Silica gel m nanocomposite electrolytes tare da interfacial conductivity gabatarwa wuce girma Li-ion conductivity na ionic ruwa electrolyte filler.

Canji zuwa batir Li-ion mai ƙarfi zai ba da damar ci gaba zuwa yawan ƙarfin kuzari na 1000 W·hour/lita da ƙari.Abubuwan da aka haɗa na matrix mesoporous oxide matrix da ke cike da abubuwan da ba su canzawa ionic ruwa electrolyte fillers an binciko su azaman ingantaccen zaɓi na electrolyte.Koyaya, sauƙi mai sauƙi na mafita na electrolyte a cikin pores masu girman nanometer yana haifar da ƙarancin haɓakar ion yayin da danko ya karu.Anan, mun nuna cewa ƙaddamarwar Li-ion na nanocomposites wanda ya ƙunshi mesoporous silica monolith tare da filler ion liquid electrolyte filler na iya zama sau da yawa sama da na tsarkakakken ion ruwa mai zazzagewa ta hanyar gabatarwar layin kankara na interfacial.Ƙarfin adsorption da yin oda na ƙwayoyin ruwa na ionic yana sa su zama marasa motsi da ƙarfi-kamar na tsaka-tsakin kankara da kanta.Wurin da ke saman Layer mesophase adsorbate yana haifar da warware ions Li+ don ingantaccen gudanarwa.Za'a iya amfani da ƙa'idar da aka nuna na haɓaka haɓakar ion zuwa tsarin ion daban-daban.

Ana sa ran masu amfani da wutar lantarki na jihohi za su samar da haɓaka na gaba don batir Li-ion su wuce rufin aiki na 800 W·hour/lita ko 300 W·hour/kg da aka sanya akan cathode da sinadarai na anode a halin yanzu.Ana tsammanin haɓakar ƙarfin ƙarfin ƙarfin batura masu ƙarfi na zuwa daga gudummawa da yawa, duk suna yin niyya ƙara yawan adadin kayan aiki a cikin tantanin halitta.Mafi yawan jama'a shine ƙaddamar da ƙarfe na lithium don maye gurbin graphite da graphite/silicon azaman anode.Ƙarfin lithium mai tsafta yana da mafi girman ƙarfin kuzari mai yuwuwa don haka zai buƙaci mafi ƙarancin sarari.Duk da haka, da yawa al'amurran da suka shafi har yanzu bukatar da za a warware, irin su irreversible dauki (da haka amfani) na lithium karfe, dendrite samuwar, da karuwa a tasiri halin yanzu yawa ga planar lithium foils idan aka kwatanta da porous graphite (silicon) electrodes, da kuma, karshe. amma ba kalla ba, "bacewar" na lithium yayin fitarwa (deplating) kuma ta haka asarar hulɗa tare da m electrolyte.Tsayayyen yanayin injina na ƙwanƙwaran yumbura haƙiƙa yana da ƙarancin yarda, kuma ana buƙatar matsawa matsa lamba don danna lithium da ƙarfi a kan ingantaccen bangaren electrolyte.Matsakaicin matsi mai ma'ana yana rage tasirin tasirin tasiri har ma da ƙari, yana haifar da samuwar dendrite na gida da ajiyar kuɗi.Polymer electrolytes sun fi dacewa da injina amma har yanzu ba su nuna isassun isassun halayen ionic ba a zafin daki.Sabbin abubuwa masu ban sha'awa masu ban sha'awa a wannan batun sune silica gel electrolytes, waɗanda kuma an kira su "ionogels," inda aka keɓe ionic liquid electrolyte (ILE) a cikin matrix silica nanoporous (1).Matsakaicin girman girman matrix silica (70 zuwa 90%) yana ba waɗannan kayan nanocomposite electrolyte daidaiton gel-kamar don haka ya sa su zama masu dacewa da injina kama da polymer electrolytes.Wadannan silica gels wani lokaci ana nuna su a matsayin matasan m electrolytes, kamar yadda suke dauke da ruwa.Duk da haka, ga silica nanocomposites, kamar yadda aka bayyana a cikin wannan takarda, ionic "ruwa" electrolyte ya zama mai ƙarfi-kamar lokacin da aka tsare shi a cikin dubban tashoshi masu girman nanometer duka ta hanyar karuwa a cikin danko da kuma ta hanyar tallan akan bangon silica wanda ke rufewa. tashar.Idan silica matrix zai yi aiki kawai a matsayin mai raba mai ƙura, to, haɓakar danko don ƙayyadaddun ruwan lantarki zai haifar da raguwar haɓakar ionic.Maimakon haka, hulɗar da ke tsakanin ƙwayoyin ILE da bangon silica pore ya sa kaddarorin nanocomposite ya bambanta da jimlar abubuwan da ke tattare da shi.Adsorption na ionic ruwa a kan oxides tare da samuwar m mesophase yadudduka har zuwa ƴan nanometers a cikin kauri an nuna a kan planar saman tare da atomic karfi microscopy (2).Zaɓin zaɓi na anions ruwa na ionic da cations akan saman oxide na iya haifar da haɓakar haɓakawar Li+ tare da waɗannan mu'amala.Tabbas, haɓakawa tare da musaya na oxide dole ne ya rama ko ma ya wuce rage yawan aiki ta hanyar ILE da aka keɓe a cikin ainihin pores.Don haka, ana son ƙarami girman pore da babban girman fage zuwa girma.Ya zuwa yanzu, ionogels tare da ion conductivities da ke gabatowa na ILE kanta an nuna su ta hanyar inganta tsarin mesoporous (3).Wannan yana nufin cewa an riga an haɓaka haɓakawar mu'amala amma ba zuwa iyakar wuce gona da iri ba.

Shirye-shiryen ionogels yana farawa daga cakuda ruwa mai kama da juna, wanda aka ƙara ILE zuwa sol-gel precursor bayani don haɓakar matrix oxide (4, 5).A cikin wannan hanyar, ILE da matrix suna samar da haɗin kai a cikin hanyar "a cikin wuri": Masu ƙira a cikin maganin suna amsawa don samar da matrix oxide a kusa da samfurin ruwa na ionic, suna ɗaukar shi a cikin tsari.A karkashin wasu yanayi kira, ILE-SCE da aka shirya (m composite electrolyte) na iya zama a cikin nau'i na monolith tare da ILE da aka saka a cikin ci gaba da mesoporous inorganic oxide cibiyar sadarwa.Ya zuwa yanzu, galibin ILE-SCE na tushen silica an shirya su ta wannan hanyar, kodayake an kuma yi misalan tare da alumina (6), titania (7), har ma da tin oxide (8).Yawancin nau'ikan sol-gel da aka ruwaito sun ƙunshi ILE, alkyl-silicate kamar tetraethyl orthosilicate (TEOS) azaman silica precursor, da formic acid azaman reagent da sauran ƙarfi (9, 10).Bisa ga tsarin da aka tsara (11) don wannan tsarin sol-gel, silica yana samuwa ne ta hanyar amsawa tsakanin TEOS da formic acid, ko da yake ana samar da ruwa yayin aikin sol-gel.Bayan wadannan nau'ikan gaurayawan "nonaqueous" na formic acid, ruwa mai ruwa sol-gel formulations tare da HCl a matsayin mai kara kuzari da H2O a matsayin reagent (da Organic sauran ƙarfi) kuma an bayyana su, duk da haka, a cikin wannan musamman yanayin don kira na silica composite da Ionic ruwa kawai (12-15).

Yawanci, ionogels suna nuna haɓakar ion ƙasa da na ma'anar ILE.Ƙarni na farko na ionogels suna da yanayin zafin daki yawanci kusan 30 zuwa 50% na ƙimar ILE mai girma, kodayake an ba da rahoton wasu misalan da suka kai 80% (9, 10, 16, 17).An riga an bincika tasirin abun ciki na ILE da sakamakon ƙwayar cuta a kan ionogel conductivity dalla-dalla (3);duk da haka, ba a san wani tsari na bincike kan tasirin inganta mu'amalar mu'amala da su ba.Wu et al.(18) kwanan nan ya ba da rahoto game da ionogel mai aiki a cikin wurin, wanda kuma ya ba da haɓaka haɓakawa idan aka kwatanta da ILE mai girma.An danganta haɓakawa ga hulɗar tsakanin anion da ƙungiyar aikin 3-glycidyloxypropyl a kan silica surface.Wannan binciken yana goyan bayan ra'ayin cewa aikin aikin saman zai iya haɓaka haɓaka haɓakar mu'amala.

A cikin wannan aikin, za mu nuna a cikin wurin samuwar wani m kankara Layer Layer a kan silica da daki-daki da inji na interfacial Li-ion conduction ta ƙara dipole hulda tsakanin saman kankara aikin Layer da adsorbed ionic ruwa mesophase Layer.Ta hanyar haɗuwa da babban yanki na ciki da ƙanƙara mai aikin aikin kankara, m nanocomposite electrolytes (nano-SCE) tare da 200% mafi girma Li-ion watsin fiye da girma ILE tunani aka samu.Ana nuna matrix silica yana da tsarin mesoporous na monolithic na gaskiya tare da kundin pore da wuraren da ke sama har zuwa 90% da 1400 m2 / g, don haka yana ba da matsananciyar haɓaka-zuwa-girma da ke ba da damar babbar gudummawar haɓaka haɓakawa tare da waɗannan musaya.Ta hanyar inganta aikin silica saman haɗe tare da haɓaka girman-zuwa-girma rabo, nano-SCE tare da ion conductivities da ya wuce 10 mS/cm na iya yuwuwar yin injiniya kuma don haka suna da kyau sosai ga manyan batura masu ƙarfi don aikace-aikacen mota.

Mayar da hankali na takardanmu shine kan hanyar haɓaka haɓakawar mu'amala ta hanyar samar da wani yanki na mesophase tare da shaida daga Raman, Fourier transform infrared (FTIR), da makaman nukiliya na maganadisu (NMR) spectroscopy.Ana nuna kwanciyar hankali da kwanciyar hankali na kayan nano-SCE ɗinmu a babban ƙarfin lantarki ta amfani da firam ɗin lithium manganese oxide (LMO) na bakin ciki.Ta wannan hanyar, mayar da hankali yana kula da kayan maimakon a kan haɗakar da lantarki da al'amurran da suka shafi taro.Hakazalika, taga electrochemical da kwanciyar hankali akan foils na ƙarfe na lithium suna da cikakkiyar siffa.Ana nuna ayyuka da haɗin kai na nano-SCE ta hanyar haɗuwa da gwaje-gwajen ƙima na lithium iron phosphate (LFP) da lithium titanate (LTO).An nuna kwanciyar hankali na electrolyte ɗin mu da rashin aiki na electrochemical na ruwan kankara ta hanyar hawan keke na dogon lokaci na ƙwayoyin Li-SCE-Li.Haɓaka ƙarfin kuzari, aikin ƙima, da aikin hawan keke na sel da aka haɗa cikakke za su zama abin da ke mayar da hankali ga takaddun bi-biyu (19, 20).

