Silica gel yakasimba nanocomposite electrolytes ine interfacial conductivity kukurudzira inodarika kuwanda kweLi-ion conductivity yeionic liquid electrolyte filler.

Shanduko kuenda kumabhatiri eLi-ion akasimba anogonesa kufambira mberi kusvika kumagetsi e1000 W·awa/lita uye nekupfuura.Macomposites emesoporous oxide matrix akazadzwa nenonvolatile ionic fluid electrolyte mafirita akaongororwa seyakasimba electrolyte sarudzo.Nekudaro, kuvharirwa kuri nyore kwemhinduro dze electrolyte mukati me nanometer-saizi pores inotungamira kune yakaderera ion conductivity sezvo viscosity inowedzera.Pano, tinoratidza kuti Li-ion conductivity yenanocomposites inoumbwa nemesoporous silica monolith ine ionic liquid electrolyte filler inogona kukwirisa zvakapetwa kakati wandei kupfuura ye pure ionic liquid electrolyte kuburikidza nekuunzwa kweazaya yechando.Yakasimba adsorption uye kurongeka kweiyo ionic mvura mamorekuru inoita kuti isafambe uye yakasimba-kunge seyakatarisana neaizi layer pachayo.Iyo dipole pamusoro peiyo adsorbate mesophase layer inoguma mukugadziriswa kweiyo Li + ions yekusimudzira conduction.Iyo yakaratidza musimboti weion conduction yekusimudzira inogona kushandiswa kune akasiyana masisitimu eion.

Solid-state electrolyte inotarisirwa kupa kuwedzera kunotevera kwemabhatiri eLi-ion kuti apfuure sirin'i inoshanda ye800 W·awa/lita kana 300 W·awa/kg akaisirwa pari zvino cathode uye anode chemistries.Kuwedzera kunotarisirwa kuwedzera kwesimba remabhatiri akasimba-nyika kunobva kune akati wandei mipiro, ese achinanga kuwedzera huwandu muzana hwezvinhu zvinoshanda muchitokisi.Iyo inonyanya kushambadzirwa ndeyekutanga kwe lithium simbi kutsiva graphite uye graphite / silicon seanode.Yakachena lithium simbi ine yakanyanya simba density inokwanisika uye nekudaro yaizoda nzvimbo shoma.Zvisinei, nyaya dzakawanda dzichiri kuda kugadziriswa, dzakadai sekusagadziriswa (uye nekudaro kushandiswa) kwe lithium metal, dendrite formation, kuwedzera kwehutano hunobudirira huripo hwe planar lithium foils kana ichienzaniswa ne porous graphite (silicon) electrodes, uye, yekupedzisira. asi kwete zvishoma, "kunyangarika" kwe lithium panguva yekubuda (deplating) uye nokudaro kurasikirwa kwekubatana ne electrolyte yakasimba.Iko kuomarara kwemechanical eceramic solid electrolytes zvechokwadi haina kutevedzera zero, uye dzvinyiriro dzakanyanyisa dzinoda kuiswa pakutsikirira lithium zvakasimba kupikisa chikamu chakasimba che electrolyte.Iyo discrete dzvinyiriro inodzikisira iyo inoshanda yepamusoro nzvimbo zvakanyanya, zvichitungamira kune yemuno dendrite kuumbwa uye spongy deposits.Mapolymer electrolyte anonyanya kuenderana nemuchina asi haasati aratidza yakakwira yakakwana ionic conductivity patembiricha yekamuri.Zvishandiso zvitsva zvinofadza zvikuru panyaya iyi isilica gel electrolytes, yakanziwo "ionogels," apo ionic liquid electrolyte (ILE) inovharirwa mu nanoporous silica matrix (1).Iyo yakanyanyisa porosity ye silica matrix (70 kusvika 90%) inopa izvi nanocomposite electrolyte zvinhu kufanana negel-kufanana nekuita kuti zvienderane nemakanika zvakafanana nemapolymer electrolytes.Aya silica gels dzimwe nguva anoratidzwa seyakasanganiswa yakasimba electrolytes, sezvo ine mvura.Nekudaro, kune iyo silica nanocomposites, seyakatsanangurwa mubepa rino, iyo ionic "mvura" electrolyte inova yakasimba-kufanana kana yakavharirwa mumakumi emanomita-saizi migero zvese nekuwedzera kwe viscosity uye nekushambadza pa silica wall inovharira iyo. channel.Kana iyo silica matrix yaizongoshanda seanoparadzanisa, saka kuwedzera kwe viscosity kune yakavharirwa mvura electrolyte kunozotungamira mukudzikira kweionic conductivity.Pane kudaro, kudyidzana pakati peILE molecules uye silica pore wall inoita kuti zvimiro zve nanocomposite zvisiyane nehuwandu hwezvikamu zvayo.Adsorption yeionic zvinwiwa pamaokisi nekugadzirwa kweakasimba mesophase akaturikidzana kusvika kune mashoma nanometer muukobvu kwakaratidzwa panzvimbo dzakarongwa neatomic force microscopy (2).Iyo yakasarudzika adsorption yeionic liquid anions uye cations pane oxide nzvimbo inogona kutungamira kune yakakwidziridzwa Li + conductivity pamwe aya mainterfaces.Ehezve, iyo yekusimudzira pamwe neiyo oxide interfaces inofanirwa kubhadhara kana kutopfuura iyo yakadzikira conductivity kuburikidza neILE yakavharirwa mukati me pores.Nekudaro, diki pore saizi uye yakakwirira pamusoro-kusvika-vhoriyamu ratios inodiwa.Parizvino, ionogels ine ion conductivities inosvika kune iyo yeILE pachayo yakaratidzirwa nekugadzirisa kwemesoporous chimiro (3).Izvi zvinoreva kuti kukwidziridzwa kwechimiro kwakange kwatovepo asi kwete kusvika pakupfuura bulk conductivity.

