Ukushintshela kumabhethri e-Li-ion esimo esiqinile kuzovumela inqubekelaphambili efinyelela ekuminyanisweni kwamandla okungu-1000 W·hour/litre nangaphezulu.Inhlanganisela ye-mesoporous oxide matrix egcwele izihlungi ze-electrolyte ezingashintshile ze-ionic zihlolisiswe njengenketho eqinile ye-electrolyte.Kodwa-ke, ukuvalelwa okulula kwezixazululo ze-electrolyte ngaphakathi kwezimbotshana ezinosayizi we-nanometer kuholela ekuziphatheni okuphansi kwe-ion njengoba i-viscosity ikhula.Lapha, sibonisa ukuthi i-Li-ion conductivity ye-nanocomposites ehlanganisa i-mesoporous silica monolith ene-ionic liquid electrolyte filler ingaba phezulu ngokuphindwe kaningana kunaleyo ye-electrolyte ye-ionic emsulwa yoketshezi ngokwethulwa kongqimba lweqhwa oluhlangana ubuso.Ukukhangisa okuqinile nokuhleleka kwama-molecule e-ionic liquid kuwenza anganyakazi futhi aqine njengongqimba lweqhwa oluhlangene ngobuso ngokwalo.I-dipole phezu kongqimba lwe-mesophase ye-adsorbate iphumela ekuxazululeni ama-ion we-Li+ ukuze kuqhutshekwe nokwenziwa ngcono.Umgomo obonisiwe wokuthuthukiswa kwe-ion conduction ungasetshenziswa kumasistimu e-ion ahlukene.

Ama-electrolyte esimo esiqinile kulindeleke ukuthi anikeze amandla alandelayo ukuze amabhethri e-Li-ion adlule usilingi ongokoqobo wama-800 W·hour/litre noma 300 W·hour/kg obekwe kumakhemikhali atholakalayo e-cathode kanye ne-anode.Ukwenyuka okulindelekile kokuminyana kwamandla kumabhethri esimo esiqinile kuvela eminikelo eminingana, konke kuqondiswe ekukhuphuleni iphesenti levolumu yezinto ezisebenzayo kuseli.Okumenyezelwe kakhulu ukwethulwa kwensimbi ye-lithium esikhundleni segraphite negraphite/silicon njenge-anode.Insimbi ye-lithium ehlanzekile inomthamo omkhulu wamandla ngangokunokwenzeka futhi ngaleyo ndlela izodinga isikhala esincane.Kodwa-ke, izinkinga eziningi zisadinga ukuxazululwa, njengokusabela okungenakuhlehliswa (futhi ngaleyo ndlela ukusetshenziswa) kwensimbi ye-lithium, ukwakheka kwe-dendrite, ukwanda kokuminyana okusebenzayo kwamanje kwe-planar lithium foil uma kuqhathaniswa ne-porous graphite (silicon) electrode, futhi, okokugcina. kodwa okungenani, "ukunyamalala" kwe-lithium ngesikhathi sokukhishwa (i-deplating) futhi ngaleyo ndlela ukulahlekelwa ukuxhumana ne-electrolyte eqinile.Imvelo eqinile ngokomshini yama-electrolyte e-ceramic aqinile ayinakuthotshelwa, futhi ukucindezela okukhulu kuyadingeka ukuze kusetshenziswe i-lithium ngokuqinile ngokumelene nengxenye ye-electrolyte eqinile.Amaphuzu okucindezela ahlukene ehlisa indawo esebenza kahle nakakhulu, okuholela ekwakhekeni kwe-dendrite yendawo kanye namadiphozi e-spongiy.Ama-electrolyte e-polymer ahambisana kakhulu nemishini kodwa awakakabonisi ukuqhutshwa kwe-ionic ephakeme ngokwanele ekamelweni lokushisa.Izinto ezintsha ezithakazelisayo kakhulu mayelana nalokhu ama-electrolyte ejeli ye-silica, abuye abizwe ngokuthi “ama-ionogel,” lapho i-ionic liquid electrolyte (ILE) ivalelwe ku-silica matrix ye-nanoporous (1).I-porosity ephezulu kakhulu ye-silica matrix (70 kuya ku-90%) inika lezi zinto ze-electrolyte ze-nanocomposite ukufana okufana nejeli futhi ngaleyo ndlela zizenze zithobelane ngokuzenzakalelayo njenge-polymer electrolyte.Lawa ma-silica gels kwesinye isikhathi akhonjiswa njengama-electrolyte aqinile ayi-hybrid, njengoba aqukethe uketshezi.Kodwa-ke, kuma-silica nanocomposites, njengalawo achazwe kuleli phepha, i-electrolyte "yoketshezi" ye-ionic iba njengokuqinile uma ivalelwe eziteshini ezinosayizi we-nanometer kokubili ngokukhuphuka kwe-viscosity kanye nokukhanyiswa odongeni lwe-silica oluvala i-silica. isiteshi.Uma i-silica matrix izosebenza nje njengesihlukanisi esinezimbotshana, khona-ke ukwanda kwe-viscosity ye-electrolyte ewuketshezi evalekile kungaholela ekwehleni kokusebenza kwe-ionic.Esikhundleni salokho, ukusebenzisana phakathi kwama-molecule e-ILE kanye nodonga lwe-silica pore kwenza izakhiwo ze-nanocomposite zihluke kwisamba sezingxenye zayo ngazinye.Ukufakwa koketshezi lwe-ionic kuma-oxide ngokwakheka kwezingqimba ze-mesophase eziqinile ezifika kuma-nanometer ambalwa ngogqinsi kubonisiwe ezindaweni eziqondile ezinemakroskopu yamandla e-athomu (2).I-adsorption ekhethiwe ye-ionic liquid anion kanye nama-cation endaweni ye-oxide kungaholela ekuthuthukisweni kokusebenza kwe-Li+ kulezi zindawo zokusebenzelana.Vele, ukuthuthukiswa okuhambisana nezindawo zokuhlangana kwe-oxide kufanele kunxephezele noma kudlule ngisho nokuncipha kokusebenza nge-ILE evalelwe phakathi kwezimbotshana.Ngakho-ke, usayizi omncane we-pore kanye nezilinganiso eziphezulu ze-surface-to-volume ziyafunwa.Kuze kube manje, ama-ionogel ane-ion conductivities asondela kuleyo ye-ILE ngokwayo aboniswe ngokwenza kahle kwesakhiwo se-mesoporous (3).Lokhu kusho ukuthi isithuthukisi se-interface besivele sikhona kodwa hhayi ezingeni lokudlula ukuqhutshwa kwenqwaba.

Ukulungiswa kwama-ionogel kuqala ngengxube ye-homogeneous liquid, lapho i-ILE yengezwa kusixazululo se-sol-gel esandulela ukuhlanganiswa kwe-oxide matrix (4, 5).Kule ndlela, i-ILE kanye ne-matrix yakha inhlanganisela ngendlela “in situ”: Izandulela kusixazululo zisabela ukuze zenze i-oxide matrix ezungeze isifanekiso soketshezi lwe-ionic, esisibekela enqubweni.Ngaphansi kwezimo ezithile zokuhlanganisa, i-ILE-SCE elungisiwe (i-electrolyte eyinhlanganisela eqinile) ingaba sesimweni se-monolith ne-ILE eshumekwe kunethiwekhi eqhubekayo ye-mesoporous inorganic oxide.Kuze kube manje, iningi lama-ILE-SCE asekelwe ku-silica alungiswe ngale ndlela, nakuba izibonelo zenziwe nge-alumina (6), i-titania (7), ngisho ne-tin oxide (8).Ukwakhiwa okuningi kwe-sol-gel okubikwayo kuqukethe i-ILE, i-alkyl-silicate efana ne-tetraethyl orthosilicate (TEOS) njenge-silica precursor, kanye ne-formic acid njenge-reagent ne-solvent (9, 10).Ngokusho kwendlela ehlongozwayo (11) yale nqubo ye-sol-gel, i-silica ikhiqizwa ngokuyinhloko ukusabela phakathi kwe-TEOS ne-formic acid, nakuba amanzi ekhiqizwa ngesikhathi senqubo ye-sol-gel.Ngaphandle kwalezi zingxube "ezingezona amanzi" ezisekelwe kwi-formic acid, ukwakheka kwe-sol-gel ene-aqueous ne-HCl njenge-catalyst kanye ne-H2O njenge-reagent (plus organic solvent) nakho kuye kwachazwa, nokho, kulesi simo mayelana nokuhlanganiswa kwenhlanganisela ye-silica uketshezi lwe-ionic kuphela (12-15).

Ngokuvamile, ama-ionogel abonisa ukusebenza kwe-ion okuphansi kunaleyo yesithenjwa se-ILE.Isizukulwane sokuqala sama-ionogel sasinezinga lokushisa legumbi ngokuvamile elilinganiselwa ku-30 ​​kuye ku-50% yenani le-ILE lenqwaba, nakuba ezinye izibonelo ezifinyelela ku-80% ziye zabikwa (9, 10, 16, 17).Umthelela wokuqukethwe kwe-ILE kanye nomphumela we-pore morphology ku-ionogel conductivity usuphenywe ngokuningiliziwe (3);Nokho, alukho ucwaningo oluhlelekile lwemiphumela yokuthuthukisa isixhumi esibonakalayo olwaziwayo.Wu et al.(18) muva nje kubikwe nge-ionogel esebenzayo e-situ, ephinde yanikeza ukuthuthukiswa kokusebenza uma kuqhathaniswa nenqwaba ye-ILE.Ukuthuthukiswa kwabalelwa ekusebenzisaneni phakathi kwe-anion neqembu elisebenzayo le-3-glycidyloxypropyl endaweni ye-silica.Lokhu kuthola kusekela umbono wokuthi ukusebenza kwendawo kungathuthukisa ngempela ukukhuthazwa kokwenziwa kwesixhumi esibonakalayo.

Kulo msebenzi, sibonisa ukwakheka kwe-in-situ kongqimba oluqinile lwamanzi e-ice ku-silica futhi siningiliza indlela yokuqhutshwa kwe-Li-ion ye-interfacial ngokukhula kokuxhumana kwe-dipole phakathi kongqimba olusebenzayo lweqhwa kanye nongqimba lwe-adsorbed ionic liquid mesophase.Ngokuhlanganiswa kwendawo ephezulu yangaphakathi kanye nongqimba olusebenzayo lweqhwa, ama-electrolyte aqinile e-nanocomposite (nano-SCE) ane-200% ephakeme ye-Li-ion conductivity kunereferensi ye-ILE ezuziwe.I-silica matrix iboniswa inesakhiwo sangempela se-monolithic mesoporous esinamavolumu embotshana kanye nezindawo ezingaphezulu ezifika ku-90% kanye ne-1400 m2/g, ngaleyo ndlela inikeze izilinganiso ezidlulele ze-surface-to-volume okuvumela umnikelo omkhulu wokuthuthukiswa kokuqhuba eduze kwalezi zixhumanisi.Ngokusebenza okuthuthukisiwe kwendawo ye-silica ehlanganiswe nokukhulisa isilinganiso sobuso-kuya-kwivolumu, i-nano-SCE ene-ion conductivities edlula kahle ku-10 mS/cm ingase yenziwe futhi ngaleyo ndlela ithandeke kakhulu kumabhethri amakhulu okusebenza kwezimoto.

Ukugxila kwephepha lethu kumshini wokwenziwa kokusebenzelana okuthuthukisiwe ngokwakhiwa kwesendlalelo se-mesophase ngobufakazi obuvela ku-Raman, i-Fourier transform infrared (FTIR), kanye ne-nuclear magnetic resonance (NMR) spectroscopy.Ukuzinza kokusebenzelana kwempahla yethu ye-nano-SCE kuma-voltage aphezulu kuboniswa kusetshenziswa ama-electrode e-lithium manganese oxide (LMO) yefilimu emincane.Ngale ndlela, ukugxila kugcina kokubalulekile kunokuhlanganiswa kwe-electrode kanye nezindaba zomhlangano weseli.Ngokufanayo, iwindi le-electrochemical kanye nokuzinza ngokumelene ne-lithium metal foils kubonakala ngokugcwele.Ukusebenza nokuhlanganiswa kwe-nano-SCE yethu kuboniswa ngokuhlanganisa nezinga lokuhlolwa kokusebenza kwe-lithium iron phosphate (LFP) namaseli e-lithium titanate (LTO).Ukuzinza kwe-electrolyte yethu kanye nokungasebenzi kwe-electrochemical kwamanzi eqhwa kuboniswe ngokuhamba kwesikhathi eside kwamaseli e-Li-SCE-Li e-symmetric.Ukuthuthukisa ukuminyana kwamandla, ukusebenza kwezinga, nokusebenza kokuhamba ngebhayisikili kwamaseli ahlanganiswe ngokugcwele kuzoba ukugxila kwamaphepha okulandelela (19, 20).