Haɓaka haɓakawar ion na fuska a cikin tsarin haɗaɗɗun nau'i biyu an san shi kusan shekaru 90 (21).Misali, an nuna har zuwa umarni huɗu na haɓaka haɓakar ionic don haɗaɗɗun gishirin lithium mai sauƙi kamar lithium iodide tare da ƙwayoyin mesoporous oxide irin su silica ko alumina idan aka kwatanta da ion conductivity na tsarkakakken lithium gishiri electrolyte (22).ions a cikin waɗannan SCEs na iya yaɗuwa da sauri tare da Li ion-rarewa (ko mai wadatar sarari) na lantarki mai ninki biyu da aka kafa a mahaɗin oxide/electrolyte.Abin baƙin ciki shine, ion conductivity da aka samu a cikin waɗannan sassauƙan sassa biyu na inorganic inorganic solid-m composites (1) bai wuce madaidaicin 1-mS/cm2 da ake buƙata don gadar 'yan ɗari-mikromita nesa tsakanin faranti na yanzu a cikin baturin Li-ion ba. .Hakanan an bincika manufar doping iri-iri tare da matrix oxide don injiniyar haɓakar ionic don polymer electrolytes (23) da ILEs (24), waɗanda ke da haɓakar haɓakar ionic mafi girma don farawa da.Bugu da kari, sinadarai masu arziƙi (stereo) na kashi na uku suna buɗe ƙarin hanyoyin sarrafa ion, kamar yadda (di) ƙwayoyin ƙarfi kamar na iya shiga cikin samuwar Layer Layer na lantarki.Duk da yake aikin warwarewar ƙungiyoyin ether a cikin polyethylene oxide polymer electrolytes suna samar da ingantaccen yanayin ion na ~ 10-6 S / cm don LiClO4 zuwa ~ 10-5 S / cm don LiN (SO2CF3) 2, abubuwan haɗin su tare da silica, alumina. , ko titania nanoparticles na iya ba da ƙarin haɓakawa fiye da ninki 10 a ma'aunin ion conductivity (25), da rashin alheri, har yanzu yana ƙasa da madaidaicin yanayin zafin ɗakin na 1 mS/cm.Maganin ILE sune gaurayawan Li-gishiri solute da ion ruwa mai narkewa, wanda zai iya samun manyan abubuwan gudanarwa na ionic tsakanin 0.1 da 10 mS/cm (26, 27).An yi ƙoƙari da yawa don haɓaka haɓakar ion ta hanyar haɗawa ko gelling shi tare da nanoparticles oxide ko don taƙaita ILE a cikin ƙananan ƙwayoyin cuta (9, 16, 28, 29).Duk da haka, ya zuwa yanzu, ba a lura da haɓakar haɓakar ion ba don sassa uku na Li-salt / ionic liquid / oxide composites (fig. S1).Ko da yake amfani da mesoporous silica microparticles baya haifar da mafi girma conductivity kamar yadda idan aka kwatanta da composites tare da m nanoparticles, da interfacial surface area da ion conduction gabatarwa bai isa ya wuce girma ILE watsin.

Mesoporous silica sanannen abu ne da ake amfani dashi a cikin catalysis.Yawanci ana yin shi ta hanyar hydrothermal ko haɗin sol-gel mai sauƙi.Hanyoyin hydrothermal yawanci suna haifar da foda mai mesoporous, amma tare da kula da tsarin zafin jiki na sol-gel, manyan gilashin gilashin gilashi ko aerogels kuma an samar da su.An kafa matrix silica ta hanyar hydrolysis da halayen motsa jiki na tetra-alkyl orthosilicates (30).Makullin sarrafa tsarin pore shine amfani da samfura, alal misali, nau'in micelle mai nau'in surfactant, wanda a kusa da shi aka kafa matrix silica.Lokacin da aka ƙara ruwa mai ionic a matsayin kwayoyin halitta, hydrated silica matrix yana hulɗa tare da ruwan ionic, yana samar da gel, kuma bayan warkewa da bushewa, ruwan ionic yana tsare a cikin matrix na nanoporous silica matrix (13).Lokacin da aka ƙara gishiri na lithium a matsayin kashi na uku, ILE da ke cikin silica matrix yana samar da silica gel electrolyte, wanda kuma ake kira ionogel (24).Duk da haka, ya zuwa yanzu, waɗannan silica gel electrolytes suna nuna halayen da ke gabatowa na ILE mai girma amma ba su wuce shi ba, sai dai wani yanayin da silica ya kasance yana aiki da sinadarai (duba Gabatarwa) (18).

Anan, mun nuna, ci gaba na tsari na haɓakawar Li-ion na nanocomposite fiye da na ILE mai tsabta.Ana amfani da misalin 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide (BMP-TFSI) anan.An ba da sanarwar cewa adsorption na ƙwayoyin ruwa na ionic akan saman silica da aka ƙare OH ana haɓaka ta kasancewar ruwan ruwan kankara na tsaka-tsaki.Ƙarfin haɗin gwiwar hydrogen tsakanin ruwan kankara da TFSI- anion yana haifar da odar kwayoyin halitta na ruwan ionic, kama da yankunan da aka ba da umarnin da ke samuwa a cikin ruwa na ionic (31).Bambanci mai mahimmanci tare da yankunan da aka kafa bazuwar a cikin babban ILE shine cewa Layer na kankara yana aiki a matsayin aikin aiki wanda (i) ya haifar da odar kwayoyin halitta akan saman oxide kuma (ii) ya gabatar da isasshen H-bonding don haifar da dipoles don saki Li + kyauta. don ingantaccen gudanarwa.Kusa da karuwa a cikin maida hankali na Li + kyauta, za mu nuna cewa ƙarfin kunnawa don yaduwa yana da ƙasa tare da haɗin haɗin haɗin gwiwa tare da Layer na ILE da aka tallata da ruwan kankara.

Ruwan ruwa mai kauri-dan-monolayers-kauri akan silica ne mai ƙarfi-kamar Layer, kamar yadda yake da ƙarfi da alaƙa da ƙungiyoyin silanol ta hanyar H-bridges don haka kuma ana kiranta da kankara Layer (32).Yawansa da kauri (ƙimantawa har zuwa uku zuwa hudu monolayers, tare da ~ 0.25 nm a kowace kankara monolayer) suna cikin ma'auni na thermodynamic tare da matsa lamba na ruwa (RH)) a cikin yanayi (fig. S2).Mun nuna cewa ion conductivity yana ƙaruwa tare da kauri daga cikin ruwan kankara kamar yadda hydrogen bonding tare da adsorbed ionic yadudduka shi ma yana ƙaruwa.Ruwan ruwan kankara yana da tsayin daka da ruwan kristal a mahallin sinadarai.Wannan ya sha bamban da na'urorin lantarki masu ƙarfi ko kuma abin da ake kira ruwa a cikin gaurayawar gishiri, inda taga wutar lantarki ke daɗa faɗaɗawa sosai amma, a ƙarshe, ruwan har yanzu yana aiki da lantarki (33).

Daban-daban daga al'ada formic acid-catalyzed ionogel girke-girke, mun yi amfani da m pH 5 cakuda tare da babban wuce haddi ruwa da PGME (1-methoxy-2-propanol) kara zuwa TEOS precursor tare da Li-TFSI gishiri da BMP-TFSI ionic ruwa.A wannan pH, da hydrolysis halayen ne jinkirin, yayin da condensation ne m (30).An yi imani da cewa Li ions suna aiki a matsayin mai haɓakawa don maganin hydrolysis, kamar yadda babu wani gelation da ya faru a cikin rashi na lithium gishiri yayin da duka biyu suna da pH guda ɗaya na 5. Matsakaicin molar ruwa na ion ruwa zuwa TEOS (kuma haka silica moieties) ne. an nuna shi azaman darajar x kuma ya bambanta tsakanin 0.25 da 2. Matsakaicin molar BMP-TFSI zuwa Li-TFSI an kiyaye shi a 3 (daidai da 1 M Li-ion bayani).Sannu a hankali bushewa ya zama dole don kiyaye amincin tsarin tsarin monolith (duba Kayan aiki da Hanyoyi).Hoto na 1A yana nuna hoto na pellet monolithic da aka samu bayan bushewar injin.Bushewar bushewar sa'o'i 72 ya wadatar don cire duk danshi har zuwa wani wuri inda aka cire duk ruwan kyauta yayin da ruwan kankara da aka ɗora ya kasance cikakke, kamar yadda FTIR ya tabbatar.Babu wani girgiza don ruwan kyauta da aka gano a 1635 cm-1 a cikin kowane samfurin bayan matakin bushewa (Fig. 2).Don kwatantawa, ana nuna bakan FTIR don samfurin nano-SCE (x = 1.5) da aka adana don mako 1 a cikin akwatin safar hannu na N2 a 60% RH.A wannan yanayin, bayyanannen kololuwar ruwa kyauta ya bayyana.Duk samfuran, a gefe guda, sun nuna sigina bayyananne don aikin aikin silanol (Si─OH lankwasawa tsakanin 950 da 980 cm−1) da kuma ruwan kankara mai ɗorewa (O─H mai shimfiɗa a ~ 3540 cm-1) da aka haɗa zuwa Ƙungiyoyin saman ─OH ta H-bonding (ƙarin cikakkun bayanai a ƙasa).An auna gwangwani kafin da bayan matakin bushewa don auna ruwan da ke cikin nano-SCE (tebur S1).Daga baya, za mu ƙididdige adadin adadin madaidaicin madaidaicin yadudduka na kankara mai ɗaure daga sama mai nauyi.An kawo busassun pellet ɗin a cikin akwatin safar hannu [<0.1-ppm (sassan kowace miliyan) H2O] kuma an adana su a cikin rufaffiyar rufaffiyar don kula da ainihin abun ciki na ruwa.An ɗauki ƙaramin ƙara daga pellet don ƙarin haɓakawa.