Kugadzirira kweionogels kunotanga kubva kune homogeneous fluid musanganiswa, umo ILE inowedzerwa kune sol-gel precursor mhinduro yekubatanidzwa kweiyo oxide matrix (4, 5).Munzira iyi, iyo ILE uye matrix zvinoumba composite nenzira ye "in situ": Iwo anotangira mumhinduro anoita kuumba oxide matrix yakatenderedza ionic liquid template, ichiiputira mukuita.Pasi pemamwe mamiriro ekugadzira, iyo yakagadziridzwa ILE-SCE (solid composite electrolyte) inogona kunge iri muchimiro che monolith ine ILE yakamisikidzwa mune inoenderera mberi mesoporous inorganic oxide network.Parizvino, mazhinji silica-based ILE-SCEs akagadzirwa nenzira iyi, kunyangwe mienzaniso yakaitwa nealumina (6), titania (7), uye kunyange tin oxide (8).Mazhinji akataurwa sol-gel maumbirwo ane ILE, alkyl-silicate senge tetraethyl orthosilicate (TEOS) sesilica precursor, uye formic acid se reagent uye solvent (9, 10).Zvinoenderana neyakarongwa nzira (11) yeiyi sol-gel process, silica inonyanya kugadzirwa nekuita pakati peTEOS uye formic acid, kunyangwe mvura inogadzirwa panguva ye-sol-gel process.Kunze kweiyi formic acid-based "nonaqueous" musanganiswa, aqueous sol-gel formulations ine HCl secatalyst uye H2O sereagent (pamwe ne organic solvent) yakatsanangurwa zvakare, zvakadaro, mune iyi nyaya yekuumbwa kwesilica inoumbwa ne. ionic mvura chete (12-15).

Kazhinji, ionogels inoratidza ion conductivity yakaderera pane iyo yeILE referensi.Chizvarwa chekutanga cheionogels chaive nekamuri tembiricha conductivities kazhinji inongosvika makumi matatu kusvika makumi mashanu muzana yehuwandu hweILE kukosha, kunyangwe mimwe mienzaniso inosvika makumi masere muzana yakashumwa (9, 10, 16, 17).Mhedzisiro yeILE yemukati uye inokonzeresa pore morphology pane ionogel conductivity yakatoongororwa zvakadzama (3);zvisinei, hapana kudzidza kwakarongeka kwemaitiro ekusimudzira maitiro anozivikanwa.Wu et al.(18) ichangobva kutaurwa pane in situ functionalized ionogel, iyo yakapawo conductivity yekusimudzira ichienzaniswa neiyo yakawanda ILE.Kuwedzeredzwa kwainzi kwakakonzerwa nekudyidzana pakati peanion uye 3-glycidyloxypropyl inoshanda boka pane silica pamusoro.Uku kutsvaga kunotsigira pfungwa yekuti kushanda kwepamusoro kunogona kunyatso kusimudzira interface conduction kukurudzira.

Mubasa iri, isu tinoratidza in situ kuumbwa kwemvura yechando yakasimba pa silica uye netsanangudzo magadzirirwo eiyo interfacial Li-ion conduction nekuwedzera kwekudyidzana kwe dipole pakati pepamusoro ice functional layer uye adsorbed ionic liquid mesophase layer.Nekusanganiswa kwenzvimbo yepamusoro yemukati uye dense ice functional layer, yakasimba nanocomposite electrolytes (nano-SCE) ine 200% yepamusoro Li-ion conductivity kupfuura yakawanda ILE referensi yakawanikwa.Iyo silica matrix inoratidzwa kuva yechokwadi monolithic mesoporous chimiro chine pore mavhoriyamu uye nzvimbo dzepamusoro dzinosvika 90% uye 1400 m2/g, nekudaro ichipa yakanyanyisa pamusoro-kusvika-vhoriyamu reshiyo inobvumira mupiro wakakura wekusimudzira conduction pamwe neaya mainterface.Nekukwenenzverwa kwekushanda kwe silica surface yakasanganiswa nekuwedzera chiyero chepamusoro-kusvika-vhoriyamu, nano-SCE ine ion conductivities inopfuura 10 mS/cm inogona kugadzirwa uye nekudaro inoyevedza mabhatiri makuru ekushandisa mota.

