingapo za BMP kumtunda, kumasula mgwirizano wake ndi Li. ion.Mwanjira iyi, kuchuluka kwa Li + yaulere kumachulukitsidwa pamawonekedwe awa, zomwe zimatsogolera kumayendedwe apamwamba a ion.Chifukwa chake, magawo oundana owundana komanso owundana kenako amayambitsa dipole lalikulu lomwe lili ndi mtengo wotsalira wochulukirapo kuti ulipire, ndikupatsanso kukhazikika kwa Li + kwaulere kotero kuti ma ion conductivity.

Pamwamba pa adsorbed ILE wosanjikiza, mwina ILE wosanjikiza wina akhoza adsorb ofanana ndi ayezi multilayers pa silika kapena dipole kukoka kwa ayezi wosanjikiza ndi wofooka kwambiri ndipo mopepuka womangidwa ILE pamwamba, amene ndiye akhoza kupereka madzi-ngati conduction kwa. ma Li + ions otulutsidwa m'munsi adsorbed wosanjikiza (mkuyu 4C).Kusintha kwa ndende ya Li + ion yaulere kunatsimikiziridwa ndi miyeso yonse ya NMR ndi Raman spectroscopy.Miyezo ya Raman imawonetsa mosadukiza kuti gawo lalikulu la ma ion a Li + aulere alipodi mu nano-SCE yokhala ndi madzi oundana ambiri omangika ku silika (mkuyu 5).Raman amayesa kuyanjana kwa cation ndi TFSI pofufuza kugwedezeka kwa gulu la N la TFSI anion (36).Mumadzi oyera a BMP-TFSI a ionic, nsonga imodzi yokha pa 741 cm−1 ikuwoneka.Pankhani ya ILE yoyera, nsonga yowonjezera ikuwoneka pa 746 cm-1 pomwe ma anions awiri a TFSI amagwirizanitsa ndi Li + ion imodzi [onani mawerengedwe a density functional theory (DFT) mu Zida ndi Njira].Kwa ma nano-SCE onse, nsonga yapamwamba pa 746 cm−1 ndi yofooka kuposa ya ILE, kusonyeza kachigawo kakang'ono ka Li-TFSI ndipo, chifukwa chake, gawo lalikulu la ma Li + cations omwe sali ogwirizana kapena aulere.Chisomocho chimachepa kwambiri kwa iwo a nano-SCE omwe amawonetsa kukweza kwapamwamba kwambiri, mwachitsanzo, omwe ali ndi ayezi wokhuthala kwambiri.Kwa nano-SCE pa mgwirizano mu bokosi la magolovu, komabe, kachigawo kakang'ono ka Li + kaulere kamayesedwa ngakhale kakang'ono kwambiri kusiyana ndi zitsanzo za vacuum-annealed.Chiŵerengero cha nsonga zapamwamba za 746 pa 741 cm−1 kusintha kwa Raman ndiye muyeso wa chiŵerengero chaulere kwa TFSI-ogwirizana ndi Li-ion (mkuyu 5B).Kuchulukirachulukira kwa kagawo kakang'ono ka Li+ ion kagawo kakang'ono ka x mtengo kumatsata njira yopititsira patsogolo kadulidwe ndi mtengo wa x mumkuyu 3B, zonse za vacuum zouma nano-SCE (tsiku 0) ndi SCE pakufanana ndi kuuma kwa bokosi la glove (tsiku. 138).

(A) Mawonekedwe a Raman a madzi a ionic (IL; mzere wabuluu wokhala ndi madontho) ndi ILE reference (ILE; mzere wa madontho) wa nano-SCE wokonzedwa (vacuum dry) wokhala ndi ma x 0.5 (wobiriwira), 1.5 (yellow) , ndi 2 (bulauni) ndi nano-SCE (x = 1.5) kuwonjezera zouma mu bokosi la magolovesi kwa masiku 30 kapena pafupi machulukitsidwe pa 0.0005% RH (wofiira).Mizere yoyima imalemba kusintha kwa Raman kwa TFSI komwe N likulu yake imalumikizidwa ku Li+ (746 cm−1) ndipo osalumikizidwa ku Li+ (741 cm−1), motsatana.(B) Chiyerekezo chaulere cholumikizira Li + cha nano-SCE monga chopangidwira (zouma zouma, zozungulira zakuda) ndikuwonjezera zouma m'mabokosi amagetsi okhala ndi 0.0005% RH kwa masiku 30 (ma diamondi abuluu), molingana ndi chiŵerengero cha mphamvu yophatikizika ya Nsonga za Raman (746 cm−1 kupitirira 741 cm−1).(C) PFG-NMR-yotengedwa ndi Li + yodziyimira yokha ya nano-SCE (ma diamondi ofiira) ndi ILE ref.(mabwalo akuda) ngati ntchito ya kapitawa pakati pa maginito a gradient maginito.Zisonyezo zapamwamba pazithunzi za Raman zidafaniziridwa pogwiritsa ntchito kuwerengetsa kwa DFT.