Ukukhuthazwa kwe-ion conductivity ye-interfacial kumasistimu ahlanganisiwe wezigaba ezimbili kwaziwa cishe iminyaka engama-90 (21).Isibonelo, kuze kufike kuma-oda amane okwanda kokusebenza kwe-ionic kukhonjiswe izinhlanganisela zosawoti we-lithium olula njenge-lithium iodide enezinhlayiya ze-mesoporous oxide ezifana ne-silica noma i-alumina uma kuqhathaniswa nokuqhutshwa kwe-ion ye-electrolyte ye-lithium kasawoti ehlanzekile (22).Ama-ion kulawa ma-SCE angasakazeka ngokushesha kakhulu kungqimba lukagesi oluphindwe kabili lwe-Li ion-(noma olucebile) olwakhiwe kusixhumi esibonakalayo se-oxide/electrolyte.Ngeshwa, i-ion conductivity etholwe kulezi zinhlanganisela ezilula ezinezingxenye ezimbili ze-inorganic solid-solid (1) ayikadluli umkhawulo ongu-1-mS/cm2 odingekayo ukuze kuvalwe ibhuloho lebanga elingamakhulu ambalwa lama-micrometer phakathi kwamapuleti amanje okuqoqwa kwebhethri e-Li-ion. .Umqondo we-heterogeneous doping ene-oxide matrix ukuze kuthuthukiswe i-ionic conductivity uye wahlolelwa ama-polymer electrolyte (23) nama-ILEs (24), anokuziphatha okuphezulu kwe-ionic kwangaphakathi kokuqala.Ukwengeza, ikhemikhali ye-molecular (stereo) ecebile yengxenye yesithathu ivula izindlela ezengeziwe ze-ion conduction, njengoba ama-molecule afana ne-polar afana ne-solvent angase abambe iqhaza ekwakhiweni kongqimba oluphindwe kabili lukagesi.Nakuba isenzo sokuxazulula samaqembu e-ether ku-polyethylene oxide polymer electrolyte kunikeza i-solid state ion conductivities engu-~10−6 S/cm ye-LiClO4 kuya ku-~10−5 S/cm ye-LiN(SO2CF3)2, izinhlanganisela zayo ne-silica, i-alumina , noma i-titania nanoparticles inganikeza ngempela ukuthuthukiswa okungaphezu kokuphindwe ka-10 ekuphatheni kwe-ion okulinganiselwe (25), ngeshwa, namanje ngaphansi komkhawulo wezinga lokushisa ongu-1 mS/cm.Izixazululo ze-ILE ziyingxube ye-Li-salt solute kanye ne-ionic liquid solvent, engase ibe nokuhamba okuphezulu kwe-ionic kwangaphakathi phakathi kuka-0.1 no-10 mS/cm (26, 27).Imizamo eminingana yenziwe yokuthuthukisa ukuqhutshwa kwe-ion ngokuyixuba noma ukuyixuba nge-oxide nanoparticles noma ukuvala i-ILE kuma-microparticles e-mesoporous (9, 16, 28, 29).Kodwa-ke, kuze kube manje, akukho ukuthuthukiswa kwe-ion conductivity okuye kwabonwa kwezingxenye ezintathu ze-Li-salt/ionic liquid/oxide composite (fig. S1).Nakuba ukusetshenziswa kwama-microparticles e-silica e-mesoporous kuholela ekusebenzeni okuphezulu uma kuqhathaniswa nezinhlanganisela ezinama-nanoparticles aqinile, indawo yobuso obuhlangene nokukhuthazwa kwe-ion conduction akwanele ukudlula ubuningi be-ILE conductivity.

I-silica ye-Mesoporous iyinto eyaziwa kakhulu esetshenziswa ku-catalysis.Ngokuvamile kwenziwa nge-hydrothermal noma i-sol-gel synthesis elula.Izinqubo ze-Hydrothermal ngokuvamile ziholela kuma-mesoporous powders, kodwa ngokulawulwa ngokucophelela kwenqubo ye-sol-gel lokushisa ekamelweni, ingilazi enkulu ye-monoliths enezimbobo noma ama-aerogels nawo akhiqizwa.I-silica matrix yakheka ngokusebenzisa i-hydrolysis kanye nokusabela kwe-condensation ye-tetra-alkyl orthosilicates (30).Okubalulekile ekulawuleni isakhiwo se-pore ukusetshenziswa kwezifanekiso, isibonelo, i-micelle yohlobo lwe-surfactant, lapho kwakheka khona i-silica matrix.Lapho uketshezi lwe-ionic lwengezwa njenge-molecule yesifanekiso, i-hydrated silica matrix isebenzisana noketshezi lwe-ionic, yenze ijeli, futhi ngemva kokuphulukisa nokomiswa, uketshezi lwe-ionic luvalelwa ngaphakathi kwe-silica matrix eqinile ye-nanoporous (13).Lapho usawoti we-lithium wengezwa njengengxenye yesithathu, i-ILE evalelwe ku-silica matrix yenza i-silica gel electrolyte, nayo ebizwa ngokuthi i-ionogel (24).Kodwa-ke, kuze kube manje, lawa ma-electrolyte ejeli ye-silica abonisa ukuqhutshwa kwe-ILE kwenqwaba kodwa kungadluli, ngaphandle kwecala elilodwa lapho i-silica yayike yasebenza ngamakhemikhali (bona Isingeniso) (18).

Lapha, sibonisa, ukukhuthazwa okuhlelekile kwe-Li-ion conductivity ye-nanocomposite kahle ngaphezu kwalokho kwe-ILE ehlanzekile.Isibonelo se-1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP-TFSI) sisetshenziswa lapha.Kucatshangwa ukuthi ukukhangisa kwama-athomu e-ionic liquid endaweni ye-silica eqediwe ye-OH kukhuthazwa ukuba khona kongqimba lwamanzi eqhwa ahlangene.Ukuhlangana okuqinile kwe-hydrogen phakathi kwamanzi eqhwa kanye ne-TFSI− anion kubangela ukuhleleka kwamangqamuzana oketshezi lwe-ionic, okufana nezizinda ezi-odwe ezizenzakalele zibe uketshezi lwe-ionic (31).Umehluko obalulekile ngezizinda ezakhiwe ngokungahleliwe ngenqwaba ye-ILE ukuthi ungqimba lweqhwa lusebenza njengesendlalelo esisebenzayo (i) esingenisa ukuhleleka kwamangqamuzana endaweni ye-oxide futhi (ii) sethula ukubopha okuqinile kwe-H ukuze kunxenxe i-dipoles ukuthi ikhulule i-Li+ yamahhala ukuze kwenziwe ngcono.Eduze kokwanda kokugxiliswa kwe-Li+ yamahhala, sizobonisa ukuthi amandla okwenza kusebenze okusabalalisa aphansi eduze kwesixhumi esibonakalayo esiyinhlanganisela nongqimba lwe-ILE olukhangiswayo kanye nongqimba lwamanzi eqhwa.

Ungqimba lwamanzi angaphezulu oluwugqinsi lwama-monolayers ambalwa ku-silica luwungqimba oluqinile, njengoba luhlanganiswe ngokuqinile namaqembu e-silanol ngamabhuloho e-H futhi ngenxa yalokho lubizwa nangokuthi ungqimba lweqhwa (32).Ukuminyana nokujiya kwayo (kulinganiselwa kufika kuma-monolayers amathathu kuya kwamane, ano ~0.25 nm nge-ice monolayer ngayinye) aku-equilibrium ye-thermodynamic nengxenye yokucindezela kwamanzi [umswakama ohlobene (RH)] endaweni (fig. S2).Sibonisa ukuthi ukuguquguquka kwe-ion kuyanda ngogqinsi longqimba lwamanzi eqhwa njengoba ukuhlangana kwe-hydrogen nezingqimba ze-ayoni ezikhangisiwe nakho kuyanda.Ungqimba lwamanzi eqhwa luzinzile lufana namanzi ayikristalu kumakhompiyutha amakhemikhali.Lokhu kuhluke kakhulu kuma-electrolyte anamanzi agxile kakhulu noma lokho okubizwa ngokuthi amanzi ezingxube zikasawoti, lapho iwindi le-electrochemical linwetshwa kakhulu kodwa, ekugcineni, amanzi asasebenza ngokwe-electrochemically (33).

Ngokuhlukile kumaresiphi ajwayelekile e-formic acid-catalyzed ionogel, sisebenzise ingxube ye-pH 5 ethambile enomthamo omkhulu wamanzi kanye ne-PGME (1-methoxy-2-propanol) yengezwe kumanduleli we-TEOS ngosawoti we-Li-TFSI kanye noketshezi lwe-ionic lwe-BMP-TFSI.Kule pH, ukusabela kwe-hydrolysis kuhamba kancane, kuyilapho ukufingqa kuhle (30).Ama-Li ions kukholakala ukuthi asebenza njenge-catalyst ye-hydrolysis reaction, njengoba kungekho ukugeleza okwenzeka lapho usawoti we-lithium ungekho kuyilapho zombili zine-pH efanayo engu-5. Isilinganiso se-molar soketshezi lwe-ionic kuya ku-TEOS (futhi ngaleyo ndlela ama-silica moieties) ikhonjiswe njengevelu engu-x futhi ibihlukanisiwe phakathi kuka-0.25 no-2. Isilinganiso se-molar ye-BMP-TFSI kuya ku-Li-TFSI sigcinwe ku-3 (ihambisana nesisombululo se-Li-ion esingu-1 M).Ukomisa kancane kwakudingeka ukuze kugcinwe ubuqotho besakhiwo sesakhiwo se-monolith (bheka Izinto Ezibalulekile Nezindlela).Umfanekiso 1A ubonisa isithombe se-monolithic pellet etholwe ngemva kokumiswa kwe-vacuum.Ukomiswa kwe-vacuum yamahora angu-72 kwanele ukususa wonke umswakama kuze kufike endaweni lapho wonke amanzi amahhala esusiwe kuyilapho ungqimba lwamanzi eqhwa adsorbed luhlala luphelele, njengoba kuqinisekiswe yi-FTIR.Akukho ukudlidliza kwamanzi amahhala okutholwe ku-1635 cm−1 kunoma yimaphi amasampula ngemva kwesinyathelo sokumisa i-vacuum (Fig. 2).Uma kuqhathaniswa, i-spectrum ye-FTIR yesampula ye-nano-SCE (x = 1.5) egcinwe isonto eli-1 ebhokisini legilavu ​​le-N2 ku-60% RH iyaboniswa.Kulokhu, kuvela isiqongo samanzi samahhala esicacile.Onke amasampuli, ngakolunye uhlangothi, abonise isignali ecacile yokusebenza kwe-silanol surface (i-Si─OH egoba phakathi kuka-950 no-980 cm−1) kanye nongqimba lwamanzi eqhwa adsorbed (O─H olunwebeka ku-~3540 cm−1) oluxhunywe ku- amaqembu angaphezulu kwe-─OH nge-H-bonding (imininingwane eyengeziwe ngezansi).Izitsha zazikalwa ngaphambi nangemva kwesinyathelo sokumisa ukulinganisa amanzi agcinwe ku-nano-SCE (ithebula S1).Kamuva, sizobala inani lama-monolayers ahambisanayo ezingqimba zeqhwa eziboshwe phezulu kusukela esisindweni eseqile.Ama-pellets afakwe ngevacuum alethwa ebhokisini lamagilavu ​​[<0.1-ppm (izingxenye ngesigidi) H2O] futhi agcinwa ezitsheni ezivaliwe ukuze kugcinwe amanzi okuqala.Ivolumu encane ithathwe ku-pellet ukuze kufakwe umlingisi oqhubekayo.