(A) Hoton pellets nano-SCE guda biyu (hagu) da aka haɗa a cikin vial;bayan gelation, ana samun pellet na gaskiya.Lura cewa pellet ɗin cikakke ne don haka an ba shi launin shuɗi don gani.Lokacin da aka cire ILE, ƙaramin farin pellet ya rage don matrix ɗin silica mai ƙarfi (dama).(B) Hoton microscopy na lantarki (SEM) na matrix SiO2 wanda ya rage bayan cire ILE.(C) Zuƙowa hoton da aka nuna a cikin (B) yana nuna yanayin yanayin matrix tare da wasu macropores.(D) Hoton watsawa na lantarki (TEM) yana nuna babban marufi na 7- zuwa 10-nm silica nanoparticles azaman tubalan ginin kayan matrix porous.(E) Matsakaicin tsarin matrix da aka ƙulla don ma'auni daban-daban na molar ILE dangane da SiO2 (x darajar).Layin da aka soke yana ba da ƙayyadaddun ƙayyadaddun ƙayyadaddun ƙayyadaddun ƙayyadaddun juzu'i na ILE da silica.Samfuran da aka rinsed acetone (baƙar fata) an bushe su a cikin iska, wanda ke ba da rugujewar tsari don x> 0.5.Babban bushewar CO2 na ethanol-rinsed nano-SCE (koren da'ira) yana hana rushewa har zuwa x = 2 don ƙarin jinkirin cire CO2 (da'irar buɗe).BET, Brunauer-Emmett-Teller.Hoto Credit: Fred Loosen, imec;Akihiko Sagara, Panasonic.

(A) Siffar IR na Nano-SCE kamar yadda aka bushe a cikin injin (baƙar fata) kuma daga baya ya ƙara bushewa a cikin akwatin safar hannu tare da 0.0005% RH na kwanaki 9 (blue) kuma an fallasa zuwa 30% RH na kwanaki 4 (ja) kuma zuwa 60 % RH na kwanaki 8 (kore), bi da bi.au, raka'a na sabani.(B) Voltammogram na cyclic na jigon Li/SCE/TiN tare da darajar x na 1.0 (blue), 1.5 (kore), da 2.0 (ja) da na ILE tunani (baki);saitin yana nuna halin yanzu a sikelin logarithmic.(C) Voltammograms na cyclic na Li/SCE (x = 2)/40-nm TiO2 tari (ja), ILE (dige baki), da ILE spiked tare da nauyin 5% (wt %) H2O (layin shuɗi mai dige-dige);a (B) da (C), ma'auni tare da ILE da ILE tare da H2O an yi su a cikin daidaitawar lantarki guda uku tare da TiN a matsayin lantarki mai aiki da Li a matsayin counter da na'urorin lantarki.An bushe SCE na tsawon kwanaki 2 a cikin akwatin safar hannu bayan bushewa.

Ƙarfafawar ionic (σi) na nano-SCE na injin mu ya karu tare da juzu'in juzu'i na ILE (ƙimar x) kamar ga abubuwan da aka haɗa (fig. S1).Duk da haka, a wannan yanayin, ƙaddamarwar ionic ya wuce na ILE mai tsabta da kanta fiye da 200% don mafi girman darajar x (Fig. 3).Bugu da ƙari kuma, yawan dogara da zafin jiki na nano-SCE tare da haɓakaccen haɓakar ion ya nuna hali daban-daban fiye da na ILE mai tsabta: Yayin da Li-TFSI a cikin BMP-TFSI ILE yana nuna canji mai mahimmanci a cikin ƙaddamarwa da kuma kunnawa makamashi (slope) a kusa da narkewa. batu na cakuda a 29 ° C, Nano-SCE tare da ingantaccen aiki ba ya.Madadin haka, yana nuna ci gaba da sauye-sauye a cikin σi tare da zafin jiki, yana nuna cewa an kafa wani nau'in lokaci ko mesophase wanda ba a bayyana a baya ba, wanda ke da alhakin haɓakar haɓakawa.Bugu da ƙari, ƙananan gangara kuma don haka ƙananan ƙarfin kunnawa don watsawa ga nano-SCE idan aka kwatanta da ILE suna nuna kaddarorin kayan abu daban-daban (fig. S3).An ba da sanarwar cewa ƙaƙƙarfan hulɗar tsakanin kwayoyin ruwa na ionic da ƙaƙƙarfan ƙanƙara mai ƙarfi akan silica scaffold yana da alhakin halayen mesophase da aka lura, kamar yadda za a tattauna tare da ƙirar da aka tsara a ƙasa.

(A) Dogaro da yanayin zafin jiki na nano-SCEs ya bushe na tsawon kwanaki 8 a cikin akwatin safar hannu (GB) tare da ƙimar x na 2 (bankunan baƙar fata), 1.75 (da'irar orange), 1.5 (triangles blue), da 1.0 (alwatika koren kore). ) da kuma na ILE reference (bude murabba'ai).(B) Ayyukan nano-SCEs kuma sun bushe a cikin GB na kwanaki 0 ( murabba'in kore ), kwanaki 10 (alwatika baƙar fata), da kwanaki 138 ( triangles blue).(C) Haɓakawa tare da tushen murabba'in lokacin bushewa na nano-SCE tare da ƙimar x na 2 ( murabba'ai na baƙar fata), 1.5 (alwatika shuɗi), 1.0 (alwatika kore), da 0.5 (lu'u lu'u-lu'u).(D) Gudanar da Nano-SCE tare da x = 2 (bangaren baƙar fata), 1.5 (alwatika masu shuɗi), da 1.0 (alwatikan kore) da aka fallasa a cikin ɗakin zafi mai cike da N2.

Yanayin argon a cikin akwatin safar hannu ya ƙunshi ƙasa da 0.1 ppm na ruwa, wanda yayi daidai da 0.0005% RH, wani ɓangaren ruwa na 0.01 Pa, ko raɓa na -88 ° C.Kamar yadda adadin ruwan yadudduka na ruwa a kan silanol-terminated silica yana cikin ma'auni tare da matsa lamba na ruwa (fig. S2), ruwan saman zai sannu a hankali ya bazu daga nano-SCE kuma ya kasance a gefuna.Hoto 3C yana nuna canjin aiki don 23 μl na nano-SCE azaman aikin lokacin zama a cikin akwatin safar hannu.Ƙarƙashin ion yana raguwa tare da bushewa har sai ya yi daidai da ƙimar da ta dace da saman silica a cikin ma'auni tare da matsi na ruwa na 0.01 Pa a cikin akwatin safar hannu.Ko da a ƙarƙashin matsanancin yanayin bushewa na akwatin safar hannu, aƙalla, wani ɓangare na monolayer na ruwa mai ɗorewa akan silanol yana nan, kamar yadda Raman spectroscopy har yanzu ya nuna sigina a 3524 cm-1, wanda ya keɓance na farko monolayer na ruwa adsorbed akan silanol. (Hoto na 4B).Ayyukan ion a ƙarƙashin cikakkun yanayi ya kasance ƙasa da na ILE na kowane mutum a kowane yanayi.Don haka, haɓakawa bai isa ba don ramawa ga asarar da aka yi a cikin ionic conductivity na ILE mai iyaka a cikin ainihin ramin.

(A) Siffar IR na nano-SCE tare da ƙimar x na 1.5 (ja), ILE reference (black), da SiO2 (blue), yana nuna cewa ƙungiyar O═S═O (1231 cm-1) tana da hannu a cikin hulɗa tare da ƙungiyoyin OH akan saman silica.(B) Raman spectra na nano-SCE tare da darajar x na 2 (baki), 1.5 (ja), da 0.5 (blue), yana nuna kasancewar ruwan kankara da aka haɗe akan silica- ƙarewar silica har ma na nano-SCE kusa da jikewa (0.0005). % RH) a cikin akwatin safar hannu (kwanaki 30).(C) Samfurin da aka tsara don mu'amalar mu'amala a cikin nano-SCE tare da rarraba Li-TFSI zuwa Li+ kyauta kamar yadda TFSI- anion ya raba wani ɓangare na mummunan cajin sa tare da shimfidar kankara-TFSI-BMP;launuka suna wakiltar abubuwa daban-daban tare da purple (silicon), ja (lithium), duhu rawaya (sulfur), orange (oxygen), blue (nitrogen), fari (hydrogen), da kore (fluorine).Layukan da suka shuɗe shuɗi suna wakiltar haɗin hydrogen tsakanin ƙungiyar O═S na TFSI anion da ƙungiyoyin OH na saman silica hydroxylated.Li+ ions da aka saita ta hanyar dipole akan Layer ɗin da aka tallatawa na iya yin ƙaura ta hanyar wayar hannu ta gaba ko watsa ruwan ruwa na ionic sama da yaduddukan mu'amala.Lura cewa ya danganta da ƙarfin haɗin hydrogen da kuma daidai cajin akan silica, ana iya ƙirƙirar Layer adsorbed da yawa kuma.Ana nuna cikakken bakan a cikin fig.S8.

Wani kallo mai ban sha'awa shine alaƙar layi tare da tushen murabba'i na lokacin bushewa kamar yadda aka nuna a cikin Fig. 3C, yana nuna cewa canjin gudanarwa yana daidai da canje-canje a cikin adadin ruwan ƙanƙara a kan silica da kuma cewa kawar da wannan ruwa mai zurfi ne. Diffusion Limited.Lura cewa "bushewa" yana faruwa ne kawai a cikin buɗaɗɗen wuri inda RH ya fi ƙasa da ma'aunin ƙanƙara.Gudanarwar bai canza sananne ba, misali, a cikin rufaffiyar sel tsabar kudin da aka yi amfani da su don ma'aunin dogaro da zafin jiki.

An auna dogaro da zafin jiki na nano-SCE don lokuta daban-daban na bushewa a cikin akwatin safar hannu.Kamar yadda conductivity na busasshen Nano-SCE ya kusanci na ILE, ci gaba da σi tare da 1 / T bayanan martaba na mesophase conductivity a hankali ya canza zuwa bayanin martaba na ILE, yana sake bayyana digo a kusa da wurin narkewa (fig. S3).Wannan kallo yana ƙara goyan bayan zato cewa Layer na kankara yana aiki azaman Layer mai aiki don hulɗar mu'amala tare da ILE, yana haifar da halayen mesophase a cikin nano-SCE.Don haka, lokacin da aka cire Layer ɗin mai aiki, ILE yana zama kawai a tsare a cikin mesoporous oxide membrane.