Kuchokera ku pulsed-field gradient NMR (PFG-NMR), choyezera chodziyimira pawokha chamitundu yosiyanasiyana yamtundu wa Li-ion chidatsimikiziridwa ngati ntchito yanthawi yayitali pakati pa gradient magnetic field pulses ∆ kwa ILE liquid reference and for nano- SCE (x = 1.5) ndi ma ion conductivity omwewo a 0,6 mS / cm (mkuyu 5C).Li + yodziyimira payokha yodziyimira payokha muzofotokozera za ILE inali yosasintha, kuwonetsa kuti mtundu umodzi wokha wa Li + wokhala ndi kuyenda kofanana kwambiri umapezeka mumadzimadzi.Kwa nano-SCE, chigawo chodziphatikizira chokhacho chinasiyana ndi ∆ ndipo chinaposa ILE mwachidule ∆, kusonyeza kukhalapo kwa mitundu yothamanga kwambiri yomwe imayankha pakapita kanthawi kochepa pakati pa maginito a maginito.The gradient mu self-diffusion coefficient imasonyeza kuti pafupi ndi kuwonjezeka kwa ndende ya Li-ion yaulere, monga momwe tafotokozera kuchokera ku Raman spectroscopy, mphamvu yoyambitsa kufalikira imatsitsidwanso mu mawonekedwe a mesophase.Izi zimathandizira kukweza kwa ma conductivity komwe kumayambitsidwa ndi (zambiri) ma Li + ions aulere mu gawo la mesophase.Pautali ∆, coefficient yodzipatulira inali yotsika kuposa ya ILE reference.Izi zimagwirizana ndi kutsika kwa ion kwa bokosi la glove-saturated nano-SCE poyerekeza ndi ILE.ILE yomwe ili pakatikati pa mesopores idzakhala ndi viscosity yapamwamba chifukwa choletsa kuyenda kwa maselo.Chifukwa chake, kupititsa patsogolo popanga ma Li-ion othamanga kwambiri pamawonekedwe a silika/ice/ILE kuyenera kuchulukitsa kuchepa kwa ma conductivity pakatikati pa pore.Izi zikufotokozera kusowa kwa kupititsa patsogolo machitidwe a tinthu tating'onoting'ono pomwe ma interfaces samapereka kukwezedwa kokwanira kwa ion conduction (mkuyu. S1).

Kukhazikika kwa electrochemical kwa nano-SCE motsutsana ndi zitsulo za lithiamu kunayesedwa pogwiritsa ntchito makonzedwe a electrode atatu (chitsanzo cha khwekhwe chikuwonetsedwa mkuyu. S7).Makhalidwe omwe alipo panopa a Li / SCE (x = 1.5) ndi Li / ILE theka la selo akuwonetsedwa mu Chithunzi 6A.Ponena za zenera la electrochemical mu Chithunzi 2, electrochemistry imakhala yochepa ndi ILE filler.Kusintha kwa lithiamu plating ndi kuvula kumawonedwa.Khola olimba electrolyte interphase (SEI) wosanjikiza aumbike pa zitsulo lifiyamu ndi RSEI pafupifupi 0,9 kilo-ohm · cm2, udindo waukulu IR dontho mu pamapindikira iU pa onse cathodic ndi anodic mbali.Mawonekedwe a cathodic muzitsulo zoyera za ILE sizinawonetsere hysteresis mpaka -2.5 mA / cm2.Komabe, kusungunuka kwa anodic kunawonetsa chiwongola dzanja chokhazikika chokhala ndi 0.06 mA/cm2 yokha.Nthambi yamakono ya cathodic pa mawonekedwe olimba a Li / SCE sanawonetsere kugwedezeka kwa mafunde a cathodic osachepera -0.5 mA / cm2.Kukana kwa SEI kunali, komabe, pafupifupi kawiri.Momwemonso, nsonga ya anodic inali yotsika ndipo nsonga yokhazikika pambuyo pa nsonga ya anodic passivation inali 0.03 mA / cm2, theka lokha la yankho la ILE loyera.Mapangidwe a SEI ndi zigawo zodutsa mu pores za SCE zimachepetsa zomwe zilipo pa lithiamu zitsulo.Ma voltammogram onse a Li/ILE ndi Li/SCE ma elekitirodi anali kubwezeredwa pa kangapo, kusonyeza kuti anodic passivation wosanjikiza ndi mankhwala SEI wosanjikiza ndi zosinthika ndi okhazikika.Ma kinetics osungunuka pang'onopang'ono pa mawonekedwe a Li/SCE amachepetsa kwambiri magwiridwe antchito a theka-maselo opangidwa ndi Li metal anode pansipa.