Tarisiro yebepa redu iri pamagadzirirwo ekusimudzira interface conductivity kuburikidza nekugadzirwa kwemesophase layer ine humbowo kubva kuRaman, Fourier shandura infrared (FTIR), uye nuclear magnetic resonance (NMR) spectroscopy.Iyo interface kugadzikana kwe yedu nano-SCE zvinhu pakakwirira voltages inoratidzwa uchishandisa yakaonda-firimu lithium manganese oxide (LMO) electrodes.Nenzira iyi, kutarisisa kunoramba kuri pazvinhu kwete pane iyo electrode kubatanidzwa uye sero gungano nyaya.Saizvozvo, iyo electrochemical hwindo uye kugadzikana kunopesana ne lithium simbi foils inoratidzwa zvizere.Kushanda uye kubatanidzwa kwenano-SCE yedu kunoratidzwa kuburikidza negungano uye chiyero chekuita miedzo ye lithium iron phosphate (LFP) uye lithium titanate (LTO) masero.Kugadzikana kwe electrolyte yedu uye kusashanda kwe electrochemical yemvura yechando kwakaratidzwa kuburikidza nekufamba kwenguva refu kwema symmetric Li-SCE-Li masero.Kukwidziridzwa kwesimba resimba, chiyero chekuita, uye kuita bhasikoro kwemasero akaunganidzwa akazara kuchave kutarisisa kwemapepa ekutevera (19, 20).

Interfacial ion conductivity kukurudzira mune maviri-chikamu anoumbwa masisitimu ave achizivikanwa kweanoda kusvika 90 makore (21).Semuyenzaniso, kusvika kumirairo ina yekuwedzera kweionic conductivity yakaratidzwa kune zvinoumba nyore lithium munyu zvakadai se lithium iodide ine mesoporous oxide particles akadai silica kana alumina kana zvichienzaniswa neion conductivity ye pure lithium salt electrolyte (22).Iwo maion ari mumaSCE aya anogona kupararira nekukasira pamwe neLi ion-yakapera (kana vacancy-rich) yemagetsi yakapetwa kaviri akaumbwa pane oxide/electrolyte interface.Nehurombo, iyo ion conductivity yakawanikwa mune aya akareruka maviri-chikamu inorganic solid-solid composites (1) haina kupfuura 1-mS/cm2 chikumbaridzo chinodiwa kubhuroka mashoma mazana-micrometer chinhambwe pakati peazvino mahwendefa ekuunganidza mubhatiri reLi-ion. .Pfungwa yeheterogeneous doping ine oxide matrix yeinjiniya iyo ionic conductivity yakaongororwazve yepolymer electrolytes (23) uye ILEs (24), iyo ine yakakwirira intrinsic ionic conductivity yekutanga nayo.Pamusoro pezvo, iyo yakapfuma molecular (stereo) chemistry yechikamu chechitatu inovhura mamwe maion conduction maitiro, sezvo (di) polar solvent-senge mamorekuru anogona kutora chikamu mukuumbwa kwemagetsi maviri layer.Nepo kugadzirisa kwemapoka ether mu polyethylene oxide polymer electrolytes inopa solid-state ion conductivities ye ~10−6 S/cm yeLiClO4 kusvika ~10−5 S/cm yeLiN(SO2CF3)2, macomposites awo ane silica, alumina. , kana titania nanoparticles inogona zvechokwadi kupa zvinopfuura gumi-kuwedzeredzwa mukuyerwa ion conductivity (25), zvinosuruvarisa, ichiri pazasi petembiricha yekamuri ye1 mS/cm.ILE mhinduro musanganiswa weLi-munyu solute uye ionic liquid solvent, inogona kutove nepamusoro intrinsic ionic conductivities pakati pe0.1 ne10 mS/cm (26, 27).Kuedza kwakawanda kwakaitwa kuwedzera iyo ion conductivity nekuisanganisa kana kuigadzira neoxide nanoparticles kana kuvhara iyo ILE mumesoporous microparticles (9, 16, 28, 29).Zvisinei, kusvika ikozvino, hapana kukwidziridzwa kweion conductivity kwave kuchionekwa kune matatu-chikamu Li-munyu / ionic liquid / oxide composite (fig. S1).Kunyangwe kushandiswa kwemesoporous silica microparticles kunoguma nepamusoro conductivity kana ichienzaniswa nemakombisi ane yakasimba nanoparticles, iyo yepakati pechiso nzvimbo uye ion conduction kukwidziridzwa haina kukwana kudarika bulk ILE conductivity.