Ma'aunai na tagar kwanciyar hankali na electrochemical sun tabbatar da cewa ruwan kankara a cikin Nano-SCE yana da kwanciyar hankali, saboda ba a sami kololuwa don rage ruwa ko oxidization a cikin inert TiN electrode (Fig. 2) ko a TiO2 bakin ciki-film electrode, wanda in ba haka ba yana aiki. a matsayin electro-catalyst don rage ruwa.Madadin haka, kwanciyar hankali na electrochemical na nano-SCE yayi kama da na ILE kuma saboda haka an iyakance shi ta hanyar iskar oxygenation na TFSI- a ƙarfin lantarki> 4.3 V da rage TFSI- da BMP + a yuwuwar <1 V da Li +/ Li (33).Don kwatantawa, ana nuna voltammogram don ILE mai nauyin 5 % (wt %) da aka ƙara ruwa (mai kama da na wasu nano-SCE; duba tebur S1).A wannan yanayin, ana auna reshen cathodic don rage ruwa nan da nan bayan Li-intercalation kololuwar anatase a 1.5 V da Li +/Li.

Matsakaicin yanayin zafi da (electro) kwanciyar hankali na nano-SCE galibi ana ƙaddara ta ILE filler.Binciken Thermogravimetric (TGA) ya nuna kwanciyar hankali na thermal na SCE da ILE har zuwa 320 ° C, ba tare da la'akari da ILE-to-silica rabo (fig. S4).Sama da wannan zafin jiki, Li-TFSI da BMP-TFSI suna ruɓe gaba ɗaya zuwa abubuwan da ba su da ƙarfi, kuma matrix silica kawai ya rage a kusa da 450°C.Yawan adadin da ya rage bayan bazuwar zafin jiki ya yi daidai sosai da juzu'in silica a cikin SCE.

Nano-SCE ba ya nuna wani fataccen microstructure a cikin na'ura mai ba da hanya tsakanin hanyoyin sadarwa (SEM) sai dai ga fili mai santsi tare da wasu facin silica da ke fitowa (fig. S5).An ƙayyade ƙayyadaddun ƙimar SCE tare da helium pycnometer kuma yana kusa da 1.5 g/cm3 don duk ƙimar x (tebur S1).Cikakken matrix silica an bayyana shi ta hanyar cirewar ILE a cikin wani ƙarfi (duba Kayan aiki da Hanyoyi).Ta hanyar bushewa a hankali a wuri mai mahimmanci na CO2, ana iya samun nau'ikan nau'ikan airgel monoliths kamar wanda aka nuna a cikin siffa 1A.Binciken SEM yana nuna alamar silica mesoporous tare da diamita na 10- zuwa 30-nm, wanda aka nannade a kusa da manyan macropores na 100 zuwa 150 nm, kamar yadda ake iya gani a cikin siffa 1 (B da C).Ƙaƙƙarfan ƙwaƙƙwaran watsawa na lantarki (TEM) (Fig. 1D) ya ƙara fallasa ƙananan ƙananan ƙwayoyin da ke kunshe da silica nanoparticles.Matsakaicin diamita na barbashi ya kasance daga 7 zuwa 14 nm don ƙimar x tsakanin 0.5 da 1.5.

Ƙayyadaddun yanki na musamman [Brunauer-Emmett-Teller (BET)], porosity, matsakaicin girman girman pore, da kuma rarraba girman pore an ƙaddara tare da N2 adsorption / desorption ma'auni (tebur S1 da fig. S6).Rushewar ɓangarori na tsarin da rashin cikar cirewar ILE da aka tallata na iya ɗan ɓarna lambobin.A hankali hakar ion ruwa ruwa da jinkirin bushewa ta amfani da supercritical CO2 bayar, duk da haka, m sakamakon kusa da tsammanin porosity lissafta daga girma juzu'in na ILE zuwa silica (Fig. 1).Yankin saman BET yana tsakanin 800 zuwa 1000 m2/g.Matsakaicin girman pore da aka samu daga gangaren isotherm ya kasance tsakanin 7 da 16 nm.Bugu da ƙari, an auna ƙananan ƙananan ƙananan pores har zuwa kimanin 200 nm (fig. S6), daidai da abubuwan SEM.Diamita na pore yayi daidai da kyau tare da sau biyu daidai kauri na ILE Layer da aka samu daga juzu'in ƙarar ILE da yanki na BET, ma'ana cewa mesopores sun cika da ILE gaba ɗaya.

Yankin saman BET da aka ruwaito shine don mesopores da macropores kawai.Don matrix-rinsed acetone, an auna micropores (~ 0.6 nm).Ana samun micropores tsakanin silica nanoparticles na silica guda ɗaya wanda ke yin tsari kamar yadda aka nuna a cikin hoton TEM na siffa 1D.Matsakaicin ƙarin yanki tsakanin 650 (x = 0.5) da 360 m2/g (x = 1.5) an kiyasta (tebur S1).

Dukansu FTIR da Raman spectra suna nuna tabbataccen shaida ga ƙungiyoyin silanol tare da ƙwayoyin ruwa na kankara a kan matrix silica mai girma-porosity tare da matsanancin tasirin saman da ya wuce 1400 m2 / g lokacin la'akari da micropores, mesopores, da macropores.Tsakanin sifili da uku na ruwa guda uku ana ƙididdige su daga yawan ruwa a cikin nano-SCE na x <1.75.Don silica planar, farkon guda uku monolayers na ruwa da aka ɗora, hakika ana ɗaukar su mara motsi da ƙarfi-kamar saboda ƙarfin haɗin gwiwar su na hydrogen zuwa saman OH da aka ƙare (32) (duba fig. S2).Ana samun shimfiɗar O─H da ke da alaƙa da silanol hydrogen da aka haɗa da ruwan kankara a 3540 cm-1 a cikin sigar FTIR.Duk nano-SCEs suna nuna, hakika, wani tsayin tsayi a 3540 cm-1 don ruwan kankara bayan bushewa mai bushewa da kuma bayan kara bushewa a cikin akwatin safar hannu (Fig. 2).Ko da na nano-SCE mai daidaitacce a 0.0005% RH (akwatin safar hannu), Raman spectroscopy har yanzu yana nuna kasancewar aƙalla na'urar monolayer (Fig. 4B).Monolayer na huɗu akan silica na planar an yi imani da cewa shi ne na wucin gadi Layer, ma'ana cewa har yanzu ana tallata shi kuma an iyakance shi amma yana iya samun ɗan motsi.Daga kashi na biyar, ruwan ya zama wayar hannu da ruwa-kamar.Ruwa mai kama da ruwa zai nuna sama a manyan lambobi a cikin bakan FTIR saboda ƙananan matakin H-bonding a cikin ruwa mai ruwa.Don nano-SCE da aka fallasa zuwa 60% RH, 3540-cm-1peak hakika yana nuna ƙarin girgizar da aka canza zuwa manyan lambobi saboda ƙarin tallan ruwan ruwa.Abin sha'awa game da wannan shine gwajin inda aka nuna samfurin zuwa 30% RH, kamar yadda ba a sa ran ruwan ruwa a kan silica a wannan zafi (fig. S2).Don wannan samfurin, kawai 3540 cm-1 kololuwar ruwan kankara ana gani a cikin FTIR.Bugu da ƙari, ba a gano kololuwar ruwa kyauta a 1635 cm-1 ko da bayan kwanaki 4 a 30% RH.Wannan yana nufin cewa ruwa ba ya ɗauka ta hanyar hygroscopic Li-TFSI da aka narkar da shi a cikin hydrophobic BMP-TFSI da zarar nano-SCE ya bushe ta hanyar magani.Sabili da haka, duk wani ƙarin ruwa a cikin SCE za a sanya shi a saman silica da aka ƙare OH.Don haka, game da silica na planar, SCE silica matrix yana cikin ma'auni tare da matsi na ruwa a cikin muhalli.

Don ƙarin gwada wannan hasashe, an auna ion conductivity nano-SCE (x = 1, 1.5, da 2) a daban-daban% RH;samfurori an fallasa su zuwa gauraya mai sarrafawa na busassun busassun gas na N2 a cikin akwati na safar hannu don kwanaki 2 don ba da damar ɗaukar ruwa da aka rufe don isa ga daidaito (Fig. 3D).Don maki a ~ 0% RH, an ɗauki ɗawainiyar daidaitaccen nano-SCE a cikin akwatin safar hannu.Abin mamaki, ion conductivity da RH (%) bayanin martaba ya bi halin da ake tsammani don tallan ruwa akan silica planar (fig. S2).Tsakanin 0 da 30% RH, ƙaddamarwa ya karu tare da haɓaka RH.kamar yadda ake tsammani don haɓaka ƙaƙƙarfan ƙaƙƙarfan ƙanƙara da kauri (daidai da yadudduka na kankara ɗaya zuwa uku akan silica planar).Lura cewa FTIR ya nuna cewa babu ruwa kyauta a cikin nano-SCE na kwanaki da yawa a 30% RH.Ana ganin sauyi a kusa da 50% RH, daidai da yanayin da ake sa ran ɗigon ruwa na wucin gadi don silica na planar.Daga ƙarshe, ana samun nau'in haɓakar haɓakar haɓakar ion zuwa kashi 60% kuma mafi girma humidities inda, kama da silica na planar, yanzu, kuma ana iya samar da wani ruwa mai kama da ruwa a cikin keɓancewa tsakanin silica da ILE da aka haɗa.Tare da FTIR, an gano wani ruwa mai ruwa a kan kankara a yanzu ta hanyar motsi na silanol / kankara / ruwa mai girgiza ganiya zuwa mafi girma makamashi (Fig. 2A).Canjin da aka lura a cikin haɓakawa yana canzawa;don haka, Nano-SCE na iya aiki azaman firikwensin zafi da kuma Li-ion electrolyte.Daga siffa. 3D, ion conductivity na nano-SCE nan da nan bayan vacuum anneal yayi dace da ma'auni hydrated silica na ~ 10% RH.Ƙarfin ion don jikewa a cikin yanayin ɗaki mai bushe (~ 0.5% RH) zai kasance a kusa da 0.6 mS/cm (na x = 2).Wannan gwaji yana nuna tasirin ruwan tsaka-tsakin fuska akan ion conductivity.Don RH> 60%, ana iya yin bayanin mafi girman halayen ion ta hanyar saurin yaduwa na Li+ mai narkewa ta hanyar ruwa mai kama da ruwa.Koyaya, a cikin yanayin ƙaƙƙarfan ƙanƙara mai ƙanƙara, yaduwar Li+ ion zai zama nau'in yaduwa mai ƙarfi kuma don haka a hankali fiye da ta ruwan ionic kanta.Madadin haka, ana danganta haɓakawa zuwa haɓakar haɓakar ƙwayoyin halitta da cations na Li-gishiri da ƙwayoyin ruwa na ionic, kamar yadda aka tsara a cikin ƙirar da ke ƙasa.