(A) Cyclic voltammogram ya nano-SCE (x = 1.5, yopangidwa pambuyo poyanika vacuum) (yofiira) ndi ILE reference (yakuda) yoyezedwa ndi ma elekitirodi atatu ndi Li monga ogwira ntchito, otsutsa, ndi maelekitirodi (kukaniza kwa SEI akuyerekeza kuchokera Kutsika kwa IR pa cathodic current ndi 0.9 ndi 1.8 kilo-ohm·cm2 kwa ILE ndi SCE, motsatana).(B) galvanic charge / discharge curves of Li/SCE (x = 1)/100-nm thin-film LiMn2O4 selo kwa mikombero isanu pa C-mitengo ya 1C, 5C, ndi 20C.(C) Cyclic voltammograms ya Li/SCE/40-μm Li4Ti5O12 ndi Li/SCE/30-μm LiFePO4 ma cell electrode powder (1 mV/s).(D) Galvanic charge/kutulutsa ma curve a Li/SCE/40-μm Li4Ti5O12 powder electrode pa 1C, 0.1C, 0.2C, ndi 0.02C.(E) Galvanic charge / discharge curves of Li/SCE/30-μm LiFePO4 powder electrode pa 1C, 0.5C, 0.2C, 0.1C, 0.05C, ndi 0.01C.(F) Mphamvu (zodzaza diamondi za delithiation ndi mabwalo otseguka a lithiation) motsutsana ndi chiwerengero cha Li/SCE/30-μm LiFePO4 ufa electrode;makulidwe a SCE m'maselo ndi pafupifupi 280 μm.Kachulukidwe ka LFP ndi LTO cathode ndi pafupifupi 1.9 ndi 11.0 mg/cm2, motero.(G) Kuthekera kuyerekeza ndi nthawi yokhotakhota ya stack ya Li/SCE/Li yoyendetsedwa pamiyeso ya 0.1, 0.2, 0.5, ndi 0.1 mA/cm2.(H) 1st, 10th, 125th, ndi polarization yotsiriza ya stack ya Li / SCE / Li yotsindika pa 0.1 mA / cm2, yowonetsedwa mu (G).Kwa (G) ndi (H), SCE ili ndi conductivity ya 0. 34 mS / cm, ndipo makulidwe a pellet ya SCE ndi 0.152 cm.

Kanema wopyapyala wa 100-nm LiMn2O4 (LMO) adagwiritsidwa ntchito ngati ma elekitirodi abwino kuyesa kukhazikika kwa nano-SCE ndi zinthu zama elekitirodi kwinaku akuchotsa zovuta zomwe zingachitike mu maelekitirodi ophatikiza tinthu (37).Mayendedwe apanjinga a filimu yopyapyala elekitirodi/SCE ikuwonetsa kukhazikika kwa mawonekedwe pakati pa ma elekitirodi ndi ma electrolyte.Muchitsanzo ichi chokhazikitsa filimu yopyapyala, imodzi yokha, yodziwika bwino, komanso yolumikizana ndi mawonekedwe a planar ilipo pakati pa electrolyte ndi electrode, mwachitsanzo, ndi nsanja yabwino yophunzirira electrochemistry ya mawonekedwe a electrolyte / electrode popanda kusintha kwa voliyumu. , etc. Komanso mu kuyesera uku, mlingo ntchito si malire ndi Li-foil counter electrode, monga kachulukidwe panopa (6 μA/cm2 kwa 1C) ndi pansi pa zokhazikika-boma anodic panopa mapiri kwa lifiyamu theka- selo (0.03 mA/cm2).Reproducible ndi khola malipiro / zokhotakhota kutulutsa analandira kwa cutoff voteji pa 4.3 V kwa C-mitengo pakati 1 ndi 20C kwa pa 20 m'zinthu (mkuyu. 6B).LMO ndi yosakhazikika mu electrolyte yamadzimadzi ya LiB.Mwachitsanzo, kuchepetsa mphamvu ndi 50% kunawonedwa pa filimu ya 100-nm LMO yotulutsidwa kwa mikombero 10 mu LiClO4/propylene carbonate electrolyte pa 1C (37).Zotsatira zathu zikuwonetsa kuti nano-SCE imagwirizana kwambiri ndi LMO kuposa ma electrolyte amadzimadzi.

Kuti tiwonetse kuphatikizidwa kwa nano-SCE, tinapanganso maselo a theka ndi Li4Ti5O12 (LTO) ndi LiFePO4 (LFP) ma electrodes a ufa.The kalambulabwalo njira anali dontho-kuponyedwa mu selo ndalama impregnate ma elekitirodi porous ndi anasiya kwa zina gelation pamaso iwo zouma ndi vakuyumu-annealed mofanana ndi pellets nano-SCE.Maselo amasonyeza khalidwe lifiya / delithiation wa maelekitirodi lolingana (mkuyu. 6C).Mafunde otsika kwambiri a LFP kuposa LTO ndi chifukwa cha kusiyana kwa makulidwe a zokutira.The mlingo ntchito pa mlandu / kutulutsa miyeso anali wochepa tsopano ndi Li-zojambula potsimikizira elekitirodi mbamuikha pa nano-SCE wosanjikiza anapanga pamwamba pa 30- kuti 40-μm-wandiweyani elekitirodi zokutira (mkuyu. 6, D ndi E).Selo ya LTO/nano-SCE/Li inafika pamlingo waukulu kwambiri wa 160 mA · ola / g pokhapokha pa C-rate ya 0.02C (mkuyu 6D).Mphamvu yofikirika imatsika kwambiri ndi C-rate yochepera 10% ya C-mitengo yokulirapo kuposa 0.1C.Mofananamo, selo la LFP / SCE / Li linafika pamtunda wake wa 140 mA · ola / g pa 0.01C (Mkuyu 6E).Chithunzi 6F chikuwonetsa kuchuluka kwa magwiridwe antchito amitundu yonse ya 30, kuwonetsa kukhazikika kwa ma cell.Zoyesererazi zikuwonetsa magwiridwe antchito a nano-SCE ngati Li-ion electrolyte komanso kuthekera kophatikizana m'maselo a Li-ion.