Mesoporous silica chinhu chinozivikanwa chinoshandiswa mu catalysis.Inowanzo gadzirwa ne hydrothermal kana nyore sol-gel synthesis.Hydrothermal maitiro anowanzo tungamira kune mesoporous poda, asi nekuchenjerera kutonga kwekamuri tembiricha sol-gel maitiro, hombe porous girazi monoliths kana aerogels akagadzirwa zvakare.Iyo silica matrix inoumbwa kuburikidza ne hydrolysis uye condensation maitiro e tetra-alkyl orthosilicates (30).Chinokosha mukutonga kwechimiro chepore ndiko kushandiswa kwema templates, semuenzaniso, surfactant-type micelle, iyo iyo silica matrix inoumbwa.Kana ionic mvura yawedzerwa seye templating molecule, iyo hydrated silica matrix inopindirana neiyo ionic mvura, ichigadzira gel, uye mushure mekurapa nekuomesa, iyo ionic mvura inovharirwa mukati meiyo yakasimba nanoporous silica matrix (13).Kana lithium munyu yawedzerwa sechikamu chechitatu, ILE yakavharirwa mu silica matrix inoumba silica gel electrolyte, iyo yakanziwo ionogel (24).Zvisinei, kusvika ikozvino, aya silica gel electrolytes anoratidza conductivities kuswedera kune iyo yakawanda ILE asi isingapfuuri iyo, kunze kwechiitiko chimwe chete apo silica yakanga yashandiswa nemakemikari (ona Nhanganyaya) (18).

Pano, tinoratidza, kurongeka kwekusimudzira kweLi-ion conductivity ye nanocomposite zvakanaka kupfuura iyo yeILE yakachena.Muenzaniso we1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP-TFSI) inoshandiswa pano.Zvinofungidzirwa kuti adsorption yeionic liquid molecules paOH-yakapera silica pamusoro inosimudzirwa nekuvapo kwe interfacial ice water layer.Kubatana kwakasimba kwehydrogen pakati pemvura yechando uye TFSI-anion induces kurongeka kwemamorekuru eiyo ionic fluid, yakafanana neiyo yakarongerwa madomasi anongoerekana agadzira mune ionic zvinwiwa (31).Musiyano wakakosha nemadomasi akaumbwa muhuwandu ILE nderekuti iyo ice layer inoita senge inoshanda dhizaini iyo (i) induces iyo molecular order pane oxide surface uye (ii) inosuma yakasimba yakakwana H-bonding kuti iite dipoles kuburitsa mahara Li + kuitira kufambisa kufambisa.Padivi pekuwedzera kwemahara Li + yekumisikidza, isu ticharatidza kuti iyo activation simba rekuparadzira yakadzikira pamwe neiyo composite interface ine adsorbed ILE layer uye ice mvura layer.

Iyo shoma-monolayers-yakakora pamusoro pemvura yakadzika pa silica ndeye yakasimba-yakafanana dhizaini, sezvo yakanyatsobatanidzwa kune silanol mapoka kuburikidza neH-mabhiriji uye nekudaro zvakare inonzi ice layer (32).Kuwanda kwayo uye ukobvu (inofungidzirwa kusvika kune matatu kusvika mana monolayers, ine ~ 0.25 nm per ice monolayer) iri mu thermodynamic equilibrium ine chikamu chemvura inodzvinyirira [relative humidity (RH)] munharaunda (fig. S2).Isu tinoratidza kuti iyo ion conductivity inowedzera nehupamhi hwemvura yechando sezvo hydrogen bonding neiyo adsorbed ionic layers inowedzerawo.Iyo ice water layer yakagadzikana yakafanana nemvura yekristaro mumakemikari emakemikari.Izvi zvinopesana zvakanyanya neiyo super yakanyungudutswa yeaqueous electrolytes kana inonzi mvura mumisanganiswa yemunyu, uko hwindo remagetsi rinowedzerwa zvakanyanya asi, pakupedzisira, mvura ichiri kushanda nesimba (33).