(A) Isithombe samapellets amabili we-nano-SCE (kwesokunxele) ahlanganiswe ku-vial;ngemuva kwe-gelation, kutholakala i-pellet ebonakalayo.Qaphela ukuthi i-pellet isobala ngokugcwele ngakho-ke inikezwe umbala oluhlaza okwesibhakabhaka ukuze ibonakale.Lapho i-ILE isusiwe, i-pellet emhlophe eshwabene ihlala i-matrix ye-silica enezimbobo kakhulu (kwesokudla).(B) Isithombe se-electron microscopy (SEM) sokuskena se-matrix ye-SiO2 esisala ngemva kokususwa kwe-ILE.(C) Sondeza isithombe esiboniswe ku-(B) esibonisa imvelo ye-mesoporous yento ye-matrix ngama-macropores athile.(D) Isithombe se-electron microscopy (TEM) yokudlulisa esibonisa ukupakishwa okuminyene kwama-silica nanoparticles angu-7- kuya ku-10-nm njengamabhulokhi wokwakha we-porous matrix material.(E) I-porosity yesakhiwo se-matrix yakhelwe izilinganiso ezihlukahlukene ze-molar ye-ILE ngokuphathelene ne-SiO2 (inani elingu-x).Umugqa onedeshi unikeza i-porosity yetiyori enqunywa kusukela kungxenyana yevolumu ye-ILE ne-silica.Amasampula ahlanjululwe i-acetone (izikwele ezimnyama) omisiwe emoyeni, okunikeza ukubhidlika kwesakhiwo kwe-x > 0.5.Ukomiswa okukhulu kwe-CO2 kwe-ethanol ehlanjululwe yi-nano-SCE (imibuthano eluhlaza) kuvimbela ukuwohloka kuze kufike ku-x = 2 ukuze kususwe kancane kancane i-CO2 (indingilizi evuliwe).BET, Brunauer-Emmett-Teller.Ikhredithi yesithombe: Fred Loosen, imec;Akihiko Sagara, Panasonic.

(A) I-IR spectra ye-nano-SCE njengoba yomiswe ku-vacuum (emnyama) futhi kamuva yomiswa nakakhulu ebhokisini legilavu ​​elingu-0.0005% RH izinsuku ezingu-9 (okuluhlaza okwesibhakabhaka) futhi livezwe ku-30% RH izinsuku ezingu-4 (bomvu) kanye nezingu-60 % RH izinsuku eziyi-8 (okuluhlaza), ngokulandelana.noma, amayunithi angenasizathu.(B) Ama-voltammograms e-cyclic yesitaki se-Li/SCE/TiN anamanani angu-x angu-1.0 (aluhlaza okwesibhakabhaka), 1.5 (oluhlaza okotshani), no-2.0 (obomvu) kanye nereferensi ye-ILE (emnyama);i-inset ibonisa yamanje esikalini se-logarithmic.(C) I-cyclic voltammograms ye-Li/SCE (x = 2)/40-nm TiO2 isitaki (ebomvu), i-ILE (amachashazi amnyama), kanye ne-ILE enesisindo esingu-5 % (wt %) H2O (umugqa oluhlaza wamachashazi edeshi);ku-(B) kanye no-(C), izilinganiso nge-ILE ne-ILE ene-H2O zenziwe ekucushweni kwama-electrode amathathu nge-TiN njenge-electrode esebenzayo kanye no-Li njengama-counter and reference electrode.I-SCE yomiswa izinsuku ezi-2 ebhokisini lamagilavu ​​ngemva kokumiswa kwe-vacuum.

I-ionic conductivity (σi) ye-vacuum-annealed nano-SCE yethu ikhuphuke ngengxenye yevolumu ye-ILE (inani elingu-x) njengezinhlanganisela zezinhlayiyana (fig. S1).Kodwa-ke, kulokhu, i-ionic conductivity idlule leyo ye-ILE ehlanzekile ngokwayo ngaphezu kuka-200% ngamanani aphezulu kakhulu we-x (Fig. 3).Ngaphezu kwalokho, ukuncika kwezinga lokushisa kwe-nano-SCE ene-ion conductivity ethuthukisiwe kubonise ukuziphatha okuhlukile kwalokho kwe-ILE ehlanzekile: Nakuba i-Li-TFSI ku-BMP-TFSI ILE ibonisa uguquko olucacile ekusebenzeni namandla okuvula (umthambeka) eduze nokuncibilika. iphuzu lengxube ku-29 ° C, i-nano-SCE ene-conductivity ethuthukisiwe ayifuni.Esikhundleni salokho, ibonisa ukuhluka okuqhubekayo kokuthi σi nezinga lokushisa, okubonisa ukuthi uhlobo olungaziwa lwesigaba noma i-mesophase luyakhiwa, olube selunesibopho sokuhamba okuthuthukisiwe.Ngaphezu kwalokho, i-slope encane futhi ngaleyo ndlela inciphise amandla okuqalisa okusabalalisa i-nano-SCE uma iqhathaniswa ne-ILE ibonisa izakhiwo zezinto ezibonakalayo (fig. S3).Kucatshangwa ukuthi ukusebenzisana okuqinile phakathi kwama-athomu e-ionic liquid kanye nongqimba lweqhwa oluqinile ku-silica scaffold kunesibopho sokuziphatha okubonwa kwe-mesophase, njengoba kuzoxoxwa ngakho ngemodeli ehlongozwayo ngezansi.

(A) Ukuncika kwezinga lokushisa kokusebenza kwama-nano-SCE omisiwe izinsuku ezingu-8 ebhokisini legilavu ​​(GB) elinamanani angu-x angu-2 (izikwele ezimnyama), 1.75 (imibuthano ewolintshi), 1.5 (onxantathu abaluhlaza), kanye no-1.0 (onxantathu abaluhlaza ) kanye nereferensi ye-ILE (izikwele ezivulekile).(B) Ukuqhutshwa kwama-nano-SCEs ngaphezu kwalokho omisiwe ku-GB izinsuku ezingu-0 (izikwele eziluhlaza), izinsuku ezingu-10 (onxantathu abamnyama), kanye nezinsuku ezingu-138 (onxantathu abaluhlaza).(C) I-Conductivity iqhathaniswa nempande eyisikwele yesikhathi sokumisa se-nano-SCE enamanani angu-x angu-2 (izikwele ezimnyama), 1.5 (onxantathu abaluhlaza okwesibhakabhaka), 1.0 (onxantathu abaluhlaza), kanye no-0.5 (amadayimane ansundu).(D) Ukuqhutshwa kwe-nano-SCE ene-x = 2 (izikwele ezimnyama), 1.5 (onxantathu abaluhlaza), kanye no-1.0 (onxantathu abaluhlaza) kudalulwe egumbini lomswakamo eligcwele i-N2.

Umkhathi we-argon ebhokisini lamagilavu ​​uqukethe amanzi angaphansi kuka-0.1 ppm, ahambisana no-0.0005% RH, ukucindezela kwamanzi okuyingxenye engu-0.01 Pa, noma iphuzu lamazolo elingu-−88°C.Njengoba inani lezendlalelo zamanzi ezikhangisiwe ku-silica enqanyuliwe ye-silanol lilingana nokucindezela okuyingxenye kwamanzi (ifig. S2), amanzi angaphezulu azosakazeka kancane kancane aphume ku-nano-SCE futhi ancibilike emaphethelweni.Umfanekiso 3C ubonisa ushintsho ekuziphatheni kuka-23 μl we-nano-SCE njengomsebenzi wesikhathi sokuhlala ebhokisini lamagilavu.I-ion conductivity iyancipha ngokoma ize igcwale ngenani elihambisana nendawo ye-silica ngokulingana nokucindezela kwengxenye yamanzi okungu-0.01 Pa ebhokisini lamagilavu.Ngisho nangaphansi kwezimo ezomile kakhulu zebhokisi lamagilavu, okungenani, i-monolayer ingxenye yamanzi adsorbed ku-silanol ikhona, njengoba i-Raman spectroscopy isabonisa isignali ku-3524 cm−1, eqondene ngqo ne-monolayer yokuqala yamanzi adsorbed ku-silanol. (Umdwebo 4B).I-ion conductivity ngaphansi kwezimo ezigcwele yayingaphansi kakhulu kweye-ILE ngayinye kuzo zonke izimo.Ngakho-ke, isithuthukisi akwanele ukunxephezela ukulahleka kokusebenza kwe-ionic ye-ILE evalekile enkabeni yembotshana.

(A) I-IR spectra ye-nano-SCE enenani elingu-x elingu-1.5 (obomvu), inkomba ye-ILE (emnyama), kanye ne-SiO2 (eluhlaza okwesibhakabhaka), ebonisa ukuthi iqembu le-O═S═O (1231 cm−1) liyabandakanyeka ukusebenzisana nama-OH-amaqembu endaweni ye-silica.(B) I-Raman spectra ye-nano-SCE enamanani angu-x angu-2 (okumnyama), 1.5 (okubomvu), no-0.5 (okuluhlaza okwesibhakabhaka), okubonisa ukuba khona kwamanzi ayiqhwa ahlanganiswe ku-silica enqanyuliwe ye-silanol ngisho ne-nano-SCE eduze nokugcwala kwendawo (0.0005 % RH) ebhokisini legilavu ​​(izinsuku ezingama-30).(C) Imodeli ehlongozwayo yokusebenzisana kwesixhumi esibonakalayo ku-nano-SCE ehlukanisa i-Li-TFSI ibe yi-Li+ yamahhala njengoba i-TFSI− anion yabelana ngengxenye yenkokhiso yayo engeyinhle ngelendlalelo yeqhwa-TFSI-BMP ekhangisiwe;imibala imelela izakhi ezihlukene ezinobunsomi (i-silicon), obomvu (i-lithium), ophuzi obumnyama (isibabule), osawolintshi (umoya-mpilo), oluhlaza okwesibhakabhaka (nitrogen), omhlophe (i-hydrogen), nohlaza (fluorine).Imigqa edeshi ensomi imelela isibopho se-hydrogen phakathi kweqembu le-O═S le-TFSI anion kanye nama-OH-amaqembu obuso be-silica e-hydroxylated.Ama-Li+ ion akhululwa yi-dipole phezu kwesendlalelo se-adsorbed angahamba ngezandlalelo ezilandelayo zeselula noma asakaze uketshezi lwe-ionic ngaphezu kwezingqimba zokusebenzelana.Qaphela ukuthi kuye ngamandla amabhondi e-hydrogen kanye neshaji elilinganayo ku-silica, ungqimba olukhangisiwe oluningi lungakhiwa futhi.I-spectra ephelele iboniswa emkhiwaneni.S8.

Ukuqaphela okuthakazelisayo ubudlelwano bomugqa nomsuka oyisikwele wesikhathi sokumisa njengoba kukhonjisiwe ku-Fig. 3C, okubonisa ukuthi ukuguquka kokusebenza kuhambisana ngokuqondile nezinguquko zenani lamanzi eqhwa akhangisiwe ku-silica nokuthi ukususwa kwala manzi angaphezulu ukusabalalisa kunomkhawulo.Qaphela ukuthi "ukoma" kwenzeka kuphela endaweni evulekile lapho i-RH iphansi kunesendlalelo seqhwa esilinganayo.I-conductivity ayizange ishintshe ngokuphawulekayo, isibonelo, kumaseli emali avaliwe asetshenziselwa izilinganiso ezincike kumazinga okushisa.

Ukuncika kwezinga lokushisa kwe-nano-SCE kukalwa izikhathi ezihlukene zokumisa ebhokisini lamagilavu.Njengoba i-conductivity ye-nano-SCE eyomisiwe isondela kuleyo ye-ILE, amaphrofayili aqhubekayo we-σi ngokumelene ne-1/T ye-mesophase conductivity kancane kancane ashintshela kuphrofayela ye-ILE, aphinde embule ukwehla okuzungeze indawo yayo yokuncibilika (fig. S3).Lokhu kubuka kusekela futhi ukucabangela kokuthi ungqimba lweqhwa lusebenza njengesendlalelo esisebenzayo sokusebenzisana ne-ILE, okubangela ukuziphatha kwe-mesophase ku-nano-SCE.Ngakho-ke, lapho ungqimba olusebenzayo lususwa, i-ILE iba nje ivalelwe kulwelwesi lwe-mesoporous oxide.