Kukhazikika kapena kusinthasintha kwa nano-SCE kudayesedwa pogwiritsa ntchito stack ya Li/SCE/Li symmetric stack.Iwo anazungulira kwa oposa 120 m'zinthu panopa osalimba 0.1 mA / cm2 kwa maola 0.5 (mkuyu. 6G) popanda nkhani kapena dendrite mapangidwe (mkuyu. 6H).Mphamvu ya polarization idakhala yaying'ono pakapita nthawi, kuwonetsa kusintha kwa kulumikizana.Komanso, selo anatsindika mpaka kachulukidwe panopa 0,5 mA / cm2, popanda mapangidwe lithiamu dendrites kapena zizindikiro za kuwonongeka kwa nano-SCE kapena mawonekedwe (mkuyu. 6G).Lifiyamu yachitsulo imadziwika kuti imapanga chitetezo cha interphase wosanjikiza kapena SEI pamwamba pake mu BMP-TFSI-based ILEs (27).Izi zimachitikanso pa mawonekedwe a lithiamu / nano-SCE;monga momwe tafotokozera mkuyu 6A, SEI ikhoza kukula pang'onopang'ono mkati mwa pores, kufotokoza kukana kwa SEI kwa nano-SCE kuposa ILE (onani pamwambapa).Umboni wa SEI wosanjikiza unapezedwa kuchokera ku IR spectra (mkuyu. S9).Mofanana ndi SEI ❖ kuyanika mu chakale LiB, amene zowonetsera graphite elekitirodi ku madzi electrolyte kupewa anachita zina, tikukhulupirira kuti SEI pano amateteza madzi ayezi wosanjikiza zina anachita ku zitsulo lifiyamu anode.Impedance spectra isanayambe komanso itatha polarization ya Li/nano-SCE (x = 1.5) kwa maola a 10 sanasonyeze kusintha kulikonse kwa kukana kwa electrolyte.Kuyeza kwapang'onopang'ono kwapang'onopang'ono kudzafunika kuti musamawononge kuyanika kwapang'onopang'ono kwa nano-SCE ndi zitsulo za lithiamu, koma zotsatirazi zikuwonetsa kale kuthekera kwake kwa cyclability yabwino ya SCE mu mabatire a lithiamu zitsulo-zochokera ku boma lolimba.Komabe, zokutira zopanga za interphase zitha kuganiziridwa kuti zikuwongolera mawonekedwe onse a impedance.

Tawonetsa kuti kukwezedwa kwa ma ion conduction pa silika wolumikizana ndi silika kumatha kutheka kudzera pakukhazikitsa gawo lamadzi la chemisorbed pamtunda wa silika wa OH.TFSI anions chemisorb pamadzi ogwiritsira ntchito madzi kudzera mu mgwirizano wa haidrojeni ndi gulu lofananira la O═S═O.Madzi pamwamba pamadzi ndi osasunthika chifukwa chake amakhomereranso TFSI wosanjikiza pamwamba.Ma cations akulu a BMP amalumikizana ndi TFSI monolayer, ndikuyambitsa kuyitanitsa kwa TFSI-BMP pamtunda.Timakhulupirira kuti pang'onopang'ono gelation m'malo amadzimadzi ndi kuyanika kwapang'onopang'ono kumathandizira kupanga mapangidwe amadzi ogwirira ntchito ndi gulu la ma ion organic pamwamba pake.Monga woyamba TFSI anion wosanjikiza amagawana mbali ya mlandu wake zoipa ndi silika hydroxylated, ndi BMP cation wosanjikiza pamwamba adzafuna kugwirizana ndi TFSI anion wina, kumene BMP angapo akhoza kugawana malipiro awo uncompensated ndi TFSI mmodzi (mwina atatu mpaka mmodzi monga mu chiŵerengero cha IL kwa Li-TFSI mu ILE).Monga mamolekyu amchere a Li-TFSI ali ndi njira yoyandikira kwambiri, ma ion a Li + adzasiyanitsidwa ndikumasulidwa kuti afalikire mwachangu pamawonekedwe awa.Kuti ma conduction apitirire, mitundu ya Li + yaulere iyi imafunikira gawo limodzi lowonjezera la madzi a ionic kuti lidutse.Pachifukwa ichi, nano-SCE yokhala ndi mtengo wochepa wa x wa 0.5 sinawonetsere kupititsa patsogolo, monga momwe ILE voliyumu / silika pamwamba pake ndi yokwanira pa monolayer imodzi yokha yotsekedwa.