Yakasiyana neyakajairwa formic acid-catalyzed ionogel mabikirwo, takashandisa yakapfava pH 5 musanganiswa ine yakakura yakawandisa yemvura uye PGME (1-methoxy-2-propanol) yakawedzerwa kune TEOS precursor ine Li-TFSI munyu uye BMP-TFSI ionic mvura.Pane iyi pH, maitiro e hydrolysis anononoka, nepo condensation yakanaka (30).MaLi ions anotendwa kuti anoita seanokonzeresa hydrolysis reaction, sezvo pasina gelation yakaitika mukushaikwa kwelithium munyu nepo vese vaine pH yakafanana ye5. Iyo molar ratio yeionic liquid kune TEOS (uye saka silica moieties) ndeye yakaratidzwa se x kukosha uye yakanga yakasiyana pakati pe 0.25 ne 2. Molar ratio yeBMP-TFSI kusvika kuLi-TFSI yakachengetwa pa3 (inoenderana ne1 M Li-ion solution).Kuomesa zvishoma nezvishoma kwaive kwakakosha kuchengetedza kutendeseka kwechimiro chemonolith chimiro (ona Zvishandiso uye Nzira).Mufananidzo 1A unoratidza mufananidzo we monolithic pellet yakawanikwa mushure mekuomesa vacuum.Iyo 72-awa vacuum drying yaive yakakwana kubvisa hunyoro hwese pasi kusvika painobviswa mvura yese yemahara nepo adsorbed ice water layer yakaramba yakasimba, sekusimbiswa neFTIR.Hapana kuzununguka kwemvura yemahara kwakaonekwa pa1635 cm-1 mune chero sampuli mushure meiyo vacuum yekuomesa nhanho (Fig. 2).Kuenzanisa, iyo FTIR spectrum ye nano-SCE sampuli (x = 1.5) yakachengetwa kwevhiki 1 mubhokisi reGrovhosi reN2 pa60% RH inoratidzwa.Muchiitiko ichi, peak yakajeka yemvura yakasununguka inooneka.Mienzaniso yese, kune rumwe rutivi, yakaratidza chiratidzo chakajeka chekushanda kwe silanol (Si ─OH kukotama pakati pe950 ne980 cm-1) uye adsorbed ice water layer (O─H inotambanudzira pa ~ 3540 cm−1) yakabatanidzwa iyo ─OH mapoka epamusoro neH-bonding (mamwe mashoko pazasi).Mabhodhoro akayerwa pamberi uye mushure mekuoma nhanho kuyera mvura yakachengetwa mu nano-SCE (tafura S1).Gare gare, isu tichaverenga nhamba yeinofanana monolayers yepamusoro-yakasungwa ice layers kubva kune yakawandisa huremu.Iyo vacuum-yakaomeswa pellets yakaunzwa mubhokisi regirovhosi [<0.1-ppm (zvikamu pamiriyoni) H2O] uye yakachengetwa mumidziyo yakavharwa kuchengetedza mvura yekutanga.Vhoriyamu diki yakatorwa kubva mupellet kuti iwedzere kuratidzwa.

(A) Mufananidzo wemaviri nano-SCE pellets (kuruboshwe) akagadzirwa mubhodhoro;mushure me gelation, pellet yakajeka inowanikwa.Cherechedza kuti pellet inonyatsojeka uye naizvozvo yakapiwa ruvara rwebhuruu rwekuonekwa.Kana iyo ILE yabviswa, brittle chena pellet inosara kune yakanyanya porous silica matrix (kurudyi).(B) Kuongorora electron microscopy (SEM) mufananidzo weSiO2 matrix inosara mushure mekubviswa kweILE.(C) Zoom yemufananidzo unoratidzwa mu (B) unoratidza mesoporous hunhu hwematrix zvinhu zvine mamwe macropores.(D) Transmission electron microscopy (TEM) mufananidzo unoratidza dense packing ye7- kusvika 10-nm silica nanoparticles sezvivharo zvekuvaka zve porous matrix material.(E) Iyo porosity yematrix yakarongwa kune akasiyana molar ratios yeILE maererano neSiO2 (x kukosha).Mutsetse wakadhindwa unopa theoretical porosity yakatemerwa kubva kuvhoriyamu chikamu cheILE uye silica.Iwo acetone-akasukurudzwa samples (dema mativi) akaomeswa mumhepo, izvo zvinopa chikamu kudonha kwechimiro che x> 0.5.Supercritical CO2 kuomeswa kwe ethanol-rinsed nano-SCE (green denderedzwa) inodzivirira kudonha kusvika x = 2 yekuwedzera kunonoka kubvisa CO2 (yakavhurika denderedzwa).BET, Brunauer-Emmett-Teller.Mufananidzo wechikwereti: Fred Loosen, imec;Akihiko Sagara, Panasonic.

(A) IR spectra ye nano-SCE yakaomeswa muvacuum (dema) uye yakazoomeswa mubhokisi regirovhosi ine 0.0005% RH kwemazuva 9 (bhuruu) uye yakafumurwa ku30% RH kwemazuva mana (tsvuku) uye ku60 % RH kwemazuva masere (girini), zvichiteerana.kana, mayunitsi asina kurongeka.(B) Cyclic voltammograms yeLi/SCE/TiN stack ine x values dze1.0 (blue), 1.5 (girini), uye 2.0 (tsvuku) uye yeILE reference (dema);iyo inset inoratidza ikozvino mu logarithmic scale.(C) Cyclic voltammograms yeLi/SCE (x = 2)/40-nm TiO2 stack (tsvuku), ILE (dotted black), uye ILE spiked ne 5 uremu % (wt %) H2O (dash-dotted blue line);mu (B) uye (C), kuyerwa neILE uye ILE neH2O zvakaitwa mumatatu-electrode configuration neTiN se electrode inoshanda uye Li se counter uye reference electrodes.Iyo SCE yakaomeswa kwemazuva maviri mubhokisi regirovhosi mushure mekuomesa vacuum.