Izilinganiso zewindi lokuzinza kwe-electrochemical ziqinisekisa ukuthi amanzi eqhwa ku-nano-SCE azinzile, njengoba kungekho ziqongo zokunciphisa amanzi noma i-oxidization ezibonwe ku-electrode ye-inert ye-TiN (Fig. 2) noma ku-electrode yefilimu encane ye-TiO2, esebenza ngenye indlela. njenge-electro-catalyst yokunciphisa amanzi.Esikhundleni salokho, ukuzinza kwe-electrochemical ye-nano-SCE kufana kakhulu nalokho kwe-ILE futhi ngaleyo ndlela kukhawulwe yi-oxidation ye-TFSI− emandleni e-electrode >4.3 V kanye nokwehliswa kwe-TFSI- ne-BMP+ ngamandla angu-<1 V ngokumelene ne-Li+/Li (33).Ukuze uqhathanise, i-voltammogram iboniswa ku-ILE enesisindo esingu-5 % (wt %) samanzi engeziwe (okuqukethwe okufanayo nakwenye i-nano-SCE; bheka ithebula elithi S1).Kulesi simo, igatsha le-cathodic lokunciphisa amanzi lilinganiswa ngokushesha ngokulandela ukuphakama kwe-Li-intercalation ye-anatase ku-1.5 V ngokumelene ne-Li+/Li.

Ukuzinza kwe-thermal kanye (electro) kwamakhemikhali we-nano-SCE kunqunywa kakhulu isigcwalisi se-ILE.Ukuhlaziywa kwe-Thermogravimetric (TGA) kubonise ukuzinza kokushisa kwe-SCE ne-ILE kufika ku-320°C, kungakhathaliseki isilinganiso se-ILE-to-silica (fig. S4).Ngaphezu kwaleli zinga lokushisa, i-Li-TFSI ne-BMP-TFSI zibola ngokuphelele zibe izingxenye eziguquguqukayo, futhi i-silica matrix kuphela ehlala cishe ku-450°C.Iphesenti elikhulu elisele ngemva kokubola okushisayo lifane kahle kakhulu nengxenye ye-silica ku-SCE.

I-nano-SCE ayizange ibonise i-microstructure ecacile ku-scan electron microscopy (SEM) ngaphandle kwendawo ebushelelezi enamapheshana e-silica alunguzayo (fig. S5).Ukuminyana okuthile kwe-SCE kwanqunywa nge-helium pycnometer futhi kwakucishe kube ngu-1.5 g/cm3 kuwo wonke amanani we-x (ithebula S1).I-silica matrix egcwele yembulwa ngokukhipha okuyisicefe kwe-ILE kusincibilikisi (bona Izinto Ezibalulekile Nezindlela).Ngokumisa ngokucophelela endaweni ebalulekile ye-CO2, i-airgel monoliths engashintshile ingatholwa njengale eboniswe ku-Fig. 1A.Ukuhlolwa kwe-SEM kukhombisa isikafula se-mesoporous silica enobubanzi obuyi-10- kuya ku-30-nm pore, esisongwe ngama-macropores amakhulu angu-100 kuya ku-150 nm, njengoba kungabonwa ku-Fig. 1 (B no-C).I-high-resolution transmission electron microscopy (TEM) (Fig. 1D) iqhubekisele phambili ukuveza isakhiwo esincane esakhiwe ama-silica nanoparticles asondelene kakhulu.Ububanzi bezinhlayiyana obumaphakathi busuka ku-7 kuye ku-14 nm kumanani angu-x phakathi kuka-0.5 no-1.5.

Indawo ethize [i-Brunauer-Emmett-Teller (BET)], i-porosity, usayizi wembotshana omaphakathi, kanye nokusatshalaliswa kosayizi wembotshana kwanqunywa ngezilinganiso ze-N2 adsorption/desorption (ithebula S1 nefig. S6).Ukugoqa ingxenye yesakhiwo nokususwa okungaphelele kwe-adsorbed ILE kungase ngandlela thize kuhlanekezele izinombolo.Ukukhishwa ngokucophelela koketshezi lwe-ionic nokomisa kancane kusetshenziswa i-CO2 eningiliziwe enikeziwe, nokho, imiphumela enokwethenjelwa eduze ne-porosity elindelekile ebalwa kusukela kungxenyana yevolumu ye-ILE kuya ku-silica (Fig. 1).Indawo ye-BET isukela phakathi kuka-800 no-1000 m2/g.Usayizi wembotshana omaphakathi otholwe emthambekeni we-isotherm wawuphakathi kuka-7 no-16 nm.Ngaphezu kwalokho, ingxenyana encane yama-pores amakhulu kuze kufike ku-200 nm yalinganiswa (fig. S6), ngokuhambisana nokubhekwa kwe-SEM.I-diameter ye-pore ihambisana kahle kakhulu nokujiya okuphindwe kabili okulinganayo kongqimba lwe-ILE olutholwe engxenyeni yevolumu ye-ILE kanye nendawo engaphezulu ye-BET, okusho ukuthi ama-mesopores agcwele ngokuphelele i-ILE.

Indawo engaphezulu ye-BET ebikiwe ingeye-mesopores nama-macropores kuphela.Nge-matrix ehlanjululwe nge-acetone, ama-micropores (~0.6 nm) nawo akalwa.Ama-micropores atholakala phakathi kwe-silica nanoparticles ngayinye eyenza isakhiwo njengalawo aboniswe kumfanekiso we-TEM we-Fig. 1D.Indawo eyengeziwe eyengeziwe ephakathi kuka-650 (x = 0.5) no-360 m2/g (x = 1.5) ilinganiselwa (ithebula S1).

Kokubili i-FTIR ne-Raman spectra ibonisa ubufakazi obucacile bamaqembu e-silanol anama-molecule wamanzi eqhwa adsorbed ku-high-porosity silica matrix enezindawo ezisebenza kahle kakhulu ezingaphezu kuka-1400 m2/g uma kucatshangelwa ama-micropores, ama-mesopores, nama-macropores.Phakathi kukaziro kanye nama-monolayers amathathu wamanzi alinganiselwa kusuka emanzini angaphezulu ku-nano-SCE ngo-x <1.75.Ku-silica eplaniwe, ama-monolayers amathathu okuqala amanzi akhangisiwe abhekwa njenganganyakazi futhi aqinile ngenxa yesibopho sawo se-hydrogen esiqinile endaweni enqanyuliwe ye-OH (32) (bona i-fig. S2).Ukwelula kwe-O─H okuhlotshaniswa ne-silanol hydrogen ehlanganiswe nongqimba lwamanzi eqhwa kutholakala ku-3540 cm−1 ku-spectra ye-FTIR.Wonke ama-nano-SCE abonisa, ngempela, inani eliphakeme elihlukile ku-3540 cm−1 lamanzi e-ice ngemva kokumiswa kwe-vacuum nangemuva kokoma okwengeziwe ebhokisini lamagilavu ​​(Fig. 2).Ngisho ne-nano-SCE elinganisiwe ku-0.0005% RH (ibhokisi legilavu), i-Raman spectroscopy isabonisa ukuba khona okungenani kwe-monolayer eyingxenye (Fig. 4B).I-monolayer yesine ku-planar silica kukholakala ukuthi iyisendlalelo esishintshayo, okusho ukuthi isakhangisiwe futhi ivinjelwe kodwa ingaba nokuhamba okuthile.Kusukela kungqimba lwesihlanu kuqhubeke, amanzi aba ahambayo futhi afane noketshezi.Amanzi afana noketshezi azovela ezinombolweni zamagagasi aphezulu ku-spectrum ye-FTIR ngenxa yezinga eliphansi le-H-bonding emanzini awuketshezi.Ku-nano-SCE evezwe ku-60% RH, i-3540-cm−1peak ikhombisa ngempela ukudlidliza okwengeziwe okushintshelwe ezinombolweni zamagagasi aphezulu ngenxa yesendlalelo samanzi esiwuketshezi esikhangisiwe.Okuthakaselayo kulokhu ukuhlola lapho isampula ivezwe ku-30% RH, njengoba awekho amanzi awuketshezi okwamanje alindeleke ku-silica kulo mswakamo (fig. S2).Kuleli sampula, isiqongo esingu-3540 cm−1 kuphela samanzi eqhwa sibonwa ku-FTIR.Ngaphezu kwalokho, akukho ukuphakama kwamanzi amahhala okutholwe ku-1635 cm−1 ngisho nangemva kwezinsuku ezi-4 ku-30% RH.Lokhu kusho ukuthi amanzi awathathwa yi-hygroscopic Li-TFSI encibilikisiwe ku-hydrophobic BMP-TFSI uma i-nano-SCE yomiswa ngokwelashwa kwe-vacuum.Ngakho-ke, noma imaphi amanzi engeziwe ku-SCE azokhangiswa endaweni ye-silica enqanyuliwe i-OH.Ngakho-ke, ngokuqondene ne-planar silica, i-silica matrix ye-SCE ilingana nokucindezela okuyingxenye kwamanzi endaweni ezungezile.

Ukuze uhlole le ncazelo ngokuqhubekayo, i-ion conductivity ye-nano-SCE (x = 1, 1.5, ne-2) ikalwa ku-% RH ehlukile;amasampula avezwe kwingxube elawulwayo yegesi ye-N2 eyomile futhi eswakanyiswe ebhokisini legilavu ​​izinsuku ezi-2 ukuvumela ukumbozwa kwamanzi adsorbed ukuthi kufinyelele ukulingana (Fig. 3D).Kumaphuzu aku-~0% RH, ukuqhutshwa kwe-nano-SCE elinganisiwe ebhokisini legilavu ​​kuthathiwe.Ngokumangalisayo, iphrofayili ye-ion conductivity iqhathaniswa ne-RH(%) ilandele ukuziphatha okulindelekile kokukhangiswa kwamanzi ku-silica epulaniwe (fig. S2).Phakathi kuka-0 no-30% we-RH, ukuqhutshwa kwe-conductivity kwanda ngokukhula kwe-RH.njengoba kulindelekile ekwandeni kokuminyana kongqimba lweqhwa nogqinsi (okuhambisana nesendlalelo seqhwa esisodwa kuya kwezintathu ku-silica eplaniwe).Qaphela ukuthi i-FTIR ibonise ukuthi awekho amanzi amahhala ayekhona ku-nano-SCE izinsuku ezimbalwa ku-30% RH.Uguquko lubonakala cishe ku-50% RH, oluhambisana nezimo lapho ungqimba lwamanzi olushintshashintshayo lulindeleke ku-silica eplaniwe.Ekugcineni, ukukhuphuka okuhlukile kokusebenza kwe-ion kutholakala ku-60% kanye nomswakama ophezulu lapho, ngokufana ne-silica epulaniwe, manje, futhi ungqimba lwamanzi olufana nolwelwesi ngokunokwenzeka lwakhiwe endaweni esibonakalayo phakathi kwe-silica ne-ILE eshumekiwe.Nge-FTIR, ungqimba lwamanzi aluketshezi kungqimba yeqhwa manje lutholwa ngokugudluzwa kwesiqongo se-silanol/iqhwa/amanzi sokudlidliza siye emandleni aphezulu (Fig. 2A).Ushintsho oluphawuliwe ku-conductivity luyabuyiselwa emuva;ngakho-ke, i-nano-SCE ingasebenza njengenzwa yomswakama kanye ne-electrolyte ye-Li-ion.Kusuka ku-Fig. 3D, ukuqhutshwa kwe-ion ye-nano-SCE ngokushesha ngemva kwe-vacuum anneal ihambisana ne-equilibrium hydrated silica engu-~10% RH.I-ion conductivity yokugcwaliswa kwesikhala ezimeni zegumbi elomile (~0.5% RH) ingaba ngu-0.6 mS/cm (ku-x = 2).Lokhu kuhlolwa kubonisa ngokusobala umthelela wamanzi ahlangene ku-ion conductivity.Ku-RH > 60%, ukuqhutshwa kwe-ion ephakeme kungachazwa ngokusakazwa ngokushesha kwe-Li+ exazululiwe ngongqimba olufana noketshezi.Kodwa-ke, esimweni sengqimba yeqhwa eqinile, ukusakazeka kwe-Li+ ion kungaba uhlobo oluqinile lokusabalalisa futhi ngaleyo ndlela kube kancane kunoketshezi lwe-ionic ngokwalo.Esikhundleni salokho, lesi sithuthukisi sibangelwa ukukhangisa okuthuthukisiwe kwama-anion eziphilayo kanye nama-cations we-Li-salt nama-molecule e-ionic liquid, njengoba kuhlongoziwe kumodeli engezansi.