Zinawonetsedwanso kuti madzi olimba ngati pamwamba kapena madzi oundana sakhala ndi electrochemically yogwira ntchito.Panthawiyi, sitingathe kusiyanitsa kuti madzi oundana omwe amalumikizana mwachindunji ndi electrode pamwamba sakuchitapo kanthu.Komabe, tidawonetsa kuti kufalikira kwamadzi pamtunda kumakhala pang'onopang'ono ndipo motero ndikosavuta kuzindikira.Timazindikira kuti kuipitsidwa kwa madzi, ngakhale kuli kochepa, kumakhala kodetsa nkhawa nthawi zonse, ndipo kuyesa kwa moyo wautali kokha kungapereke yankho lotsimikizika ngati madzi amangika mokwanira.Komabe, zigawo zina zogwira ntchito zomwe zimapereka kukwezedwa kofananira kapena zokulirapo tsopano zitha kupangidwa.Pachifukwa ichi, gulu la Li lawonetsa kale kuthekera kwa glycidyloxypropyl wosanjikiza ngati gulu logwira ntchito (18).Madzi oundana amachokera ku silika ndipo motero ndi oyenera kuphunzira momwe magwiridwe antchito amagwirira ntchito pakukweza ma ion conduction mwadongosolo, monga momwe zidawonetsedwera bwino apa.Komanso, mesophase wosanjikiza ndi dipole ake adzadalira okusayidi ndi pa adsorbed organic mamolekyu motero akhoza kuchunidwa ndi onse.Mu labotale, tawonetsa kale kusiyana kwakukulu pakukweza ma ion conduction amadzimadzi osiyanasiyana a ionic.Kuphatikiza apo, mfundo yomwe ikuwonetsedwa ndi yodziwika bwino yokhudzana ndi ma ion conduction ndipo imatha kugwiritsidwanso ntchito pamakina osiyanasiyana a ayoni oyenera, mwachitsanzo, pamabatire a sodium, magnesium, calcium, kapena aluminiyamu.Pomaliza, ma electrolyte a nanocomposite okhala ndi mawonekedwe owongolera omwe akuwonetsedwa pano ndi lingaliro m'malo mwa chinthu chimodzi, chomwe chingathe kupitilira (nano) chopangidwa ndi zinthu zomwe zimafunidwa za ion conduction, nambala yoyendera, zenera la electrochemical, chitetezo, ndi mtengo wamibadwo yamtsogolo ya batri. .

Nano-SCE idakonzedwa pogwiritsa ntchito njira ya sol-gel.Lithium bis(trifluoromethylsulfonyl)imide Li-TFSI;Sigma-Aldrich;99.95%), 0.5 ml ya deionized H2O, 0.5 ml ya TEOS (Sigma-Aldrich; 99.0%), 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide (BMP-TFSI; Sigma-Aldrich; 9815%). ml ya PGME adasakanizidwa mu botolo lagalasi.Chiŵerengero cha molar, x, pakati pa [BMP][TFSI] ndi TEOS mu chisakanizocho chinali chosiyana pakati pa 0.25 ndi 2. Chiŵerengero cha molar cha Li [TFSI] ndi [BMP][TFSI] chinakhazikitsidwa pa 0.33: 1.Kuchuluka kwa Li[TFSI] ndi [BMP][TFSI] kudatsimikiziridwa kuchokera ku mareyishoni awa.Mwachitsanzo, pamene x = 1, zowonjezera [BMP][TFSI] ndi Li[TFSI] mu yankho zinali 0.97 ndi 0.22 g, motsatana.Zosakanizazo zinagwedezeka kwa mphindi 1 kuti apange njira za monophasic.Njira zothetsera izi zinasungidwa muzitsulo zotsekedwa popanda kusonkhezera kupanga ma gels mu chipinda chowongolera kutentha ndi chinyezi (SH-641, ESPEC Corp.) ndi kutentha ndi RH% yoyikidwa pa 25 ° C ndi 50%, motero.Kutengera x, zosakanizazo zidatenga, pafupifupi, masiku 5 mpaka 9 kuti apange gel omveka bwino.Pambuyo pa gelation, Mbale zokhala ndi 2.4- mpaka 7.4-ml gel osakaniza zidayamba zowumitsidwa pa 40 ° C kwa masiku anayi athunthu pakupanikizika pang'ono (80 kPa) kenako ndikusunthira mu uvuni wa vacuum kwa maola 72 pa 25 ° C.Pamene chinyontho chotsaliracho chinachotsedwa, chopukutiracho chinachepa pang'onopang'ono kuchokera kukakamiza koyambirira kuzungulira 50 Pa mpaka kukakamiza komaliza kwa 5 Pa pambuyo pa tsiku la 1.Chifukwa cha kuchuluka kwa madzi ndi PGME zomwe zinayenera kuchotsedwa, ma pellets a SCE omwe adatuluka adatsika kuchokera ku 20% (x = 0.5) mpaka ~ 50% (x = 2) ya voliyumu yoyambirira ya gel.Kulemera kwa ma gels omwe adatulukawo adayezedwa ndi semimicro balance (SM 1245Di-C, VWR).

TGA idachitidwa pa Q5000 IR (TA Instruments, New Castle, DE, USA) pansi pa nayitrogeni.Panthawi yoyezera, zitsanzo zinatenthedwa mpaka 700 ° C pa kutentha kwa 2 ° C / min.FTIR spectrometry idachitidwa pogwiritsa ntchito Bruker Vertex 70 mu nambala yoweyula kuyambira 4000 mpaka 400 cm−1 munjira yopatsira.Iye pycnometry adachitidwa pogwiritsa ntchito Micromeritics AccuPyc II 1340.