Iyo ionic conductivity (σi) yevacuum-annealed nano-SCE yedu yakawedzera nevhoriyamu chikamu cheILE (x kukosha) seye particle composite (fig. S1).Zvisinei, munyaya iyi, ionic conductivity yakapfuura iyo yeILE yakachena pachayo nepamusoro pe200% yepamusoro-soro x maitiro (Fig. 3).Uyezve, kutsamira kwetembiricha ye nano-SCE ine yakawedzera ion conductivity yakaratidza hunhu hwakasiyana pane hweiyo yakachena ILE: Ipo Li-TFSI muBMP-TFSI ILE inoratidza shanduko yakajeka mukufambiswa uye activation simba (kutsetseka) kwakatenderedza kunyungudika. poindi yemusanganiswa pa29 ° C, iyo nano-SCE ine inosimudzira conductivity haiiti.Pane kudaro, inoratidza mutsauko unoenderera mu σi nekushisa, zvichiratidza kuti yaimbozivikanwa mhando yechikamu kana mesophase inoumbwa, iyo inozoita basa rekusimudzira conductivity.Uyezve, diki mutserendende uye nokudaro kuderedza activation simba kuti diffusion nokuda nano-SCE zvichienzaniswa ILE inoratidza zvakasiyana zvinhu zvinhu (fig. S3).Zvinofungidzirwa kuti kudyidzana kwakasimba pakati peiyo ionic liquid mamorekuru uye yakasimba ice layer pane silica scaffold inokonzera yakacherechedzwa maitiro emesophase, sezvichakurukurwa nemuenzaniso wakatsanangurwa pazasi.

(A) Kutsamira kwetembiricha ye conductivity ye nano-SCEs yakaomeswa kwemazuva masere mubhokisi regirovhosi (GB) ine x kukosha kwe2 (makona madema), 1.75 (orenji madenderedzwa), 1.5 (blue triangles), uye 1.0 (girinhi katatu ) uye yeILE reference (yakavhurika mativi).(B) Conductivity ye nano-SCEs yakawedzera kuomeswa muGB kwemazuva 0 (girinhi mativi), mazuva gumi (matatu matatu), uye 138 mazuva (blue triangles).(C) Conductivity maringe neskweya midzi yekuomesa nguva ye nano-SCE ine x makoshero e2 (black squares), 1.5 (blue triangles), 1.0 (green triangles), uye 0.5 (brown diamonds).(D) Conductivity ye nano-SCE ine x = 2 (makona matema), 1.5 (makona matatu ebhuruu), uye 1.0 (makona matatu egirinhi) akafumurwa muN2-yakazadzwa humidity chamber.

Mhepo yeArgon mubhokisi regirovhosi ine isingasviki 0.1 ppm yemvura, iyo inoenderana ne0.0005% RH, chidimbu chemvura chinomanikidza che 0.01 Pa, kana dova re -88 ° C.Sezvo nhamba yemvura yakashambadza yakanyungudutswa pane silanol-terinated silica iri mukuenzana nechikamu chekumanikidzwa kwemvura (fig. S2), mvura yepamusoro inopararira zvishoma nezvishoma kubva mu nano-SCE uye sublimate pamicheto.Mufananidzo 3C unoratidza shanduko mukufambiswa kwe23 μl ye nano-SCE sebasa renguva yekugara mubhokisi regirovhosi.Iyo ion conductivity inodzikira nekuomeswa kusvika yazara pamutengo unoenderana nesilica pamusoro pakuenzanisa nemvura yechikamu chekumanikidza kwe0.01 Pa mubhokisi regirovhosi.Kunyangwe pasi pekuoma kwakanyanya kwebhokisi regirovhosi, zvirinani, chikamu chemonolayer yemvura yakashambadzirwa pa silanol iripo, sezvo Raman spectroscopy ichiri kuratidza chiratidzo pa 3524 cm−1, iyo yakananga kune yekutanga monolayer ye adsorbed mvura pa silanol. (Mufananidzo 4B).Iyo ion conductivity pasi pemamiriro akazara yaive pasi peiyo yemunhu ILE mune zvese zviitiko.Nokudaro, kukwidziridzwa hakuna kukwana kubhadhara kurasikirwa muionic conductivity yeILE yakavharirwa mukati me pore.