Siphakamisa imodeli lapho ama-molecule e-ionic liquid adsorbed endaweni ye-silica ngamabhuloho e-H anengqimba yeqhwa enganyakazi kumaqembu e-silanol (Fig. 4).Imvelo yangaphakathi yokusabela kwe-hydrolysis condensation inikeza ukuminyana kwe-silanol okuphezulu kakhulu (4 × 1014 kuya ku-8 × 1014 cm−2, okuhambisana kahle nokuminyana kwe-monolayer yeqhwa ene-~8 × 1014 yama-molecule wamanzi nge-cm2 ngayinye) (34).Ubufakazi bokusebenzelana kwamangqamuzana phakathi kwama-athomu e-O we-TFSI anion kanye ne-silica bunikezwa i-FTIR, ebonisa ukuphindwa kabili kwe-O═S═O peak yayo yonke i-nano-SCE uma kuqhathaniswa nereferensi ye-ILE (Fig. 4A; i-spectra ephelele emkhiwaneni S8).Ukushintsha kwesiqongo esingeziwe mayelana nokungu-−5 cm−1 ukusuka ku-1231 cm−1 kubonisa ukuhlangana kwamaqembu e-O═S═O okungenani ingxenye yama-anion e-TFSI.Ngakho-ke, ukuhlanganiswa kwe-H kwama-anions e-TFSI kungqimba lwamanzi eqhwa kucatshangwa.Ngokulandelayo, ama-cations amakhulu e-BMP e-hydrophobic ahlotshaniswa nesendlalelo sokuqala se-TFSI, aqedela isendlalelo sokuqala esikhangisiwe sama-molecule e-ionic liquid.Ngokuqondene nongqimba lweqhwa, ama-molecule e-BMP-TFSI adsorbed acatshangwa ukuthi awanyakazi, ngaleyo ndlela andisa ungqimba lweqhwa oluqinile endaweni ye-silica.Njengoba i-anion ye-TFSI ineqembu le-O═S═O elilinganayo, i-athomu eyodwa yomoya-mpilo ingasebenzisana nendawo ye-silica eyi-hydroxylated kuyilapho enye yakha amaphuzu okunamathela kuma-cations e-BMP.I-TFSI anion futhi inamaqembu amabili we-O═S═O, aqinisekisa ukukhangiswa okuqinile nokuhleleka okuminyene kwe-anion monolayer.I-Adsorption isebenza kahle kakhulu esimweni sengqimba yeqhwa eliminyene elinokuminyana okuphezulu kakhulu kwama-OH-amaqembu njengamaphoyinti angaba khona okunamathela.Ebukhoneni bamaqembu e-silanol kuphela, ukukhangiswa kungase kungabi namandla ngokwanele ukwakha isendlalelo se-adsorbate esiqhubekayo.Ngaphezu kwalokho, inani elandayo le-ice monolayers laziwa ngokukhulisa amandla ebhondi ye-hydrogen (35).Qaphela ukuthi ukusebenzisana kwamangqamuzana phakathi kwendawo ye-BMP kanye ne-TFSI monolayer e-odiwe kuzohluka kulokho okusoketshezini lwe-ionic lapho i-anion ye-TFSI inenkululeko yokujikeleza futhi ingekho ukuhlukaniswa okuvela endaweni engaphansi.Inkokhelo yendawo enkulu ye-BMP isakazwa phezu kwama-athomu amaningi ngokuhlukaniswa kwamabhondi angaphakathi kanye nokusebenzisana kwamangqamuzana nendawo yawo yamakhemikhali futhi, ikakhulukazi, i-anion ye-TFSI ekhangisiwe.I-H-bonding phakathi kweqembu le-O le-TFSI anion kanye nokuqedwa kwe-OH kwengqimba yeqhwa manje sethula i-dipole phezu kongqimba lokuqala olukhangisiwe, okukhuthaza ukuhleleka okwengeziwe kwamangqamuzana ngokuhlangana.Kukholakala ukuthi kuleli qophelo, ama-athomu amancane e-Li-TFSI akhangisa ungqimba lwamangqamuzana lapho i-TFSI anion manje inxephezela inkokhiso eyinsalela ye-dipolalar ye-cations ye-BMP eyodwa noma ngaphezulu kungqimba olungaphezulu, yingakho ikhulula ukuhlangana kwayo ne-Li. ion.Ngale ndlela, ukugxila kwe-Li + yamahhala kuyanda kulesi sikhombimsebenzisi, okuholela ekuqhubeni okuphezulu kwe-ion.Ngakho-ke, izingqimba zeqhwa eziminyene nezijiyile zibe sethula i-dipole enkulu enenkokhiso ephezulu eyinsalela ukuze kunxeshezelwe, kunikeze ukugxiliswa kwamahhala kwe-Li+ okuphezulu ngokulinganayo kanjalo nokuqhutshwa kwe-ion.

Ngaphezulu kwesendlalelo se-ILE esikhangisiwe, noma olunye ungqimba lwe-ILE lungakhangiswa ngokufana nezingqimba eziningi zeqhwa ku-silica noma ukudonsa kwe-dipole kwengqimba yeqhwa kubuthaka kakhulu futhi i-ILE eboshwe kancane ingaphezulu, enganikeza ukuqhutshwa okufana noketshezi ama-Li+ ions akhishwe kungqimba oluphansi lwe-adsorbed (Fig. 4C).Ushintsho ekugxiliseni kwamahhala kwe-Li+ ion luqinisekiswe yizo zombili izilinganiso ze-NMR ne-Raman spectroscopy.Izilinganiso ze-Raman zibonisa ngokungaqondile ukuthi ingxenye enkulu yama-Li+ ion amahhala akhona ngempela ku-nano-SCE enezingqimba eziningi zamanzi eqhwa aboshwe ku-silica (Fig. 5).I-Raman ikala ukuhlotshaniswa kwe-cation ne-TFSI ngokuhlola ukudlidliza kweqembu le-N le-anion ye-TFSI (36).Oketshezini oluhlanzekile lwe-ionic ye-BMP-TFSI, kubonakala kuphela isiqongo esisodwa esingu-741 cm−1.Endabeni ye-ILE ehlanzekile, inani eliphakeme elengeziwe libonakala ku-746 cm−1 lapho ama-anion amabili e-TFSI exhumanisa ne-Li+ ion eyodwa [bona izibalo ze-density functional theory (DFT) kokuthi Izinto kanye Nezindlela].Kuwo wonke ama-nano-SCEs, ukushuba okuphezulu kokuthi 746 cm−1 kubuthakathaka kunalokho kwe-ILE, okubonisa ingxenye encane ye-Li-TFSI ehlotshaniswayo futhi, ngenxa yalokho, ingxenye enkulu yama-cations we-Li+ angahlobene noma amahhala.Ukuphakama kwehla kakhulu kulawo ma-nano-SCE abonisa ukuthuthukiswa okuphezulu kakhulu kokusebenza, okungukuthi, lawo anongqimba lweqhwa olujiyile kakhulu.Ku-nano-SCE ekulinganisweni ebhokisini lamagilavu, noma kunjalo, ingxenyana ye-Li+ yamahhala iyalinganiswa nakuba incane kakhulu kunamasampuli afakwe i-vacuum-annealed.Isilinganiso sokuqina kokuqina kokungu-746 ngaphezulu kuka-741 cm−1 amashifu e-Raman bese iyisilinganiso sesilinganiso samahhala kuma-Li-ions ahlobene ne-TFSI (Fig. 5B).Ukwenyuka komugqa kwengxenye yamahhala ye-Li+ ion enenani elingu-x kulandela kahle inkambiso yokuthuthukiswa kokusebenza ngevelu engu-x ku-Fig. 3B, kokubili kwe-vacuum eyomisiwe ye-nano-SCE (usuku 0) kanye ne-SCE ngokulingana nokomisa kwebhokisi lamagilavu ​​(usuku 138).

(A) I-Raman spectra yoketshezi lwe-ionic (IL; umugqa oluhlaza okwesibhakabhaka onamachashazi) kanye nereferensi ye-ILE (ILE; umugqa wamachashazi odeshi) njenge-nano-SCE elungisiwe (i-vacuum eyomile) enamanani angu-x angu-0.5 (oluhlaza), 1.5 (ophuzi) , kanye no-2 (brown) kanye ne-nano-SCE (x = 1.5) ngaphezu kwalokho omiswe ebhokisini legilavu ​​izinsuku ezingu-30 noma eduze nokugcwala ku-0.0005% RH (okubomvu).Imigqa eqondile ilebula i-Raman shift ye-TFSI nesikhungo sayo esingu-N sixhunywe ku-Li+ (746 cm−1) futhi ayihlanganiswa ku-Li+ (741 cm−1), ngokulandelanayo.(B) Isilinganiso samahhala sokuxhumanisa i-Li+ ye-nano-SCE njengoba ihlanganisiwe (i-vacuum eyomisiwe, imibuthano emnyama) futhi ngaphezu kwalokho yomiswa emabhokisini amagilavu ​​ngo-0.0005% RH izinsuku ezingama-30 (amadayimane aluhlaza), ahambisana nesilinganiso sokuqina okuhlanganisiwe Iziqongo ze-Raman (746 cm−1 ngaphezu kuka-741 cm−1).(C) I-PFG-NMR–isuselwa ku-Li+ i-self diffusion coefficient ye-nano-SCE (amadayimane abomvu) kanye ne-ILE ref.(izikwele ezimnyama) njengomsebenzi wesikhawu phakathi kwe-gradient magnetic field pulses.Iziqongo zetiyori ku-Raman spectra zalingiswa kusetshenziswa ukubala kwe-DFT.

Kusuka ku-pulsed-field gradient NMR (PFG-NMR), i-coefficient yokuzihlukanisa yezinhlobo ezahlukene ze-Li-ion zeselula yanqunywa njengomsebenzi wesikhawu phakathi kwe-gradient magnetic field pulses ∆ yereferensi yoketshezi ye-ILE kanye ne-nano- I-SCE (x = 1.5) ene-ion conductivity efanayo ye-0.6 mS/cm (Fig. 5C).I-Li+ self-diffusion coefficient kureferensi ye-ILE ibihlala njalo, okubonisa ukuthi uhlobo olulodwa kuphela noma eziningi ze-Li ezinokuhamba okufanayo ezikhona oketshezini.Ku-nano-SCE, i-self-diffusion coefficient ihluka ngo-∆ futhi yeqa leyo ye-ILE ngamafuphi ∆, okubonisa ukuba khona kwezinhlobo ezihamba ngokushesha eziphendula kuphela ngezikhathi ezimfushane phakathi kwama-pulses magnetic field.I-gradient ku-coefficient yokuzihlukanisa iphakamisa ukuthi eduze kokwanda kokugxiliswa kwe-Li-ion yamahhala, njengoba kuchazwe ku-Raman spectroscopy, amandla okwenza kusebenze okusabalalisa ehliswa kusendlalelo esibonakalayo se-mesophase futhi.Lokhu kusekela ukuthuthukiswa kokusebenza okwethulwa yi-Li+ ion yamahhala (engaphezulu) kungqimba lwe-mesophase.Esikhathini eside ∆, i-coefficient yokuzihlukanisa yayiphansi kunaleyo yereferensi ye-ILE.Lokhu kuqinisekisa ukuqhutshwa kwe-ion okuphansi kakhulu kwebhokisi lamagilavu-saturated nano-SCE uma kuqhathaniswa ne-ILE.I-ILE evalelwe kumgogodla we-mesopores izoba ne-viscosity ephakeme ngenxa yokuvinjelwa kokunyakaza kwamangqamuzana.Ngakho-ke, ukuthuthukiswa ngokudala ama-Li-ion ahlakazeka ngokushesha kusixhumi esibonakalayo se-silica/ice/ILE kufanele kugcwalise ngokwedlulele ukwehla kokusebenza kumongo wembotshana.Lokhu kuchaza ukungabikho kwesithuthukisi kumasistimu asekelwe kuyizinhlayiyana lapho izixhumi ezibonakalayo zinganikezi iphromoshini ye-ion conduction eyanele (fig. S1).