Kuti muyeze ma ionic conductivity, kagawo kakang'ono ka SCE adatengedwa kuchokera ku vial ya amayi mkati mwa bokosi la glove lodzaza ndi Ar (0.1-ppm H2O ndi 0.1-ppm O2).Pafupifupi 23 μl ya SCE inadzazidwa ndi mphete ya polytetrafluoroethylene (PTFE) yokhala ndi 4.34-mm mkati mwake ndi 1.57-mm kutalika, kupanga pellet.Pellet mu mpheteyo idayikidwa pakati pa ma disks awiri osapanga dzimbiri (SS) (0.2 mm thick; MTI).Miyezo yosokoneza idachitidwa pogwiritsa ntchito PGSTAT302 (Metrohm), yokhala ndi matalikidwe a AC a 5 mV mumayendedwe oyambira 1 MHz mpaka 1 Hz.The ion conductivity (σi) idatsimikiziridwa kuchokera kumayendedwe apamwamba kwambiri ndi axis yeniyeni mu ziwembu za Nyquist.Pambuyo pa kuyeza kwa conductivity, nano-SCE pellet idaloledwa kuti iume mu bokosi la glove.Pakuyezera kudalira kutentha, milu ya SS/SCE/SS idasindikizidwa mu selo yandalama.Pambuyo kusindikiza, madutsidwe anakhalabe mosalekeza kwa masiku angapo (onani mkuyu. S3).Kutentha kwa selo yandalama kumayendetsedwa ndi jekete yotentha yokhala ndi kusamba kotentha pogwiritsa ntchito H2O/ethylene glycol ngati sing'anga yogwira ntchito.Poyamba ma cellwo anaziziritsidwa mpaka pafupifupi −15°C ndiyeno kutenthedwa pang’ono mpaka 60°C.

Kuchokera pa pellet iliyonse ya nano-SCE, pafupifupi 23 μl idabweretsedwa mu mphete (4.34-mm m'mimba mwake ndi 1.57-mm kutalika) poyezera magetsi mkati mwa bokosi lamagetsi lodzaza ndi N2 lokhala ndi chinyezi chowongolera.Mphete yokhala ndi SCE idayikidwa pakati pa ma disks awiri a SS (0.2 mm thick; MTI).Miyezo yosokoneza idachitidwa pogwiritsa ntchito PGSTAT302 (Metrohm) yokhala ndi matalikidwe a AC a 5 mV ndi ma frequency kuyambira 1 MHz mpaka 1 Hz yoyendetsedwa ndi pulogalamu ya Nova.Zitsanzozo zinasungidwa pamtengo uliwonse wa RH% kwa maola 48 isanayambe kuyang'aniridwa mpaka kukhazikika.Kukhazikika kwa ionic kwa mtengo wopatsidwa wa RH% (σi) kudatsimikiziridwa kuchokera kumayendedwe apamwamba kwambiri ndi ma axis enieni mu ziwembu za Nyquist.

Kapangidwe ka pellet yokhala ndi Li[BMP][TFSI] ILE komanso yopanda Li [BMP] [TFSI] ILE idawunikiridwa ndi SEM pogwiritsa ntchito chida cha Thermo Fisher Scientific Apreo pa 1.5 mpaka 2.0 kV pomwe imagwira ntchito mofananira ndi chojambulira chapawiri pogwiritsa ntchito chowunikira cha T1 ndi T2 mofananira. kusintha kwazithunzi zamoyo, ndipo chowunikira cha T2 chinagwiritsidwa ntchito pojambula zithunzi za SEM zowonetsedwa;chitsanzocho chinakhazikitsidwa pa tepi ya carbon conductive.TEM idapangidwa pogwiritsa ntchito Tecnai yogwira ntchito pa 300 kV.

ILE idachotsedwa pa pellet ya SCE m'njira ziwiri zosiyana.Njira imodzi yopezera silika waporous idachitidwa ndikumiza SCE mu acetone kwa maola 12 kuti muchotse Li[BMP][TFSI] ILE.Kutsuka uku kunabwerezedwa katatu.Njira ina inali yoviika SCE mu ethanol.Pankhaniyi, Mowa anachotsedwa ntchito madzi CO2 yovuta chowumitsira mfundo.

Zida ziwiri zosiyana zidagwiritsidwa ntchito poyanika kwambiri, zomwe ndi Automegasamdri-916B, Tousimis (njira 1) ndi chida chopangidwa ndi JASCO Corporation (njira 2).Pogwiritsa ntchito chida choyamba, kuyanika kumayamba ndi kuchepa kwa kutentha mpaka 8 ° C.Pambuyo pake, CO2 idatsukidwa m'chipindamo, ndikuwonjezera kukakamiza kwa 5.5 MPa.Mu sitepe yotsatira, CO2 inatenthedwa mpaka 41 ° C, ndikuwonjezera kupanikizika kwa 10 MPa, ndikusungidwa motere kwa 5 min.Pomaliza, mu gawo lokha magazi, kupanikizika kunatsitsidwa kwa nthawi ya 10 min.Pogwiritsa ntchito chida chopangidwa mwachizolowezi, njira yofananira idatsatiridwa.Komabe, nthawi ndi zovutazo zinali zosiyana kwambiri.Pambuyo poyeretsa, kupanikizika kunawonjezeka kufika ku 12 MPa pa kutentha kwa 70 ° C ndikukhalabe kwa maola 5 mpaka 6.Pambuyo pake, kupanikizika kunachepetsedwa pang'onopang'ono kuchokera ku 12 mpaka 7 MPa, 7 mpaka 3 MPa, ndi 3 mpaka 0 MPa pa nthawi ya 10, 60, ndi 10 min, motero.