Muna ba da shawarar samfurin inda kwayoyin ruwa na ionic ke adsorbed a kan silica surface ta hanyar H-gadaji tare da m kankara Layer a kan silanol kungiyoyin (Fig. 4).Halin yanayi na haɓakar haɓakar haɓakar haɓakar hydrolysis yana ba da mafi girman ƙimar silanol (4 × 1014 zuwa 8 × 1014 cm−2, wanda yayi daidai da ƙarancin ƙanƙara ɗaya na ƙanƙara tare da ~ 8 × 1014 kwayoyin ruwa da cm2) (34).Shaida don hulɗar kwayoyin halitta tsakanin O atom na TFSI anions da silica ana ba da ita ta FTIR, wanda ke nuna ninki biyu na O═S═O kololuwa ga duk nano-SCE idan aka kwatanta da ma'anar ILE (Fig. 4A; cikakken bakan gizo). a cikin S8).Juya ƙarin kololuwa tare da -5 cm−1 daga 1231 cm−1 yana nuna haɗin kai na ƙungiyoyin O═S═O don aƙalla ɓangaren TFSI.Saboda haka, ana ɗaukar H-bonding na TFSI anions akan ruwan kankara.Daga baya, manyan hydrophobic BMP cations suna haɗuwa da Layer na TFSI na farko, suna kammala Layer na farko da aka tallata na kwayoyin ruwa na ionic.Dangane da dusar ƙanƙara, ƙwayoyin BMP-TFSI da aka tallata ana tsammanin ba su da motsi, don haka ƙara ƙaƙƙarfan ƙanƙara mai kama da kankara a saman silica.Kamar yadda TFSI anion yana da ƙungiyar O═S═O mai ma'ana, atom ɗin oxygen ɗaya zai iya yin hulɗa tare da saman silica na hydroxylated yayin da ɗayan ya samar da maki mai mannewa ga cations na BMP.Hakanan TFSI anion yana da ƙungiyoyin O═S═O guda biyu, suna ba da tabbacin tallan tallace-tallace da tsari mai yawa na anion monolayer.Adsorption ya fi dacewa a yanayin ƙanƙara mai ƙanƙara tare da mafi girman yawa na ƙungiyoyin OH a matsayin madaidaicin maki.A gaban ƙungiyoyin silanol kawai, tallan bazai yi ƙarfi ba don samar da Layer adsorbate mai ci gaba.Bugu da ƙari, an san yawan adadin ƙanƙara monolayers don ƙara ƙarfin haɗin hydrogen (35).Lura cewa hulɗar kwayoyin halitta tsakanin cation BMP da TFSI monolayer da aka ba da umarnin zai bambanta da wancan a cikin ruwa na ionic inda TFSI anion yana da 'yanci na juyawa kuma babu polarization daga saman da ke ƙasa.Haƙiƙa ana rarraba cajin babban cation ɗin BMP akan yawancin zarra ta hanyar karkatar da haɗin kai da kuma hulɗar kwayoyin halitta tare da yanayin sinadarai da, musamman, anion na TFSI.H-bonding tsakanin ƙungiyar O na TFSI anion da OH-termination na ƙanƙara Layer yanzu yana gabatar da dipole akan Layer na farko da aka tallata, yana haifar da ƙarin odar kwayoyin ta hanyar ƙungiya.An yi imani da cewa a wannan lokacin, ƙananan ƙwayoyin Li-TFSI suna yadawa akan Layer na kwayoyin halitta wanda TFSI anion yanzu ya biya ragowar ƙimar dipolar ɗaya ko fiye na BMP cations a saman Layer, don haka ya sassauta haɗin gwiwa tare da Li. ion.Ta wannan hanyar, ƙaddamarwar Li + kyauta yana ƙaruwa a wannan ƙirar, yana haifar da haɓakar ion mafi girma.Don haka, yaduddukan ƙanƙara mai yawa da kauri sannan gabatar da babban dipole tare da ƙarin cajin da ya rage don ramawa, yana ba da mafi girman ƙimar Li+ kyauta kuma don haka haɓakar ion.

A saman Layer na ILE da aka tallatawa, ko dai wani Layer na ILE zai iya yin kama da nau'in kankara masu yawa akan silica ko kuma juzu'in juzu'in dusar ƙanƙara yana da rauni sosai kuma ILE mai ɗaure da sauƙi yana saman, wanda zai iya samar da ruwa-kamar gudanarwa don Li + ions da aka saki a cikin ƙananan Layer adsorbed (Fig. 4C).Canjin maida hankali na Li+ ion kyauta an tabbatar da shi ta duka ma'aunin gani na NMR da Raman.Ma'auni na Raman a kaikaice yana nuna cewa babban juzu'in ions Li+ na kyauta suna nan a cikin nano-SCE tare da ƙarin ruwan kankara da ke ɗaure zuwa silica (Fig. 5).Raman yana auna haɗin cation tare da TFSI ta hanyar bincikar girgizar ƙungiyar N-kungiyar TFSI (36).A cikin tsantsar ruwan ionic BMP-TFSI, kololu guda kawai a 741 cm-1 ana gani.A cikin yanayin ILE mai tsabta, ana ganin ƙarin kololuwa a 746 cm-1 inda TFSI anions guda biyu suka daidaita tare da Li + ion guda ɗaya [duba ƙididdigar aikin aikin density (DFT) a cikin Materials da Hanyoyi].Ga duk nano-SCEs, ƙarfin kololuwa a 746 cm−1 ya fi na ILE rauni, yana nuna ƙaramin juzu'i na Li-TFSI mai alaƙa kuma, saboda haka, babban juzu'in da ba a haɗa shi ba ko kyauta Li+ cations.Kololuwar tana raguwa sosai ga waɗancan nano-SCE waɗanda ke nuna mafi girman haɓaka haɓakawa, watau waɗanda ke da mafi ƙanƙara Layer na kankara.Don nano-SCE a ma'auni a cikin akwatin safar hannu, har yanzu, ana auna juzu'in Li+ kyauta duk da cewa ya fi na samfuran da aka cire.Matsakaicin mafi girman ƙarfin 746 akan 741 cm-1 Raman canzawa sannan shine ma'auni na rabon kyauta zuwa Li-ions masu alaƙa da TFSI (Fig. 5B).Haɓaka layin layi a cikin juzu'in Li+ ion kyauta tare da darajar x da kyau yana bin yanayin haɓaka haɓaka aiki tare da ƙimar x a cikin siffa 3B, duka don bushewar nano-SCE (ranar 0) da SCE a daidaici tare da bushewar akwatin safar hannu (rana 138).

(A) Raman spectra na ruwa mai ionic (IL; layin shuɗi mai dige) da ILE tunani (ILE; layin dash-dige) na kamar yadda aka shirya nano-SCE (bushe injin) tare da ƙimar x na 0.5 (kore), 1.5 (rawaya) , da 2 (launin ruwan kasa) da nano-SCE (x = 1.5) bugu da kari kuma an bushe su a cikin akwatin safar hannu na tsawon kwanaki 30 ko kusa da jikewa a 0.0005% RH (ja).Layukan tsaye suna yiwa alamar canjin Raman don TFSI tare da N cibiyar haɗin gwiwa zuwa Li+ (746 cm-1) kuma ba a daidaita su zuwa Li+ (741 cm-1), bi da bi.(B) Ratio na kyauta don daidaitawa Li + na nano-SCE kamar yadda aka haɗa (bushe bushes, baƙar fata) kuma bugu da ƙari kuma an bushe a cikin akwatunan safar hannu tare da 0.0005% RH na kwanaki 30 (lu'u lu'u lu'u lu'u-lu'u), wanda ya dace da rabon ƙarfin haɗin gwiwa na Kololuwar Raman (746 cm-1 sama da 741 cm-1).(C) PFG-NMR-wanda aka samu Li + haɗin kai na nano-SCE (jajayen lu'u-lu'u) da ILE ref.(Baƙaƙen murabba'i) azaman aikin tazara tsakanin ƙwanƙwasa ƙwanƙwasa ƙwanƙolin maganadisu.An kwaikwayi kololuwar ka'idar akan kallon Raman ta amfani da lissafin DFT.

Daga pulsed-filin gradient NMR (PFG-NMR), ƙimar rarraba kai na nau'in nau'in Li-ion ta hannu daban-daban an ƙaddara azaman aikin tazara tsakanin ƙwanƙwarar filin magnetic gradient ∆ don bayanin ruwa na ILE da nano- SCE (x = 1.5) tare da daidaitattun ion na 0.6 mS / cm (Fig. 5C).Ƙididdigar rarraba kai ta Li+ a cikin bayanin ILE ya kasance akai-akai, yana nuna cewa nau'in Li guda ɗaya ne kawai ko nau'in motsi iri ɗaya masu kama da juna a cikin ruwa.Ga nano-SCE, ƙimar rarraba kai ya bambanta da ∆ kuma ya zarce na ILE a takaice ∆, yana nuna kasancewar nau'ikan motsi da sauri waɗanda ke amsawa kawai a cikin ɗan gajeren lokaci tsakanin bugunan filin maganadisu.Ƙarƙashin ƙaƙƙarfan ƙayyadaddun rarraba kai yana nuna cewa kusa da haɓakar tattarawar Li-ion kyauta, kamar yadda aka faɗo daga Raman spectroscopy, ƙarfin kunnawa don watsawa yana saukar da shi a cikin mesophase interface Layer shima.Wannan yana goyan bayan haɓaka aikin haɓakawa wanda ions Li+ kyauta suka gabatar a cikin Layer mesophase.A tsawon ∆, ƙimar rarraba kai ya yi ƙasa da na ILE.Wannan yana tabbatar da ƙarancin ƙarancin ion don akwatin safar hannu-cikakken nano-SCE idan aka kwatanta da ILE.ILE da ke cikin tsakiyar mesopores zai sami ɗanko mafi girma saboda ƙuntatawa na motsin kwayoyin halitta.Don haka, haɓakawa ta hanyar ƙirƙirar Li-ions masu saurin yaɗuwa a silica/ice/ILE interface dole ne ya rama raguwar haɓakawa a cikin ainihin ramin.Wannan yana bayyana rashi na haɓakawa a cikin tsarin tushen barbashi inda musaya ba su samar da isassun haɓaka haɓakar ion ba (fig. S1).