Ukuzinza kwe-electrochemical ye-nano-SCE ngokumelene nensimbi ye-lithium kwahlolwa kusetshenziswa ukusethwa kwe-electrode emithathu (i-schematic of setup iboniswa ku-fig. S7).Isici esinamandla samanje se-Li/SCE (x = 1.5) kanye ne-Li/ILE isigamu seseli siboniswa ku-Fig. 6A.Ngokuqondene newindi le-electrochemical ku-Fig. 2, i-electrochemistry inqunyelwe isigcwalisi se-ILE.I-lithium plating eguqulekayo kanye nokuhlubula kuyabonwa.Ungqimba oluqinile lwe-electrolyte interphase (SEI) lwakhiwe ku-metallic lithium ene-RSEI engaba ngu-0.9 kilo-ohm·cm2, ebophezele ukwehla okukhulu kwe-IR ku-iU curve kuzo zombili izinhlangothi ze-cathodic ne-anodic.I-cathodic current ezixazululweni ze-ILE ezihlanzekile azizange zibonise noma iyiphi i-hysteresis kuze kufike ku- -2.5 mA/cm2.Kodwa-ke, ukuqedwa kwe-anodic kubonise ukuphakama kwe-passivation ene-anodic current yesimo esiqinile engu-0.06 mA/cm2 kuphela.Igatsha lamanje le-cathodic ku-solid-solid Li/SCE interface alizange libonise i-hysteresis yama-cathodic currents ngaphansi kuka- -0.5 mA/cm2.Ukumelana kwe-SEI, nokho, kwakucishe kuphindwe kabili.Ngokufanayo, inani eliphakeme le-anodic laliphansi futhi isimo samanje esizinzile ngemva kokuphakama kwe-anodic passivation kwaba ngu-0.03 mA/cm2, ingxenye kuphela yesixazululo se-ILE esihlanzekile.Ukwakhiwa kwezendlalelo ze-SEI kanye ne-passivation kuma-pores we-SCE kunciphisa okwamanje ku-lithium metal.Kokubili ama-voltammogram ama-electrode e-Li/ILE kanye ne-Li/SCE aye aphinda akhiqizwa emijikelezweni eminingi, okubonisa ukuthi ungqimba lwe-anodic passivation kanye nongqimba lwamakhemikhali e-SEI luyabuyiseleka emuva futhi luzinzile.I-kinetics yokupheliswa kancane kancane kusixhumi esibonakalayo se-Li/SCE ikhawulela kakhulu ukusebenza kwengxenye yamaseli enziwe nge-Li metal anode ngezansi.

(A) I-Cyclic voltammogram ye-nano-SCE (x = 1.5, njengoba ihlanganiswe ngemva kokumiswa kwe-vacuum) (bomvu) kanye nereferensi ye-ILE (emnyama) ikalwa ekucushweni kwama-electrode amathathu ngo-Li njengama-electrode asebenzayo, aphikisayo, nereferensi (ukumelana kwe-SEI kulinganiselwa kusukela Ukwehla kwe-IR ku-cathodic current ngu-0.9 kanye no-1.8 kilo-ohm·cm2 ku-ILE ne-SCE, ngokulandelanayo).(B) Amajika e-galvanic charge/discharge yeseli ye-Li/SCE (x = 1)/100-nm yefilimu elincanyana ye-LiMn2O4 emijikelezweni emihlanu kumazinga e-C angu-1C, 5C, no-20C.(C) I-Cyclic voltammograms ye-Li/SCE/40-μm Li4Ti5O12 kanye ne-Li/SCE/30-μm LiFePO4 powder electrode cell (1 mV/s).(D) I-galvanic charge/i-discharge curves ye-Li/SCE/40-μm Li4Ti5O12 powder electrode ku-1C, 0.1C, 0.2C, kanye no-0.02C.(E) I-galvanic charge/i-discharge curves ye-Li/SCE/30-μm LiFePO4 powder electrode ku-1C, 0.5C, 0.2C, 0.1C, 0.05C, kanye no-0.01C.(F) Amandla (amadayimane agcwele ukuchithwa kanye nezikwele ezivulekile ze-lithiation) ngokumelene nenombolo yomjikelezo we-Li/SCE/30-μm LiFePO4 powder electrode;ubukhulu be-SCE kumaseli bungaba ngu-280 μm.Ukuminyana kwe-LFP ne-LTO cathode cishe ku-1.9 kanye no-11.0 mg/cm2, ngokulandelana.(G) Amajika anamandla aqhathaniswa nesikhathi esitaki se-Li/SCE/Li ajikeleziswa ngokuminyana kwamanje okungu-0.1, 0.2, 0.5, kanye no-0.1 mA/cm2.(H) I-1st, 10th, 125th, kanye ne-polarization yokugcina yesitaki se-Li/SCE/Li esigcizelelwe kokuthi 0.1 mA/cm2, eboniswa ku-(G).Ku-(G) kanye no-(H), i-SCE ine-conductivity engu-0. 34 mS/cm, kanti ukujiya kwe-pellet ye-SCE kungu-0.152 cm.

Ifilimu elincanyana elingu-100-nm LiMn2O4 (LMO) lisetshenziswe njengemodeli ye-electrode ephozithivu ukuhlola kokubili ukuqina kwe-nano-SCE nokokusebenza kwe-electrode kuyilapho isusa izinkinga zokusebenzelana ezingaba khona kuma-electrode ayinhlanganisela yezinhlayiyana (37).Ukusebenza kwebhayisikili kwesitaki sefilimu encane ye-electrode/SCE kukhombisa ukuzinza kwesixhumi esibonakalayo phakathi kwe-electrode ne-electrolyte.Kule modeli yokusetha ifilimu elincanyana, ukuxhumana okukodwa kuphela, okuchazwe kahle, kanye ne-planar interface okukhona phakathi kwe-electrolyte ne-electrode, okungukuthi, iyinkundla ekahle yokufunda i-electrochemistry yesixhumi esibonakalayo se-electrolyte/electrode ngaphandle kwezinkinga zokushintsha umthamo. , njll. Futhi kulokhu kuhlolwa, ukusebenza kwesilinganiso akukhawulelwe i-electrode ekhawunta ye-Li-foil, njengoba ukuminyana kwamanje (6 μA/cm2 ku-1C) kungaphansi kwalokho kwethafa le-anodic lesimo esiqinile sethafa le-lithium uhhafu- iseli (0.03 mA/cm2).Amajika wokushaja/okukhiphayo akhiqizwayo futhi azinzile atholakala ku-voltage yokunqamula ku-4.3 V ku-C-rates phakathi kuka-1 no-20C emijikelezweni engaphezu kuka-20 (Fig. 6B).I-LMO ayizinzile ku-electrolyte ewuketshezi ye-LiB.Isibonelo, ukuncishiswa kwamandla ngo-50% kubonwe enkokhelweni yefilimu ye-LMO engu-100-nm ekhishelwe imijikelezo eyi-10 ku-LiClO4/propylene carbonate electrolyte ku-1C (37).Imiphumela yethu ibonisa ukuthi i-nano-SCE ihambisana kakhulu ne-LMO kune-electrolyte ewuketshezi evamile.

Ukuze sibonise ukuhlanganiswa kwe-nano-SCE, siphinde sakha ama-half-cell nge-Li4Ti5O12 (LTO) kanye ne-LiFePO4 (LFP) powder electrodes.Isixazululo sesandulela saphonswa esitokisini semali ukuze kufakwe ama-electrodes anezimbotshana futhi sishiywe ukuze kuqhutshekwe ne-gelation ngaphambi kokuba omiswe futhi kufakwe i-vacuum-annealed ngokufanayo namapellets e-nano-SCE.Amaseli abonisa isici lithiation/delithiation of the electrode ehambisanayo (Fig. 6C).Amagagasi aphezulu aphansi e-LFP kune-LTO abangelwa umehluko wokujiya koqweqwe.Ukusebenza kwezinga phakathi nezilinganiso zokushaja/ukukhipha manje kwase kunqunyelwe i-electrode yekhawunta ye-Li-foil ecindezelwe kungqimba lwe-nano-SCE olwakhiwe phezu kwezingubo ze-electrode ezingama-30 kuya ku-40-μm (Fig. 6, D no-E).Iseli ye-LTO/nano-SCE/Li ifinyelele umthamo wayo omkhulu ongu-160 mA·hour/g kuphela ku-C-rate ephansi engu-0.02C (Fig. 6D).Umthamo ofinyelelekayo wehla ngokushesha nge-C-rate engaphansi kuka-10% kumazinga ka-C amakhulu kuno-0.1C.Ngokufanayo, iseli ye-LFP/SCE/Li ifinyelele umthamo wayo omkhulu ongaba ngu-140 mA·hour/g ku-0.01C (Fig. 6E).Umfanekiso 6F ubonisa ukusebenza kwesilinganiso sengqikithi yemijikelezo engu-30, ebonisa ukumiswa kweseli okuzinzile.Lokhu kuhlola kubonisa ukusebenza kwe-nano-SCE njenge-electrolyte ye-Li-ion kanye nokuba nokwenzeka kokuhlanganiswa kumaseli e-Li-ion.

Ukuzinza noma ukuvuthwa kwe-nano-SCE kwahlolwa kusetshenziswa isitaki sokulinganisa se-Li/SCE/Li.Yayihamba ngebhayisikili imijikelezo engaphezu kwe-120 ekumineni kwamanje kwe-0.1 mA / cm2 amahora angu-0.5 (Fig. 6G) ngaphandle kwezinkinga noma ukwakheka kwe-dendrite (Fig. 6H).I-voltage ye-polarization yaba yincane ngokuhamba kwesikhathi, okubonisa ukuthuthukiswa kokuxhumana.Ngaphezu kwalokho, iseli laligcizelelwe kuze kube manje ukuminyana kwe-0.5 mA / cm2, ngaphandle kokubunjwa kwe-lithium dendrites noma izimpawu zokuwohloka kwe-nano-SCE noma isikhombimsebenzisi (Fig. 6G).I-Metallic lithium yaziwa ngokwenza isendlalelo se-interphase esivikelayo noma i-SEI endaweni yayo kuma-ILE asekelwe ku-BMP-TFSI (27).Lokhu kusabela kwenzeka futhi kusixhumi esibonakalayo se-lithium/nano-SCE;njengoba kuxoxwe ngaphansi kwe-Fig. 6A, i-SEI ingase ikhule kancane ngaphakathi kwama-pores, ichaza ukumelana okuphezulu kwe-SEI kwe-nano-SCE kune-ILE (bheka ngenhla).Ubufakazi besendlalelo se-SEI butholwe ku-IR spectra (fig. S9).Ngokufanayo nokwembozwa kwe-SEI ku-LiB yakudala, ehlola i-electrode yegraphite kusukela ku-electrolyte ewuketshezi igwema ukusabela okwengeziwe, sikholelwa ukuthi i-SEI lapha iphinde ivikele ungqimba lwamanzi eqhwa ekuphenduleni okwengeziwe okuvela ku-metallic lithium anode.I-Impedance spectra ngaphambi nangemva kwe-polarization ye-Li/nano-SCE (x = 1.5) yamahora angu-10 ayizange ibonise noma yikuphi ukuguqulwa kokumelana nobuningi be-electrolyte.Izilinganiso zokusebenza kokuhamba ngebhayisikili okude zizodingeka ukuze zingafaki ukomiswa kancane kwe-nano-SCE ngensimbi ye-lithium, kodwa le miphumela isivele ikhombisa amandla ayo okuhamba kahle kwe-SCE kumabhethri e-lithium metal-based solid-state.Noma kunjalo, izimbotshana zokwenziwa ze-interphase zingacatshangwa njengokuthuthukisa i-impedance yesixhumi esibonakalayo ngokuphelele.