Nayitrogeni physisorption isotherms anayesedwa pa T = 77 K pogwiritsa ntchito Micromeritics 3Flex surface characterization analyzer.Silika yopangidwa ndi porous idatulutsidwa kwa maola 8 pa 100 ° C pansi pa vacuum ya 0.1-mbar.Silika ya porous yochokera ku kuyanika kwakukulu idatulutsidwa kwa maola 18 pa 120 ° C pansi pa vacuum ya 0.1-mbar.Pambuyo pake, nitrogen physisorption isotherms anayesedwa pa T = 77 K pogwiritsa ntchito Micromeritics TriStar 3000 automated gas adsorption analyzer.

Miyezo ya PFG-NMR idachitidwa pogwiritsa ntchito JEOL JNM-ECX400.Mayendedwe olimbikitsa a echo pulse adagwiritsidwa ntchito poyezera kufalikira.Kuchepetsa kwamphamvu kwa echo, E, kumafotokozedwa mu equation (38)E=exp(−γ2g2δ2D(Δ−δ/3))(1)pamene g ndi mphamvu ya kugunda kwa gradient, δ ndi nthawi ya gradient. kugunda, ∆ ndi kapitawi pakati pa nsonga zotsogola za ma gradient pulses, γ ndi chiŵerengero cha magnetogyric, ndipo D ndi gawo lodzigawanitsa la mamolekyu.Ma coefficients odzipatulira okha adayerekezedwa ndikuyika ma echo ma sign omwe adapezedwa posintha ∆ ndi Eq.1. 7Li adasankhidwa kuti adziwe kufalikira kwa ion ya lithiamu.Miyezo yonse idachitidwa pa 30 ° C.

Kukhazikitsa kwa ma Raman spectroscopy kunali makina opangira kunyumba pogwiritsa ntchito argon ion yomwe imatha kuyatsidwa ndi kuwala kwa laser 458-nm komwe kumalumikizidwa ndi maikulosikopu ya Olympus IX71, ndipo kuwala kobalalika kumbuyo kudadutsa pa TriVista triple spectrometer setup (Princeton Instruments). ), yomwe idagwiritsidwa ntchito kufalitsa ma siginecha owoneka omwe amapezeka pogwiritsa ntchito kamera yamadzimadzi ya nayitrogeni yoziziritsa.Chifukwa cha kuyamwa kwakukulu kwa kuwala pamafundewa, mphamvu zochepa za laser zidagwiritsidwa ntchito kupewa kutentha kwa laser (<100 W · cm-2).

DFT ground-state geometry kukhathamiritsa ndi kusanthula pafupipafupi mawerengero anagwiritsa ntchito wotchuka B3LYP hybrid functional ndi 6-311++G** maziko seti, ndi Grimme's atomu-pairwise dispersion dispersion correction (39) ndi Becke-Johnson damping scheme (D3BJ), monga zakhazikitsidwa mu ORCA 3.0.3 (40).Zowonera za Raman zidapangidwa pogwiritsa ntchito ORCA, ndipo mawonekedwe azinthu zama cell adakwaniritsidwa pogwiritsa ntchito pulogalamu ya Avogadro (41) yokhala ndi zosintha zothandizidwa ndi ORCA.

Miyezo yonse ya electrochemical ndi kukonzekera kwachitsanzo kogwirizanako kunachitika mu bokosi la glove lodzaza ndi argon (PureLab, PL-HE-4GB-1800; <1-ppm O2 ndi H2O milingo) yopatulidwira mawonekedwe a electrochemical.Pellet ya SCE inayikidwa pa riboni ya Li (Sigma-Aldrich; 99.9%) yothandizidwa pa mbale yamkuwa monga electrode ya counter electrode ndi ma disks awiri a Li disk (5-mm m'mimba mwake) anayikidwa pamwamba pa pellet ya SCE kuti afotokoze ndikugwira ntchito. ma elekitirodi.Kukonzekera kukuwonetsedwa mkuyu.S7.Zikhomo za golidi zidagwiritsidwa ntchito polumikizana ndi zolembera za lithiamu ndi maelekitirodi ogwira ntchito.Miyezo ya cyclic voltammetry ndi impedance idachitidwa pogwiritsa ntchito PGSTAT302 (Metrohm) yoyendetsedwa ndi pulogalamu ya Nova.Cyclic voltammetry idapangidwa ndi sikelo ya 20 mV/s.Miyezo yosokoneza idachitidwa ndi matalikidwe a AC a 5 mV ndi ma frequency kuyambira 1 MHz mpaka 0.1 Hz.

Elekitilodi ya filimu yopyapyala ya 40-nm ya anatase ya TiO2 idayikidwa ndi atomic layer deposition (ALD) pa 300-mm silicon wafer yokhala ndi 40-nm TiN pansi yoyikanso ndi ALD.Ndi electrode yoyesera kwambiri yowonetsera Li-ion conductivity kupyolera mu electrolytes, monga TiO2 samavutika ndi kuwonongeka kwa mankhwala kapena kupsinjika kwa makina (palibe kusintha kwakukulu kwa voliyumu) panthawi yoyendetsa njinga.Kuti muyese selo la Li / SCE / TiO2, ma ILE-SCEs adadzazidwa ndi mphete ya PTFE ndi mainchesi a 4.3 mm ndi makulidwe a 0.15 cm;ndiye, mpheteyo idayikidwa pakati pa filimu ya Li ndi filimu ya TiO2.