An gwada kwanciyar hankali na electrochemical na nano-SCE akan ƙarfe na lithium ta amfani da saitin lantarki guda uku (ana nuna tsarin saitin a fig. S7).Halin halin yanzu-mai yiwuwa na Li/SCE (x = 1.5) da Li/ILE rabin-cell ana nuna su a cikin siffa 6A.Amma ga taga electrochemical a cikin siffa 2, electrochemistry yana iyakance ta ILE filler.Ana lura da plating lithium mai jujjuyawa da tsiri.An kafa wani barga mai ƙarfi mai ƙarfi na lantarki (SEI) a lithium na ƙarfe tare da RSEI na kusan 0.9 kilo-ohm · cm2, alhakin babban digo na IR a cikin lanƙwan iU a duka bangarorin cathodic da anodic.Halin halin yanzu na cathodic a cikin mafita na ILE mai tsabta bai nuna wani hysteresis ba zuwa -2.5 mA/cm2.Koyaya, rushewar anodic ya nuna kololuwar wucewa tare da tsayayyen yanayin halin yanzu na 0.06 mA/cm2 kawai.Reshen cathodic na yanzu a ƙaƙƙarfan ƙaƙƙarfan ƙa'idar Li/SCE ya nuna babu ƙaranci ga igiyoyin katodic ƙasa da -0.5 mA/cm2.Juriya na SEI ya kasance, duk da haka, kusan ninki biyu.Hakazalika, kololuwar anodic ya kasance ƙasa kuma tsayayyen halin yanzu bayan ƙarancin wucewar anodic shine 0.03 mA/cm2, rabin kawai na tsantsar maganin ILE.Samuwar SEI da yadudduka passivation a cikin pores na SCE yana iyakance halin yanzu a ƙarfe na lithium.Duka nau'ikan voltammogram na Li/ILE da Li/SCE electrodes an sake yin su akan zagayowar zagayowar da yawa, wanda ke nuni da cewa Layer passivation na anodic da sinadari na SEI mai jujjuyawa ne kuma karko.Jinkirin narkar da motsin motsin motsin motsi na Li/SCE yana iyakance aikin rabin sel waɗanda aka yi tare da anodes na ƙarfe a ƙasa.

(A) Cyclic voltammogram na nano-SCE (x = 1.5, kamar yadda aka haɗe bayan bushewar bushewa) (ja) da kuma ILE reference (black) wanda aka auna a cikin daidaitawar lantarki guda uku tare da Li a matsayin aiki, counter, da na'urorin lantarki (juriya na SEI da aka kiyasta daga IR drop akan cathodic halin yanzu shine 0.9 da 1.8 kilo-ohm · cm2 don ILE da SCE, bi da bi).(B) Galvanic caji/fitarwa masu lankwasa na Li/SCE (x = 1)/100-nm bakin ciki-fim LiMn2O4 cell don zagayowar biyar a C-rates na 1C, 5C, da 20C.(C) Cyclic voltammograms na Li/SCE/40-μm Li4Ti5O12 da Li/SCE/30-μm LiFePO4 foda kwayoyin lantarki (1 mV/s).(D) Galvanic caji / fidda masu lankwasa na Li/SCE/40-μm Li4Ti5O12 foda lantarki a 1C, 0.1C, 0.2C, da 0.02C.(E) Galvanic caji / fidda masu lankwasa na Li/SCE/30-μm LiFePO4 foda lantarki a 1C, 0.5C, 0.2C, 0.1C, 0.05C, da 0.01C.(F) Ƙarfin (cikakken lu'u-lu'u don lalatawa da kuma buɗe murabba'ai don lithiation) tare da lambar sake zagayowar na Li/SCE/30-μm LiFePO4 foda lantarki;kaurin SCE a cikin sel ya kai kusan 280 μm.Yawan LFP da LTO cathode shine kusan 1.9 da 11.0 mg/cm2, bi da bi.(G) Matsakaicin madaidaicin lokaci na tarin Li/SCE/Li da aka yi keken keke a yawan 0.1, 0.2, 0.5, da 0.1 mA/cm2.(H) Na 1st, 10th, 125th, and last polarization of Li/SCE/Li stack an jaddada a 0.1 mA/cm2, wanda aka nuna a (G).Don (G) da (H), SCE yana da ƙarfin aiki na 0. 34 mS/cm, kuma kauri na pellet SCE shine 0.152 cm.

An yi amfani da fim na bakin ciki na 100-nm LiMn2O4 (LMO) azaman samfurin ingantacciyar lantarki don gwada daidaiton Nano-SCE da kayan lantarki yayin kawar da abubuwan da suka dace da abubuwan da suka dace a cikin abubuwan da suka hada da na'urorin lantarki (37).Ayyukan hawan keke na sikirin-film electrode/SCE stack yana nuna kwanciyar hankali na mu'amala tsakanin lantarki da electrolyte.A cikin wannan tsarin saitin fina-finai na bakin ciki, guda ɗaya ne kawai, madaidaicin ma'anar, kuma tuntuɓar mu'amalar tsarin tsarin yana kasancewa tsakanin electrolyte da electrode, watau, dandamali ne da ya dace don yin nazarin electrochemistry na mahaɗan electrolyte/electrode ba tare da batutuwan canjin girma ba. , da dai sauransu Har ila yau, a cikin wannan gwaji, ƙimar aikin ba'a iyakance shi ta hanyar lantarki na Li-foil counter ba, kamar yadda yawancin halin yanzu (6 μA/cm2 don 1C) ke ƙasa da na tsayayyen yanayin anodic na yanzu don lithium rabin- cell (0.03 mA/cm2).Reproducible da kuma barga caji/fitarwa masu lankwasa ana samu don yanke wutan lantarki a 4.3 V don C-rates tsakanin 1 da 20C na kan 20 hawan keke (Fig. 6B).LMO ba shi da kwanciyar hankali a cikin ruwan lantarki na LiB.Misali, an lura da raguwar ƙarfin 50% akan cajin fim na 100-nm LMO wanda aka fitar don hawan keke na 10 a cikin LiClO4 / propylene carbonate electrolyte a 1C (37).Sakamakonmu ya nuna cewa nano-SCE ya fi dacewa da LMO fiye da na'urar lantarki ta al'ada.

Don nuna haɗin kai na nano-SCE, mun kuma ƙirƙira rabin-kwayoyin halitta tare da Li4Ti5O12 (LTO) da LiFePO4 (LFP) foda lantarki.Maganin farko an jefar da shi a cikin tantanin halitta don zubar da layukan da ba su da ƙarfi sannan a bar su don ƙarin gelation kafin a bushe su kuma a shafe su, kamar na nano-SCE pellets.Kwayoyin suna nuna halayen lithiation/delithiation na madaidaitan lantarki (Fig. 6C).Ƙananan kololuwar igiyoyi na LFP fiye da LTO sun faru ne saboda bambancin kauri na shafi.Ayyukan ƙima yayin ma'aunin caji/fitarwa yanzu an iyakance shi ta hanyar lantarki na Li-foil counter da aka danna akan Layer nano-SCE da aka kafa a saman 30- zuwa 40-μm-kauri mai kauri (Fig. 6, D da E).LTO / nano-SCE / Li cell ya kai iyakar ƙarfinsa na 160 mA·hour / g kawai a ƙananan C-rate na 0.02C (Fig. 6D).Ƙarfin da ake samu yana raguwa da sauri tare da ƙimar C tare da ƙasa da 10% don ƙimar C mafi girma fiye da 0.1C.Hakazalika, LFP / SCE / Li tantanin halitta ya kai iyakar ƙarfinsa na kusan 140 mA·hour / g a 0.01C (Fig. 6E).Hoto na 6F yana nuna aikin ƙima don jimlar zagayowar 30, yana nuna daidaitawar tantanin halitta.Waɗannan gwaje-gwajen suna nuna aikin nano-SCE azaman Li-ion electrolyte da yuwuwar haɗuwa a cikin ƙwayoyin Li-ion.

An gwada kwanciyar hankali ko zagayawa na nano-SCE ta amfani da tari mai ma'ana ta Li/SCE/Li.An yi hawan keke don fiye da hawan keke na 120 a halin yanzu na 0.1 mA / cm2 na 0.5 hours (Fig. 6G) ba tare da wata matsala ba ko samuwar dendrite (Fig. 6H).Wutar lantarki ta polarization ya zama ƙarami akan lokaci, yana nuna haɓaka lamba.Bugu da ƙari, an ƙarfafa tantanin halitta har zuwa nau'i na yanzu na 0.5 mA / cm2, ba tare da wani samuwar lithium dendrites ba ko alamun lalacewa na nano-SCE ko mai dubawa (Fig. 6G).Metallic lithium an san shi don samar da Layer interphase mai kariya ko SEI akan saman sa a cikin BMP-TFSI-based ILEs (27).Wannan halayen kuma yana faruwa ne a mahallin lithium/nano-SCE;kamar yadda aka tattauna a ƙarƙashin siffa 6A, SEI na iya girma dan kadan a cikin pores, yana bayyana mafi girman juriya na SEI don nano-SCE fiye da ILE (duba sama).An sami tabbacin Layer SEI daga spectra IR (fig. S9).Hakazalika da suturar SEI a cikin LiB na gargajiya, wanda ke kallon lantarki na graphite daga ruwan lantarki na ruwa don guje wa ƙarin amsawa, mun yi imanin cewa SEI a nan kuma yana ba da kariya ga ruwan ƙanƙara daga ƙarin amsawa daga ƙarfe lithium anode.Ƙwararren ƙwanƙwasa kafin da bayan polarization na Li/nano-SCE (x = 1.5) na tsawon sa'o'i 10 bai nuna wani canji a cikin juriya na electrolyte ba.Za a buƙaci ma'aunin aikin hawan keke na dogon lokaci don ware jinkirin bushewar Nano-SCE ta ƙarfe na lithium, amma waɗannan sakamakon sun riga sun nuna yuwuwar sa don kyakkyawan yanayin hawan keke na SCE a cikin batura masu ƙarfi na tushen lithium karfe.Duk da haka, ana iya la'akari da rufin interphase na wucin gadi don inganta haɓakar haɗin gwiwar gaba ɗaya.