Sibonise ukuthi iphromoshini ye-ion conduction ezindaweni zokusebenzelana ne-silica ingafinyelelwa ngokwethula isendlalelo samanzi esine-chemisorbed ezindaweni ze-silica eziqedwe nge-OH.I-TFSI anions chemisorb kulolu ngqimba olusebenzayo lwamanzi ngokusebenzisa i-hydrogen bonding neqembu le-symmetric O═S═O.Isendlalelo samanzi asinyakazi ngakho-ke siphinde sikhombe isendlalelo se-TFSI esikhangisiwe phezulu.Ama-cations amakhulu e-BMP ahlotshaniswa ne-TFSI monolayer, ngaleyo ndlela ethula ukuhleleka kwamangqamuzana kwe-TFSI-BMP phezulu.Sikholelwa ukuthi i-gelation ehamba kancane endaweni enamanzi kanye nokomisa kancane kuyasiza ekwakhekeni okuhlangene kongqimba lwamanzi olusebenzayo kanye nongqimba oluhlelekile lwama-ion ephilayo phezu kwalo.Njengoba ungqimba lwe-anion lokuqala lwe-TFSI luhlanganyela ingxenye yenkokhelo yalo engemihle ne-silica eyi-hydroxylated, ungqimba lwendawo lwe-BMP phezulu luzofuna ukuhlotshaniswa nenye i-anion ye-TFSI, lapho i-BMP eminingi ingabelana ngezindleko zayo ezinganxeshezelwa nge-TFSI eyodwa (mhlawumbe ezintathu kuya kweyodwa njengaku isilinganiso se-IL kuya ku-Li-TFSI ku-ILE).Njengoba ama-molecule e-Li-TFSI kasawoti anendlela eseduze kakhulu, ama-Li+ ion azohlukana futhi akhululwe ukuze asakazeke ngokushesha kulesi sixhumi esibonakalayo.Ukuze uthole ukuqhutshwa okuthuthukisiwe, lezi zinhlobo ze-Li+ zamahhala zidinga okungenani isendlalelo esisodwa se-ionic liquid ukuze sidlule.Ngenxa yalesi sizathu, i-nano-SCE enenani eliphansi le-x lika-0.5 alizange libonise ukuqhutshwa okuthuthukisiwe, njengoba indawo ye-ILE yevolumu/silica yanele i-monolayer eyodwa evaliwe.

Kwaphinde kwaboniswa ukuthi amanzi angaphezulu okuqinile afana nangaphezulu noma ungqimba lweqhwa alusebenzi ngokwe-electrochemically.Kuleli qophelo, asikwazi ukukhipha ukuthi amanzi eqhwa athintana ngqo ne-electrode surface awaphenduli.Kodwa-ke, sibonise ukuthi ukuphuma kwamanzi kwamanzi angaphezulu kuhamba kancane futhi ngakho-ke akunakeki kahle ukuthi angabonwa.Siyaqaphela ukuthi ukungcoliswa kwamanzi, ngisho noma kukuncane, kuyohlale kukhathaza, futhi ukuhlolwa komjikelezo wempilo omude kuphela okunganikeza impendulo eqondile yokuthi amanzi aboshelwe ngokwanele yini.Kodwa-ke, ezinye izendlalelo zendawo ezisebenzayo ezinikeza iphromoshini efanayo noma enkulu nakakhulu manje zingathuthukiswa.Mayelana nalokhu, iqembu lika-Li selivele libonise amandla ongqimba lwe-glycidyloxypropyl njengeqembu elisebenzayo (18).Amanzi eqhwa adabuka e-silica ngakho-ke afaneleka kahle ukufunda umthelela wokusebenza kwendawo ekuthuthukisweni kwe-ion conduction ngendlela ehlelekile, njengoba kuboniswe ngempumelelo lapha.Ukwengeza, ungqimba lwe-mesophase kanye ne-dipole yalo kuzoncika ku-oxide kanye nama-molecule e-organic adsorbed futhi ngaleyo ndlela kungashunwa yizo zombili.Elabhorethri, sesivele sibonise umehluko omkhulu ekuthuthukisweni kokwenziwa kwe-ion koketshezi oluhlukile lwe-ionic.Ngaphezu kwalokho, umgomo obonisiwe uwujenerikhi ekuqhubeni kwe-ion futhi ngaleyo ndlela ungasetshenziswa kumasistimu e-ion ahlukene afanele, isibonelo, amabhethri e-sodium, i-magnesium, i-calcium, noma i-aluminium ion.Sengiphetha, i-electrolyte ye-nanocomposite ene-interface conduction eboniswe lapha ingumqondo kunento eyodwa, engathuthukiswa (i-nano) ithuthukiswe ezindaweni ezifiselekayo ze-ion conduction, inombolo yokuthutha, iwindi le-electrochemical, ukuphepha, kanye nezindleko zezizukulwane zamaseli ebhethri ezizayo. .

I-nano-SCE yalungiswa kusetshenziswa indlela ye-sol-gel.I-Lithium bis(trifluoromethylsulfonyl)imide Li-TFSI;Sigma-Aldrich;99.95%), 0.5 ml ye-H2O eyenziwe deionized, 0.5 ml ye-TEOS (Sigma-Aldrich; 99.0%), 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP-TFSI; Sigma-Aldrich; 9815%). ml we-PGME axutshwe ebhodleleni lengilazi.Isilinganiso se-molar, x, phakathi kwe-[BMP][TFSI] ne-TEOS enhlanganisweni yahluka phakathi kuka-0.25 no-2. Isilinganiso se-molar ye-Li[TFSI] kanye ne-[BMP][TFSI] imiswe kokuthi 0.33:1.Amanani we-Li[TFSI] kanye ne-[BMP][TFSI] anqunywe kulezi zilinganiso.Isibonelo, uma x = 1, okwengezwe okuthi [BMP][TFSI] kanye ne-Li[TFSI] esixazululweni kube ngu-0.97 no-0.22 g, ngokulandelanayo.Izingxube zanyakaziswa iminithi elingu-1 ukuze zenze izixazululo ze-monophasic.Lezi zixazululo zabe sezigcinwa ezitsheni ezivaliwe ngaphandle kokugqugquzela ukwenza ama-gel ekamelweni elilawulwa ukushisa nomswakama (SH-641, ESPEC Corp.) ngezinga lokushisa kanye ne-RH% ebekwe ku-25 ° C no-50%, ngokulandelana.Ngokuncika ku-x, izingxube zathatha, ngokwesilinganiso, izinsuku ezi-5 kuya kweziyisi-9 ukwenza ijeli ecacile.Ngemuva kokugezwa, izitsha ezinejeli engu-2.4- kuya ku-7.4-ml zaqale zomiswa ku-40°C izinsuku ezine ezigcwele ngomfutho oncishiswe kancane (80 kPa) bese zithuthelwa kuhhavini wevacuum amahora angu-72 ku-25°C.Njengoba umswakama osele ususiwe, i-vacuum yehla kancane kancane kusukela ekucindezelweni kokuqala okuzungeze i-50 Pa kuya ekucindezelweni kokugcina okungaguquki kwe-5 Pa ngemva kosuku olu-1.Ngenxa yenani elikhulu lamanzi kanye ne-PGME okwakudingeka ikhishwe, ama-pellets e-SCE aye ancipha esuka ku-20% (x = 0.5) kuya ku-~50% (x = 2) wevolumu yejeli yokuqala.Isisindo samajeli atholakele sikalwa ngebhalansi ye-semimicro (SM 1245Di-C, VWR).

I-TGA yenziwe ku-Q5000 IR (TA Instruments, New Castle, DE, USA) ngaphansi kwe-nitrogen.Ngesikhathi sokulinganisa, amasampula ashise abe ngu-700 ° C ngezinga lokushisa elingu-2 ° C/min.I-FTIR spectrometry yenziwa kusetshenziswa i-Bruker Vertex 70 enombolweni yegagasi esukela ku-4000 kuya ku-400 cm−1 kumodi yokudlulisela.I-pycnometry yenziwa kusetshenziswa i-Micromeritics AccuPyc II 1340.

Ukukala ukuqhutshwa kwe-ionic, umthamo omncane we-SCE uthathwe ku-vial kamama ngaphakathi kwebhokisi legilavu ​​eligcwele i-Ar (0.1-ppm H2O no-0.1-ppm O2).Cishe u-23 μl we-SCE ugcwaliswe ngendandatho ye-polytetrafluoroethylene (PTFE) enobubanzi bangaphakathi obungu-4.34-mm nobude obungu-1.57-mm, okwenza i-pellet.I-pellet eseringini yabe isihlanganiswa phakathi kwamadiski amabili ensimbi engagqwali (SS) (ugqinsi oluyi-0.2 mm; i-MTI).Izilinganiso zokuthikamezeka zenziwe kusetshenziswa i-PGSTAT302 (Metrohm), ene-AC amplitude engu-5 mV ebangeni lefrikhwensi ukusuka ku-1 MHz ukuya ku-1 Hz.I-ion conductivity (σi) yanqunywa kusukela ekunqamuleni kwemvamisa ephezulu nge-eksisi yangempela kuziqephu zeNyquist.Ngemuva kwesilinganiso se-conductivity, i-nano-SCE pellet yavunyelwa ukuthi iqhubeke yomile ebhokisini leglavu.Ngesilinganiso sokuncika kwezinga lokushisa, izitaki ze-SS/SCE/SS zavalwa kuseli lwemali.Ngemva kokubekwa uphawu, i-conductivity yahlala ingashintshi izinsuku ezimbalwa (bheka umkhiwane. S3).Izinga lokushisa lohlamvu lwemali lilawulwa ngejazi elishisayo elinokugeza okushisayo kusetshenziswa i-H2O/ethylene glycol njengendawo yokusebenza.Amaseli aqale apholiswa aze afike ku-−15°C bese eshisisa kancane kancane abe ngu-60°C.

Kusuka ku-nano-SCE pellet ngayinye, cishe u-23 μl walethwa eringini (ububanzi obungu-4.34-mm obungaphakathi nobude obungu-1.57-mm) ukuze kuthathwe izilinganiso zikagesi ngokuqondile ngaphakathi kwebhokisi legilavu ​​eligcwele i-N2 elinomswakama olawulwayo.Iringi ene-SCE yabe isifakwa phakathi kwamadiski amabili e-SS (ugqinsi ngo-0.2 mm; i-MTI).Izilinganiso zokuthikamezeka zenziwe kusetshenziswa i-PGSTAT302 (Metrohm) ene-AC amplitude engu-5 mV kanye nemvamisa esukela ku-1 MHz ukuya ku-1 Hz elawulwa ngesofthiwe ye-Nova.Amasampula agcinwe enanini ngalinye le-RH% amahora angama-48 ngaphambi kokuthi kuqashwe ukuqhutshwa kwe-conductivity kuze kube ukuzinza.I-ionic conductivity ezinzile yenani le-RH% elinikeziwe (σi) yanqunywa kusukela ekunqamuleni kwefrikhwensi ephezulu nge-eksisi yangempela eziqephu zeNyquist.

Zonke izilinganiso ze-electrochemical kanye nokulungiswa kwesampula okuhlobene kwenziwe ebhokisini legilavu ​​eligcwele i-argon (PureLab, PL-HE-4GB-1800; <1-ppm O2 kanye namazinga we-H2O) elinikezelwe ukulinganiswa kwe-electrochemical.

I-morphology ye-pellet ene-Li[BMP][TFSI] ILE nangaphandle kwayo yahlolwa nge-SEM kusetshenziswa ithuluzi le-Thermo Fisher Scientific Apreo ku-1.5 kuya ku-2.0 kV lapho isebenza ngemodi yokucabanga ye-dual-detector kusetshenziswa umtshina we-T1 kanye ne-T2 ngokuhambisana ukulungiswa kwesithombe esibukhoma, kanye nomtshina we-T2 wasetshenziselwa ukurekhoda izithombe ze-SEM ezibonisiwe;isampula yalungiswa ku-carbon conductive tape.I-TEM yenziwa kusetshenziswa i-Tecnai esebenza ku-300 kV.

I-ILE ikhishwe ku-SCE pellet ngezindlela ezimbili ezihlukene.Inketho eyodwa yokuthola i-silica enezimbotshana yenziwa ngokucwilisa i-SCE ku-acetone amahora angu-12 ukuze kukhishwe i-Li[BMP][TFSI] ILE.Lokhu kugeza kwaphindwa kathathu.Enye inketho kwaba ngokucwilisa i-SCE ku-ethanol.Kulesi simo, i-ethanol yasuswa ngokusebenzisa isomisi sephuzu elibalulekile le-CO2.

Amathuluzi amabili ahlukene asetshenziselwa ukomisa okubaluleke kakhulu, okungukuthi, i-Automegasamdri-916B, i-Tousimis (indlela 1) kanye nethuluzi elakhelwe ngokwezifiso yi-JASCO Corporation (indlela 2).Lapho usebenzisa ithuluzi lokuqala, ukulandelana kokomisa kwaqala ngokuncipha kwezinga lokushisa lehle liye ku-8°C.Kamuva, i-CO2 yahlanzwa egumbini, okwandisa ukucindezela ku-5.5 MPa.Esinyathelweni esilandelayo, i-CO2 yashiswa ibe ngu-41 ° C, ikhulisa ukucindezela ku-10 MPa, futhi igcinwe kanjalo imizuzu engu-5.Ukuphetha, esinyathelweni sokopha, ingcindezi yehliswa phakathi nesikhathi se-10 min.Lapho usebenzisa ithuluzi elakhiwe ngokwezifiso, ukulandelana okufanayo kwalandelwa.Nokho, isikhathi nokucindezela kwahluka kakhulu.Ngemva kwesinyathelo sokuhlanza, ingcindezi yanda yaba ngu-12 MPa ekushiseni kuka-70 ° C futhi yahlala injalo amahora angu-5 kuya kwangu-6.Kamuva, ingcindezi yehliswa ngezikhathi ezithile ukusuka ku-12 kuya ku-7 MPa, 7 kuya ku-3 MPa, kanye ne-3 kuya ku-0 MPa ngokuhamba kwesikhathi kwe-10, i-60, ne-10 min, ngokulandelana.