(A) IR spectra ye nano-SCE ine x kukosha kwe1.5 (tsvuku), ILE referensi (dema), uye SiO2 (bhuruu), zvichiratidza kuti O═S═O boka (1231 cm−1) kusangana neOH-mapoka pane silica pamusoro.(B) Raman spectra ye nano-SCE ine x kukosha kwe2 (dema), 1.5 (tsvuku), uye 0.5 (bhuruu), ichiratidza kuvapo kwemvura yechando yakasungirirwa pa silanol-terminated silica kunyangwe nano-SCE padyo nesaturation (0.0005 % RH) mubhokisi regirovhosi (mazuva makumi matatu).(C) Modhi yakarongedzerwa yeiyo interface yekudyidzana mu nano-SCE ne dissociation Li-TFSI kupinda yemahara Li + sezvo TFSI- anion inogovera chikamu chechaji yayo yakaipa neiyo adsorbed ice-TFSI-BMP layer;mavara anomiririra zvinhu zvakasiyana nepepuru (silicon), tsvuku (lithium), yakasviba yero (sarufa), orenji (okisijeni), bhuruu (nitrogen), chena (hydrogen), uye girini (fluorine).Mitsetse yepepuru ine dashed inomiririra hydrogen bond pakati peO═S boka reTFSI anion uye OH-mapoka ehydroxylated silica pamusoro.Iyo Li + ions yakasunungurwa nedipole pamusoro peiyo adsorbed layer inogona kufamba kuburikidza neanotevera nharembozha kana kuparadzira ionic mvura yakaturikidzana pamusoro peiyo interface layer.Ziva kuti zvichienderana nekusimba kwezvisungo zvehydrogen uye mutero wakaenzana pasilica, akawanda adsorbed layer anogona kuumbwa zvakare.Full spectra inoratidzwa mufig.S8.

Chinofadza chekucherechedza hukama hwemutsara nesquare root yenguva yekuomeswa sezvinoratidzwa muFig. 3C, zvichiratidza kuti shanduko ye conductivity inonyatsoenderana nekuchinja kwehuwandu hwe adsorbed ice water pa silica uye kuti kubviswa kwemvura iyi yepamusoro diffusion limited.Cherechedza kuti "kuoma" kunongoitika munzvimbo yakazaruka apo RH yakaderera pane yekuenzanisa ice layer.Iyo conductivity haina kuchinja inocherechedzwa, semuenzaniso, mumaseru akavharwa emari anoshandiswa kuyera-inotenderera kuyerwa.

Kutsamira kwekushisa kwe nano-SCE kwakayerwa nguva dzakasiyana dzekuomesa mubhokisi regirovhosi.Sezvo iyo conductivity yeakaomeswa nano-SCE yakasvika kune iyo yeILE, iyo inoenderera σi inopesana ne1 / T profiles ye mesophase conductivity zvishoma nezvishoma yakachinja kune iyo profil yeILE, zvakare ichiburitsa kudonhedza kwakapoteredza kunyungudika kwayo (fig. S3).Kucherekedza uku kunoenderera mberi nekutsigira fungidziro yekuti ice layer inoshanda senge dhizaini yekudyidzana neILE, ichipa maitiro emesophase mu nano-SCE.Nekudaro, kana iyo inoshanda layer yabviswa, iyo ILE inongovharirwa mumesoporous oxide membrane.

Kuyera kwehwindo rekugadzikana kwe electrochemical inosimbisa kuti mvura yechando mu nano-SCE yakagadzikana, sezvo pasina nhongonya dzekudzikisa mvura kana oxidization yakaonekwa painert TiN electrode (Fig. 2) kana paTiO2 yakaonda-firimu electrode, iyo inobata zvimwe. se electro-catalyst yekuderedza mvura.Pane kudaro, kugadzikana kwe electrochemical ye nano-SCE kwakafanana zvikuru neILE uye nokudaro kunogumira ne oxidation ye TFSI- pa electrode potentials> 4.3 V uye kuderedzwa kweTFSI- uye BMP + pane zvinogona <1 V versus Li +/Li (33).Kuenzanisa, voltammogram inoratidzwa kune ILE ine 5 uremu % (wt%) mvura yakawedzerwa (yakafanana yemukati kune imwe nano-SCE; ona tafura S1).Muchiitiko ichi, bazi re cathodic rekuderedza mvura rinoyerwa pakarepo richitevera Li-intercalation peak ye anatase pa 1.5 V kupesana neLi +/Li.

Iyo inopisa uye (electro) kugadzikana kwemakemikari ye nano-SCE inonyanya kutsanangurwa neILE filler.Thermogravimetric analysis (TGA) yakaratidza kugadzikana kwekushisa kweSCE uye ILE kusvika ku320 ° C, pasinei neILE-to-silica ratio (fig. S4).Pamusoro peiyi tembiricha, iyo Li-TFSI neBMP-TFSI inoora zvachose kusvika kuzvinhu zvinoshanduka, uye chete silica matrix inoramba yakatenderedza 450 ° C.Iyo yakawanda muzana yakasara mushure mekuora kwemafuta zvechokwadi yakanyatsoenderana nechikamu chesilica muSCE.