Mun nuna cewa ion conduction gabatarwa a silica musaya za a iya samu ta hanyar gabatar da wani chemisorbed ruwa Layer a kan OH-kare silica saman.TFSI anions chemisorb akan wannan Layer mai aiki na ruwa ta hanyar haɗin hydrogen tare da ƙungiyar O═S═O.Ruwan saman saman ba shi da motsi don haka ma ya rataye Layer ɗin TFSI da aka tallatawa zuwa saman.Manyan BMP cations suna alaƙa da monolayer na TFSI, don haka suna gabatar da odar kwayoyin halitta na TFSI-BMP a saman.Mun yi imanin cewa jinkirin gelation a cikin yanayi mai ruwa da kuma jinkirin bushewa yana taimakawa wajen samar da aikin ruwa mai aiki da kuma tsari na ions na kwayoyin halitta a samansa.Kamar yadda na farko TFSI anion Layer ya raba wani ɓangare na mummunan cajinsa tare da silica hydroxylated, BMP cation Layer a saman zai nemi haɗin gwiwa tare da wani TFSI anion, ta yadda BMP da yawa za su iya raba cajin da ba a biya su ba tare da TFSI ɗaya (wataƙila uku zuwa ɗaya kamar yadda yake a cikin TFSI). rabo daga IL zuwa Li-TFSI a cikin ILE).Kamar yadda kwayoyin gishiri na Li-TFSI ke da mafi kusancin hanya, Li+ ions za su rabu kuma za a ba su kyauta don yaduwa cikin sauri tare da wannan layin sadarwa.Don ingantacciyar gudanarwa, waɗannan nau'ikan Li+ masu kyauta suna buƙatar ƙarin ƙarin Layer na ruwa na ionic guda ɗaya don wucewa.Saboda wannan dalili, nano-SCE tare da ƙananan darajar x na 0.5 bai nuna haɓakar haɓakawa ba, kamar yadda girman ILE / silica surface area ya isa ga monolayer ɗaya kawai.

An ci gaba da nuna cewa ruwa mai kauri mai kama da kankara ba ya aiki ta hanyar lantarki.A wannan lokaci, ba za mu iya ware cewa ruwan kankara da ke hulɗar kai tsaye tare da farfajiyar lantarki ba ya amsawa.Duk da haka, mun nuna cewa fitar da ruwan saman yana jinkirin kuma don haka ba zai iya ganewa ba don ganowa.Mun gane cewa gurɓataccen ruwa, ko da ƙanana ne, koyaushe zai zama abin damuwa, kuma gwaje-gwaje na tsawon rayuwa kawai za su iya ba da tabbataccen amsa kan ko ruwan yana da isasshen ƙarfi.Koyaya, ana iya haɓaka wasu yadudduka masu aiki waɗanda ke ba da kwatankwacin ko ma fi girma girma girma a yanzu.Dangane da wannan, ƙungiyar Li ta riga ta nuna yuwuwar yuwuwar Layer glycidyloxypropyl azaman ƙungiyar aiki (18).Ruwan ƙanƙara na asali ne ga silica don haka ya dace da nazarin tasirin aikin aikin sama akan haɓakar haɓakar ion bisa tsari, kamar yadda aka nuna cikin nasara anan.Bugu da ƙari, mesophase Layer da dipolensa zai dogara ne akan oxide da kuma a kan kwayoyin halitta da aka tallata don haka ana iya daidaita su ta duka biyu.A cikin dakin gwaje-gwaje, mun riga mun nuna babban bambance-bambance a cikin haɓaka haɓakar ion don ruwa na ion daban-daban.Bugu da ƙari, ƙa'idar da aka nuna ita ce ta gabaɗaya ga gudanarwar ion kuma ana iya amfani da ita don tsarin ion daban-daban masu dacewa, misali, don sodium, magnesium, calcium, ko batir ion aluminum.A ƙarshe, nanocomposite electrolyte tare da dubawar dubawa da aka nuna a nan ra'ayi ne maimakon abu ɗaya, wanda zai iya zama gaba (nano) injiniya zuwa abubuwan da ake so na gudanarwar ion, lambar sufuri, taga electrochemical, aminci, da farashi don tsararrun ƙwayoyin baturi na gaba. .

An shirya nano-SCE ta amfani da hanyar sol-gel.Lithium bis (trifluoromethylsulfonyl) imide Li-TFSI;Sigma-Aldrich;99.95%), 0.5 ml na deionized H2O, 0.5 ml na TEOS (Sigma-Aldrich; 99.0%), 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide (BMP-TFSI; Sigma-Aldrich; 98.5%), da 11. ml na PGME aka gauraye a cikin gilashin gilashi.Matsakaicin molar, x, tsakanin [BMP] [TFSI] da TEOS a cikin cakuda ya bambanta tsakanin 0.25 da 2. Matsakaicin molar na Li[TFSI] da [BMP] [TFSI] an daidaita shi a 0.33: 1.Adadin Li[TFSI] da [BMP][TFSI] an ƙayyade su daga waɗannan ma'auni.Misali, lokacin x = 1, ƙara [BMP] [TFSI] da Li[TFSI] a cikin maganin sune 0.97 da 0.22 g, bi da bi.An girgiza cakuda don 1 min don samar da mafita na monophasic.Wadannan mafita an adana su a cikin rufaffiyar rufaffiyar ba tare da motsawa don samar da gels a cikin dakin da aka sarrafa zafi da zafi (SH-641, ESPEC Corp.) tare da zafin jiki da RH% saita a 25 ° C da 50%, bi da bi.Dangane da x, gaurayawan sun ɗauki, a matsakaita, kwanaki 5 zuwa 9 don samar da fili mai tsabta.Bayan gelation, vials tare da 2.4- zuwa 7.4-ml gel an fara bushe su a 40 ° C na tsawon kwanaki hudu a dan kadan rage matsa lamba (80 kPa) sa'an nan kuma a motsa a cikin tanda na tsawon sa'o'i 72 a 25 ° C.Yayin da aka cire sauran danshi, injin ya ragu a hankali daga matsa lamba na farko a kusa da 50 Pa zuwa matsi na ƙarshe na 5 Pa bayan kusan kwana 1.Saboda yawan ruwa da PGME da za a cire, sakamakon SCE pellets sun ragu daga 20% (x = 0.5) zuwa ~ 50% (x = 2) na ainihin gel girma.An auna nauyin gels da aka samu tare da ma'auni na semimicro (SM 1245Di-C, VWR).

An yi TGA akan Q5000 IR (TA Instruments, New Castle, DE, USA) ƙarƙashin nitrogen.A lokacin ma'auni, samfurori sun yi zafi zuwa 700 ° C a yanayin zafi na 2 ° C / min.FTIR spectrometry an yi ta amfani da Bruker Vertex 70 a cikin lambar kalaman da ke jere daga 4000 zuwa 400 cm−1 a cikin yanayin watsawa.An yi pycnometry ta amfani da Micromeritics AccuPyc II 1340.

Don auna ƙarfin motsin ionic, ƙaramin ƙarar SCE an ɗauko daga uwar vial a cikin akwatin safar hannu mai cike da Ar (0.1-ppm H2O da 0.1-ppm O2).Kusan 23 μl na SCE an cika shi a cikin zoben polytetrafluoroethylene (PTFE) tare da diamita na ciki na 4.34-mm da tsayi 1.57-mm, yana samar da pellet.An yi sandwid ɗin pellet ɗin da ke cikin zoben tsakanin fayafai biyu na bakin karfe (SS) (kauri 0.2 mm; MTI).An yi ma'aunin rashin ƙarfi ta amfani da PGSTAT302 (Metrohm), tare da girman AC na 5 mV a cikin kewayon mitar daga 1 MHz zuwa 1 Hz.An ƙaddara ion conductivity (σi) daga tsattsauran ra'ayi mai girma tare da ainihin axis a cikin makircin Nyquist.Bayan ma'aunin aiki, an ƙyale pellet nano-SCE ya ƙara bushewa a cikin akwatin safar hannu.Don ma'aunin dogaro da zafin jiki, SS/SCE/SS an rufe su a cikin tantanin halitta.Bayan hatimi, daftarin aiki ya kasance akai-akai na kwanaki da yawa (duba fig. S3).Ana sarrafa zafin jiki na sel tsabar kudin tare da jaket na thermal tare da wanka mai zafi ta amfani da H2O/ethylene glycol azaman matsakaicin aiki.An fara sanyaya ƙwayoyin sel zuwa kusan -15 ° C sannan a mataki-mataki mai zafi zuwa 60 ° C.

Daga kowane pellet nano-SCE, an kawo kusan 23 μl cikin zobe (diamita na ciki-4.34-mm da tsayin 1.57-mm) don ma'aunin lantarki kai tsaye a cikin akwatin safar hannu mai cike da N2 tare da sarrafa zafi.Sa'an nan kuma an sanya zoben tare da SCE tsakanin fayafai SS guda biyu (kauri 0.2 mm; MTI).An yi ma'aunin rashin ƙarfi ta amfani da PGSTAT302 (Metrohm) tare da girman AC na 5 mV da mitar da ke jere daga 1 MHz zuwa 1 Hz da aka sarrafa ta software ta Nova.An adana samfuran a kowane ƙimar RH% na sa'o'i 48 kafin a kula da halayen aiki har sai an daidaita su.Ƙimar ƙarfin ionic da aka daidaita don ƙimar RH% (σi) da aka ba da ita an ƙaddara daga tsattsauran ra'ayi mai girma tare da ainihin axis a cikin makircin Nyquist.

Halin halittar pellet tare da kuma ba tare da Li [BMP] [TFSI] ILE an duba shi tare da SEM ta amfani da kayan aikin Thermo Fisher Scientific Apreo a 1.5 zuwa 2.0 kV wanda ke aiki a cikin yanayin hoto mai dual-nemo ta amfani da mai gano T1 da T2 a layi daya don gyare-gyaren hoto mai rai, kuma an yi amfani da mai gano T2 don yin rikodin hotunan SEM da aka nuna;samfurin da aka gyarawa a kan carbon conductive tef.An yi TEM ta amfani da Tecnai mai aiki a 300 kV.

An cire ILE daga pellet na SCE ta hanyoyi biyu daban-daban.Zaɓuɓɓuka ɗaya don samun silica mai ɓarna an yi ta hanyar nutsar da SCE a cikin acetone na awanni 12 don cire Li[BMP][TFSI] ILE.An maimaita wannan kurkura sau uku.Wani zaɓi shine ta hanyar jiƙa SCE a cikin ethanol.A wannan yanayin, an cire ethanol ta amfani da ruwa mai mahimmanci na CO2.

An yi amfani da kayan aiki daban-daban guda biyu don bushewa mai mahimmanci, wato, Automegasamdri-916B, Tousimis (hanyar 1) da kayan aiki na al'ada ta JASCO Corporation (hanyar 2).Lokacin amfani da kayan aiki na farko, jerin bushewa ya fara tare da raguwar zafin jiki zuwa 8 ° C.Daga baya, CO2 an wanke ta cikin ɗakin, yana ƙara matsa lamba zuwa 5.5 MPa.A cikin mataki na gaba, CO2 ya kasance mai zafi zuwa 41 ° C, yana ƙara matsa lamba zuwa 10 MPa, kuma an kiyaye shi don 5 min.Don ƙarewa, a cikin matakin zubar da jini, an saukar da matsa lamba akan lokaci na 10 min.Lokacin amfani da kayan aikin da aka gina na al'ada, an bi irin wannan jerin.Koyaya, lokaci da matsin lamba sun bambanta sosai.Bayan matakin tsarkakewa, an ƙara matsa lamba zuwa 12 MPa a zazzabi na 70 ° C kuma ya kasance kamar haka na 5 zuwa 6 hours.Daga baya, an rage matsa lamba a cikin tazara daga 12 zuwa 7 MPa, 7 zuwa 3 MPa, da 3 zuwa 0 MPa akan tsawon lokaci na 10, 60, da 10 min, bi da bi.