Ama-isotherm e-nitrogen physisorption akalwe ku-T = 77 K kusetshenziswa i-Micromeritics 3Flex surface characterization analyzer.I-silica enezimbotshana eyatholakala yabe isikhishwa umoya amahora angu-8 ku-100°C ngaphansi kwevacuum engu-0.1-mbar.I-silica enezimbotshana etholwe ekomisweni okumangalisayo yakhishwa umoya amahora angu-18 ku-120°C ngaphansi kwevacuum engu-0.1-mbar.Ngemva kwalokho, ama-isotherm e-nitrogen physisorption alinganiswa ku-T = 77 K kusetshenziswa i-Micromeritics TriStar 3000 automated adsorption analyzer.

Izilinganiso ze-PFG-NMR zenziwe kusetshenziswa i-JEOL JNM-ECX400.Ukulandelana kwe-echo pulse okukhuthazwayo kwasetshenziselwa izilinganiso zokusabalalisa.Ukuncishiswa kwesignali ye-echo evamile, u-E, kuchazwa esilinganisweni (38)E=exp(−γ2g2δ2D(Δ−δ/3))(1)lapho u-g engamandla okushaya kwegradient, δ ubude besikhathi ishayela, ∆ isikhawu phakathi kwamaphethelo ahamba phambili ama-gradient pulses, γ isilinganiso samagnetogyric, futhi u-D yi-coefficient yokuzihlukanisa yama-molecule.Ama-coefficients azihlukanisayo alinganiselwa ngokufaka amasignali e-echo atholwe ngokushintsha ∆ nge-Eq.1. I-7Li ikhethiwe ukuze kunqunywe i-coefficient yokusabalalisa ye-ion ye-lithium.Zonke izilinganiso zenziwe ku-30 ​​° C.

Ukusethwa kwe-Raman spectroscopy kwakuwuhlelo lokuzenzela kusetshenziswa i-argon ion ekwazi ukushunwa isibani esivusa amadlingozi se-laser engu-458-nm esahlanganiswa nesibonakhulu esihlanekezelwe se-Olympus IX71, futhi ukukhanya okuhlakazeke emuva kwadluliselwa ngokusetha kwe-TriVista triple spectrometer (Princeton Instruments). ), esasetshenziselwa ukusabalalisa amasignali okubona atholwa kusetshenziswa ikhamera yedivayisi ehlanganisiwe ye-nitrogen epholile.Uma kubhekwa i-optical absorbance ephezulu kulawa maza wamaza, amandla e-laser aphansi asetshenziswa ukugwema ukushisisa nge-laser (<100 W·cm−2).

Ukulungiswa kwe-DFT yezwe eliphansi lejiyomethri nokubalwa kwefrikhwensi yokuhlaziya kusebenzise i-B3LYP hybrid functional edumile kanye nesethi yesisekelo engu-6-311++G**, nokulungiswa kokuhlakazwa kwe-athomu okubili kwe-athomu ye-Grimme (39) ngohlelo lwe-Becke-Johnson damping (D3BJ), njengoba isetshenziswe ku-ORCA 3.0.3 (40).I-Raman spectra yalingiswa kusetshenziswa i-ORCA, futhi ukubonakala kwezakhiwo zamangqamuzana kwafinyelelwa kusetshenziswa iphakheji yesofthiwe ye-Avogadro (41) enesibuyekezo esisekelwa i-ORCA.

Zonke izilinganiso ze-electrochemical kanye nokulungiswa kwesampula okuhlobene kwenziwe ebhokisini legilavu ​​eligcwele i-argon (PureLab, PL-HE-4GB-1800; <1-ppm O2 kanye namazinga we-H2O) elinikezelwe ukulinganiswa kwe-electrochemical.I-pellet ye-SCE yafakwa kuribhoni we-Li (Sigma-Aldrich; 99.9%) esekelwe epuleti yethusi njengoba i-electrode ephikisayo kanye namadiski amabili apuntshiwe aphuma e-Li (ububanzi obuyi-5-mm) abekwe phezu kwepellet ye-SCE ukuze kusetshenziswe ireferensi nokusebenza. ama-electrode.Ukusetha kuboniswa ku-fig.I-S7.Izikhonkwane zegolide zazisetshenziselwa ukuxhumana nereferensi ye-lithium nama-electrode asebenzayo.Izilinganiso ze-cyclic voltammetry ne-impedance zenziwe kusetshenziswa i-PGSTAT302 (Metrohm) elawulwa ngesofthiwe ye-Nova.I-voltammetry ye-cyclic yenziwe ngesilinganiso sokuskena esingu-20 mV/s.Izilinganiso zokuthikamezeka zenziwe nge-AC amplitude engu-5 mV kanye nemvamisa esukela ku-1 MHz ukuya ku-0.1 Hz.

I-electrode yefilimu encane engu-40-nm anatase TiO2 yafakwa nge-atomic layer deposition (ALD) ku-300-mm ye-silicon wafer ene-40-nm TiN underlayer nayo efakwe yi-ALD.Kuyi-electrode yokuhlola enhle kakhulu yokuboniswa kwe-Li-ion conductivity ngokusebenzisa ama-electrolyte, njengoba i-TiO2 ingahlushwa ukuwohloka kwamakhemikhali noma ukucindezeleka komshini (akukho ukuguqulwa kwevolumu okubalulekile) ngesikhathi sokuhamba ngebhayisikili.Ukukala iseli ye-Li/SCE/TiO2, ama-ILE-SCE agcwaliswe ngendandatho ye-PTFE enobubanzi obungu-4.3 mm nobukhulu obungu-0.15 cm;ke, indandatho yafakwa phakathi kwe-Li foil nefilimu ye-TiO2.

I-Nano-SCE/thin-film electrode half stacks, ene-electrode ye-LMO, yenziwe ngokuhlanganisa ifilimu ye-nano-SCE kuma-electrode.Isamba esingu-150 μl se-x = 1.5 isisombululo, esinezinsuku ezingu-2, saphonsa indandatho yengilazi (ububanzi, 1.3 mm) efakwe kumafilimu e-electrolyte.Iringi yabe ivalwa nge-parafilm, futhi ikhambi laligcinwa esitsheni esivalekile ukuze lifakwe ijeli izinsuku ezi-4.Ijeli/isitaki se-electrode esakhiwe kanjalo somiswa ukuze kwakhe izitaki ze-nano-SCE/electrode.Ubukhulu be-nano-SCE, obunqunywe kusetshenziswa i-micrometer, babungu-300 μm.Okokugcina, i-lithium foil (ubukhulu obungu-1.75 mm, 99.9%; Sigma-Aldrich) yacindezelwa ku-nano-SCE/electrode stack njenge-anode.I-electrode yefilimu elincanyana engu-100-nm LiMn2O4 (LMO) yafakwa yi-radio frequency sputtering ngaphansi kokugeleza kwe-Ar ku-wafer ye-silicon eboshwe ngezingqimba ezingaphansi ezingu-80-nm Pt (DC sputtering)/10-nm TiN (ALD).Lesi sitaki sifakwe amaminithi angu-20 ku-800°C emkhathini we-oxygen.

Amafilimu e-electrode e-LiFePO4 (LFP) alungiswe nge-blade coating.Okokuqala, i-carbon black kanye ne-LFP (2 kuya ku-3 μm) yengezwe kwisisombululo esinamanzi esine-carboxymethylcellulose (CMC) ukuze kwakhiwe ingxube eyathi kamuva i-homogenized kusetshenziswa i-mixer yeplanethi.Khona-ke, umkhiqizo owenziwe nge-homogenized waxutshwa namanzi enziwe nge-deionized kanye ne-fluorinated acrylic latex (JSR, TRD202A) ku-vacuum mixer ukuze kwakheke udaka lokumbozwa kwe-electrode.I-slurry elungisiwe yaphonswa kuma-aluminium foil ukuze kufakwe amafilimu e-electrode kusetshenziswa i-blade coater.Lawa ma-electrode amanzi agcotshwe ngokushesha afakwa ngaphambili kuhhavini osemkhathini onomoya onganyakazi ku-70°C imizuzu eyi-10 futhi aphinde omiswa ku-140°C amahora angu-4 kuhhavini wevacuum.Amafilimu omisiwe e-electrode ahlanganisa i-91 wt % LiFePO4, 3 wt % carbon black, 2 wt % CMC, kanye ne-4 wt % TRD202A.Ugqinsi lwefilimu luyi-30 μm (kunqunywa kusetshenziswa i-micrometer nesibonakhulu se-electron yokuskena).

Amafilimu e-electrode e-Li4Ti5O12 (LTO) enziwe kumafoyili ethusi ngendlela efanayo.Ukwakhiwa kwama-electrode omisiwe ngu-85 wt % Li4Ti5O12, 5 wt % carbon black, 5 wt % CMC, kanye ne-5 wt % fluorinated acrylic latex (TRD2001A).Ubukhulu befilimu bungama-40 μm.

Isixazululo se-SCE saphonswa phansi kwifilimu ye-LFP esekelwe kuyizinhlayiyana kanye ne-LTO electrode.Okokuqala, i-100 μl ye-x = 1.5 isixazululo, esinezinsuku ezi-2, yaphonswa kufilimu ye-electrode, enobubanzi obungu-15 mm, yafakwa kuseli lwemali (#2032, MTI).Ngemuva kokuthi i-SCE ekhulelwe ifakwe i-gelled, ifilimu yomiswa ku-25 ° C amahora angu-72 kuhhavini ye-vacuum (<5 × 10-2 mbar) ukwenza i-nano-SCE ne-electrode stack.Ubukhulu be-nano-SCE babungu-380 μm.Okokugcina, i-lithium foil yacindezelwa ezitaki ze-SCE/electrode njenge-anode, futhi iseli lemali lavalwa.Izilinganiso ze-electrochemical zenziwe kusetshenziswa i-Solartron 1470E potentiostat ekamelweni lokushisa.

Impahla eyengeziwe yalesi sihloko iyatholakala ku-http://advances.sciencemag.org/cgi/content/full/6/2/eaav3400/DC1

Ithebula S1.Izakhiwo zesakhiwo se-silica matrix ku-nano-SCE yokukhulisa ingxenyena ye-molar yoketshezi lwe-ionic ukuya ku-silica (inani elingu-x) elinqunywa kusukela ku-N2 adsorption/desorption noma izilinganiso ze-BET nokubonwa kwe-TEM.

Lena indatshana yokufinyelela evulekile esatshalaliswa ngaphansi kwemigomo yelayisensi ye-Creative Commons Attribution-NonCommerce, evumela ukusetshenziswa, ukusatshalaliswa, nokukhiqizwa kabusha kunoma iyiphi imidiya, inqobo nje uma ukusetshenziswa okuwumphumela kungekona okokuhweba futhi inqobo nje uma umsebenzi wokuqala ufanelekile. ikhonjiwe.

QAPHELA: Sicela ikheli lakho le-imeyili kuphela ukuze umuntu omncomayo ikhasi azi ukuthi ubufuna alibone, nokuthi aliyona i-imeyili eyimfucuza.Asithathi noma yiliphi ikheli le-imeyili.

Lo mbuzo owokuhlola ukuthi uyisivakashi esingumuntu noma cha kanye nokuvikela ukuthunyelwa kogaxekile okuzenzakalelayo.

Ngu-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 Mies.

Ngu-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 Mies.

© 2020 Inhlangano YaseMelika Yokuthuthukiswa Kwesayensi.Wonke Amalungelo Agodliwe.I-AAAS inguzakwethu we-HINARI, AGORA, OARE, CHORUS, CLOCKSS, CrossRef kanye ne-COUNTER.Science Advances ISSN 2375-2548.