Nano-SCE/thin-film elekitirodi theka stacks, ndi LMO electrode, anapangidwa ndi synthesizing filimu nano-SCE pa maelekitirodi.Chiwerengero chonse cha 150 μl cha x = 1.5 yankho, chokhala ndi masiku awiri, chinaponyedwa mu mphete yagalasi (m'mimba mwake, 1.3 mm) yoyikidwa pa mafilimu a electrolyte.Mpheteyo idasindikizidwa ndi parafilm, ndipo yankho limasungidwa m'chidebe chosindikizidwa chotere kuti gel osakaniza kwa masiku 4.Magulu opangidwa ndi gel / electrode motere adawumitsidwa kuti apange milu ya nano-SCE/electrode.Makulidwe a nano-SCE, otsimikiziridwa pogwiritsa ntchito micrometer, anali 300 μm.Pomaliza, chojambula cha lithiamu (1.75 mm wandiweyani, 99.9%; Sigma-Aldrich) adapanikizidwa pa nano-SCE / electrode stack ngati anode.Elekitilodi ya filimu yopyapyala ya 100-nm LiMn2O4 (LMO) idayikidwa ndi ma radio frequency sputtering pansi pa Ar flow pa silicon wafer yokutidwa ndi 80-nm Pt (DC sputtering)/10-nm TiN (ALD) pansi.Mundawuwu udasungidwa kwa mphindi 20 pa 800 ° C mumlengalenga wa oxygen.

Mafilimu a electrode a LiFePO4 (LFP) adakonzedwa ndi zokutira masamba.Choyamba, kaboni wakuda ndi LFP (2 mpaka 3 μm) adawonjezeredwa ku yankho lamadzi lomwe lili ndi carboxymethylcellulose (CMC) kuti apange chisakanizo chomwe chinasinthidwa pambuyo pake pogwiritsa ntchito chosakaniza mapulaneti.Kenako, mankhwala homogenized anali wothira madzi deionized ndi fluorinated acrylic latex (JSR, TRD202A) mu vakuyumu chosakanizira kupanga slurry kwa electrode ❖ kuyanika.Dothi lokonzekera lidaponyedwa pazitsulo za aluminiyamu kuti asungire mafilimu a electrode pogwiritsa ntchito chophimba chamasamba.Maelekitirodi onyowa omwe amakutidwa nthawi yomweyo amawunikiridwa mu uvuni wam'mlengalenga wokhala ndi mpweya wosasunthika pa 70 ° C kwa mphindi 10 ndipo adawumitsidwanso pa 140 ° C kwa maola 4 mu uvuni wosasunthika.Makanema owuma a elekitirodi anali ndi 91 wt % LiFePO4, 3 wt% wakuda wakuda, 2 wt % CMC, ndi 4 wt % TRD202A.Kukula kwa filimuyo ndi 30 μm (kutsimikiziridwa pogwiritsa ntchito micrometer ndi microscope ya electron).

Mafilimu a electrode a Li4Ti5O12 (LTO) anapangidwa pazitsulo zamkuwa mofanana.Kapangidwe ka maelekitirodi owuma ndi 85 wt % Li4Ti5O12, 5 wt% carbon black, 5 wt % CMC, ndi 5 wt % fluorinated acrylic latex (TRD2001A).Kutalika kwa filimuyi ndi 40 μm.

Yankho la SCE linaponyedwa pa filimu yochokera ku LFP ndi LTO electrode.Choyamba, 100 μl wa x = 1.5 yankho, zaka 2 masiku, anaponyedwa pa filimu elekitirodi, ndi awiri a 15 mm, anaika mu selo ndalama (#2032, MTI).Pambuyo pa SCE yopangidwa ndi gelled, filimuyo inaumitsidwa pa 25 ° C kwa maola 72 mu uvuni wa vacuum (<5 × 10-2 mbar) kuti apange nano-SCE ndi electrode stack.Makulidwe a nano-SCE anali 380 μm.Pomaliza, chojambula cha lithiamu chinapanikizidwa pazitsulo za SCE / electrode monga anode, ndipo selo lachitsulo linasindikizidwa.Miyezo ya electrochemical idapangidwa pogwiritsa ntchito Solartron 1470E potentiostat kutentha kwapakati.

Zowonjezera za nkhaniyi zikupezeka pa http://advances.sciencemag.org/cgi/content/full/6/2/eaav3400/DC1

Gulu S1.Mapangidwe a silika masanjidwewo mu nano-SCE powonjezera gawo la molar la madzi a ionic kupita ku silika (x mtengo) wotsimikizika kuchokera ku N2 adsorption/desorption kapena BET miyeso ndi kuwunika kwa TEM.

Imeneyi ndi nkhani yotseguka yoperekedwa pansi pa chilolezo cha Creative Commons Attribution-NonCommercial, chomwe chimaloleza kugwiritsa ntchito, kugawa, ndi kubereka mumtundu uliwonse, malinga ngati kugwiritsidwa ntchito kwake sikungapindule ndi malonda ndipo ngati ntchito yoyambayo ili yoyenera. otchulidwa.

ZINDIKIRANI: Timangopempha adilesi yanu ya imelo kuti munthu amene mukumupangira tsambalo adziwe kuti mumafuna kuti aliwone, komanso kuti si imelo yopanda pake.Sitijambula imelo iliyonse.

Funsoli ndi loyesa ngati ndinu mlendo kapena ayi komanso kupewa kutumiza sipamu zokha.

By 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 Meee.

Nthawi yotumiza: Jul-15-2020