Nitrogen physisorption isotherms an auna su a T = 77 K ta amfani da Micromeritics 3Flex surface hali analyzer.Silica ɗin da aka samu sannan an fitar da iskar gas na sa'o'i 8 a 100 ° C a ƙarƙashin injin 0.1-mbar.Silica mai ƙura da aka samu daga bushewa mai ƙarfi an fitar da iskar gas na sa'o'i 18 a 120 ° C a ƙarƙashin injin 0.1-mbar.Bayan haka, an auna isotherms na physisorption nitrogen a T = 77 K ta amfani da Micromeritics TriStar 3000 mai sarrafa iskar gas mai sarrafa kansa.

An yi ma'aunin PFG-NMR ta amfani da JEOL JNM-ECX400.An yi amfani da jerin bugun bugun bugun jini mai kuzari don ma'aunin yaduwa.An kwatanta siginar siginar echo na yau da kullun, E, a cikin lissafin (38) E = exp (-γ2g2δ2D (Δ-δ / 3)) (1) inda g shine ƙarfin bugun bugun jini, δ shine tsawon lokacin gradient. bugun jini, ∆ shine tazara tsakanin manyan gefuna na bugun jini, γ shine ma'aunin magnetogyric, kuma D shine daidaitawar kai-da-kai na kwayoyin.An ƙididdige ƙididdiga masu rarraba kai ta hanyar daidaita siginar faɗakarwa waɗanda aka samu ta hanyar canza ∆ tare da Eq.1. An zaɓi 7Li don ƙayyade ƙididdige yawan adadin lithium ion.An yi duk ma'auni a 30 ° C.

Saitin spectroscopy na Raman tsarin gida ne ta amfani da argon ion wanda zai iya daidaita shi zuwa hasken wutar lantarki na 458-nm Laser wanda aka haɗa shi a cikin na'urar ganowa ta Olympus IX71 mai jujjuyawar, kuma hasken da aka watsar da baya ya wuce ta hanyar saitin spectrometer TriVista sau uku (Instruments Princeton). ), wanda aka yi amfani da shi don tarwatsa siginar gani da aka gano ta amfani da kyamarar na'ura mai sanyaya mai sanyaya nitrogen.Idan aka ba da babban abin sha na gani a waɗannan madaidaicin raƙuman ruwa, an yi amfani da ƙananan ƙarfin laser don guje wa dumama laser (<100 W · cm-2).

DFT haɓaka jumloli na ƙasa-jihar da ƙididdigar mitar nazari sun yi amfani da mashahurin aikin matasan B3LYP da saiti na 6-311++ G**, tare da gyaran tarwatsawar zarra ta Grimme (39) tare da tsarin damping na Becke-Johnson (D3BJ), kamar yadda aiwatar a cikin ORCA 3.0.3 (40).An kwaikwayi sifofin Raman ta amfani da ORCA, kuma an sami hangen nesa na kaddarorin kwayoyin halitta ta amfani da fakitin software na Avogadro (41) tare da sabuntawar tallafin ORCA.

Duk ma'auni na electrochemical da shirye-shiryen samfurin da suka danganci an yi su a cikin akwatin safar hannu mai cike da argon (PureLab, PL-HE-4GB-1800; <1-ppm O2 da H2O matakan) da aka keɓe don halayen halayen lantarki.An sanya pellet ɗin SCE akan ribbon Li (Sigma-Aldrich; 99.9%) wanda aka goyan baya akan farantin tagulla yayin da na'urar lantarki da naushi biyu na Li disks (diamita 5-mm) an sanya su a saman pellet ɗin SCE don tunani da aiki. lantarki.Ana nuna saitin a fig.S7.An yi amfani da fil ɗin zinariya don tuntuɓar ma'anar lithium da na'urorin lantarki masu aiki.An yi ma'aunin voltammetry na cyclic da ma'aunin impedance ta amfani da PGSTAT302 (Metrohm) sarrafawa ta software ta Nova.An yi voltammetry na cyclic tare da ƙimar sikanin 20 mV/s.An yi ma'aunin impedance tare da girman AC na 5 mV da mitar da ke jere daga 1 MHz zuwa 0.1 Hz.

An ajiye na'urar lantarki ta 40-nm anatase TiO2 na bakin ciki-fim ta hanyar jigon atomic Layer (ALD) akan wafer silicon 300-mm tare da 40-nm TiN underlayer shima ALD ya ajiye shi.Yana da kyakkyawan gwajin lantarki don nunin halayen Li-ion ta hanyar electrolytes, kamar yadda TiO2 ba ya sha wahala daga lalata sinadarai ko damuwa na inji (babu wani canji mai mahimmanci) yayin hawan keke.Don auna ƙwayar Li / SCE / TiO2, ILE-SCEs an cika su a cikin zoben PTFE tare da diamita na 4.3 mm da kauri na 0.15 cm;sa'an nan, zoben da aka sandwiched tsakanin wani Li foil da TiO2 fim.

Nano-SCE/nano-film electrode rabin tararraki, tare da lantarki na LMO, an ƙirƙira su ta hanyar haɗa fim ɗin nano-SCE akan wayoyin.Jimlar 150 μl na x = 1.5 bayani, shekaru na kwanaki 2, an jefar da shi a cikin zoben gilashi (diamita, 1.3 mm) wanda aka saka a kan fina-finai na electrolyte.Sa'an nan kuma an rufe zobe da parafilm, kuma an ajiye maganin a cikin irin wannan akwati da aka rufe don gel na tsawon kwanaki 4.Tarin gel/electrode da aka kafa kamar haka an bushe shi don samar da tarin nano-SCE/electrode.Kaurin nano-SCE, da aka ƙayyade ta amfani da micrometer, shine 300 μm.A ƙarshe, an matse foil ɗin lithium (kauri 1.75 mm, 99.9%; Sigma-Aldrich) akan tarin nano-SCE/electrode azaman anode.LiMn2O4 (LMO) na bakin ciki-fim na 100-nm electrode na bakin ciki an ajiye shi ta hanyar mitar rediyo a ƙarƙashin Ar kwarara akan wafer silicon da aka lulluɓe da 80-nm Pt (DC sputtering) / 10-nm TiN (ALD).An shafe wannan tari na minti 20 a 800 ° C a cikin yanayin oxygen.

LiFePO4 (LFP) fina-finan lantarki an shirya su ta hanyar rufin ruwa.Na farko, an ƙara baƙar fata na carbon da LFP (2 zuwa 3 μm) zuwa maganin ruwa mai ɗauke da carboxymethylcellulose (CMC) don samar da cakuda wanda aka haɗa shi daga baya ta hanyar amfani da mahaɗar duniya.Sa'an nan, samfurin homogenized da aka gauraye da deionized ruwa da fluorinated acrylic latex (JSR, TRD202A) a cikin injin mahaɗin don samar da wani slurry ga electrode shafi.An jefa slurry ɗin da aka shirya akan foils na aluminium don saka fina-finai na lantarki ta amfani da abin rufe fuska.Wadannan jikayen na'urorin lantarki da aka rufa da su nan da nan an sanya su a cikin tanda na yanayi tare da iska mai ƙarfi a 70 ° C na minti 10 kuma an ƙara bushewa a 140 ° C na 4 hours a cikin tanda.Busassun fina-finan lantarki sun ƙunshi 91 wt % LiFePO4, 3 wt % carbon baki, 2 wt % CMC, da 4 wt% TRD202A.Kaurin fim ɗin shine μm 30 (an ƙaddara ta amfani da micrometer da duban microscope na lantarki).

Li4Ti5O12 (LTO) fina-finan lantarki an yi su a kan foils na tagulla kamar yadda aka saba.A abun da ke ciki na busassun lantarki ne 85 wt % Li4Ti5O12, 5 wt % carbon baki, 5 wt % CMC, da 5 wt % fluorinated acrylic latex (TRD2001A).Kaurin fim ɗin shine 40 μm.

Maganin SCE an jefar da shi akan fim ɗin LFP mai tushen barbashi da LTO electrode.Na farko, 100 μl na x = 1.5 bayani, shekaru na kwanaki 2, an jefar da shi a kan fim din lantarki, tare da diamita na 15 mm, an sanya shi a cikin kwayar tsabar kudi (#2032, MTI).Bayan da SCE mai ciki ya kasance gelled, an bushe fim ɗin a 25 ° C na tsawon awanni 72 a cikin tanda (<5 × 10-2 mbar) don yin tari na nano-SCE da na'urar lantarki.Nano-SCE kauri ya kasance 380 μm.A ƙarshe, an danna foil na lithium akan ma'aunin SCE/electrode a matsayin anode, kuma an rufe tantanin kuɗin tsabar kudin.An yi ma'aunin lantarki na lantarki ta amfani da Solartron 1470E potentiostat a zafin jiki.

Ana samun ƙarin kayan wannan labarin a http://advances.sciencemag.org/cgi/content/full/6/2/eaav3400/DC1

Table S1.Kaddarorin tsarin silica matrix a cikin nano-SCE don haɓaka juzu'in molar ruwa na ionic ruwa zuwa silica (darajar x) da aka ƙayyade daga N2 adsorption/desorption ko ma'aunin BET da kuma abubuwan lura na TEM.

Wannan labarin buɗaɗɗen shiga ne wanda aka rarraba ƙarƙashin sharuɗɗan lasisin Haɗaɗɗen Haɗin Kai-NonCommercial, wanda ke ba da izinin amfani, rarrabawa, da haifuwa a kowane matsakaici, muddin sakamakon amfani da shi ba don fa'idar kasuwanci ba ne kuma idan aikin na asali ya kasance daidai. ambato.

NOTE: Muna buƙatar adireshin imel ɗin ku kawai don mutumin da kuke ba da shawarar shafin ya san cewa kuna son su gani, kuma ba saƙon takarce ba ne.Ba mu kama kowane adireshin imel ba.

Wannan tambayar don gwada ko kai baƙo ne ko a'a kuma don hana ƙaddamar da spam mai sarrafa kansa.

Daga 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 M. Vereeckeen

Lokacin aikawa: Yuli-15-2020