Iyo nano-SCE yakaratidza hapana yakajeka microstructure mu scanning erekitironi maikorosikopi (SEM) kunze kwenzvimbo yakatsetseka ine mamwe silica mapechi achidongorera kunze (fig. S5).Iyo chaiyo density yeSCE yakatemwa nehelium pycnometer uye yaive yakatenderedza 1.5 g/cm3 kune ese x kukosha (tafura S1).Iyo yakazara silica matrix yakaratidzwa nekutemesa kutorwa kweILE mune solvent (ona Zvishandiso uye Nzira).Nokunyatsoomesa panzvimbo yakaoma ye CO2, intact airgel monoliths inogona kuwanikwa seyakaratidzwa muFig. 1A.SEM inspection inoratidza scaffold yemesoporous silica ine 10- kusvika 30-nm pore dhayamita, iyo yakaputirwa kumativi makuru macropores e100 kusvika 150 nm, sezvinoonekwa muFig. 1 (B uye C).High-resolution transmission electron microscopy (TEM) (Fig. 1D) yakawedzera kufumura microstructure inoumbwa nepedyo packed silica nanoparticles.Avhareji yepakati dhayamita yaibva pa7 kusvika pa14 nm ye x values pakati pe0.5 ne1.5.

Iyo chaiyo nzvimbo yepamusoro [Brunauer-Emmett-Teller (BET)], porosity, chiyero chepore saizi, uye pore saizi kugoverwa kwakatemwa neN2 adsorption / desorption zviyero (tafura S1 uye fig. S6).Kuputsika kwechidimbu kwechimiro uye kubviswa kusina kukwana kweadsorbed ILE kunogona kufananidzira zvisizvo nhamba.Kungwarira kutorwa kweiyo ionic fluid uye kunonoka kuomesa uchishandisa supercritical CO2 yakapihwa, zvisinei, yakavimbika mhedzisiro iri pedyo neinotarirwa porosity yakaverengerwa kubva kuvhoriyamu chikamu cheILE kusvika silica (Fig. 1).Nzvimbo yeBET yepamusoro inosvika pakati pe800 ne1000 m2 / g.Iyo yepakati pore saizi yakawanikwa kubva pamateru eisotherm yaive pakati pe7 ne16 nm.Mukuwedzera, chikamu chiduku chepores yakakura kusvika ku200 nm yakayerwa (fig. S6), maererano neSEM zvakaonekwa.Iyo dhayamita yepore inoenderana zvakanyanya nekaviri kuenzana kwakaenzana kweILE layer yakawanikwa kubva kuILE vhoriyamu chikamu uye iyo BET pamusoro penzvimbo, zvichireva kuti mesopores akazara neILE.

Iyo yakashumwa BET pamusoro nzvimbo ndeye mesopores uye macropores chete.Kune acetone-rinsed matrix, micropores (~ 0.6 nm) akayerwa zvakare.Iyo micropores inowanikwa pakati peiyo silica nanoparticles inogadzira chimiro seyakaratidzwa muTEM mufananidzo weFig. 1D.Nzvimbo yepamusoro yepamusoro yepamusoro pakati pe650 (x = 0.5) uye 360 m2 / g (x = 1.5) inofungidzirwa (tafura S1).

Ose ari maviri FTIR neRaman spectra anoratidza humbowo hwakajeka hwemapoka e silanol ane adsorbed ice mvura mamorekuru pane yakakwira-porosity silica matrix ine yakanyanyisa inoshanda nzvimbo inodarika 1400 m2/g kana uchifunga nezve micropores, mesopores, uye macropores.Pakati pe zero uye matatu emvura monolayers anofungidzirwa kubva kune yakawandisa mvura mu nano-SCE ye x <1.75.Kune planar silica, matatu ekutanga monolayers emvura adsorbed zvechokwadi anoonekwa seasingafambi uye akasimba-senge nekuda kwesimba rawo rehydrogen bonding kune OH-yakaguma pamusoro (32) (ona fig. S2).Iyo O─H yakatambanudzwa yakabatana ne silanol hydrogen yakasungirirwa kune yechando mvura layer inowanikwa pa 3540 cm-1 mu FTIR spectra.Yese nano-SCEs inoratidza, zvechokwadi, yakasarudzika peak pa 3540 cm-1 yemvura yechando mushure mekutsvaira kwevacuum uye mushure mekuwedzera kuomesa mubhokisi regirovhosi (Fig. 2).Kunyangwe kune yakaenzana nano-SCE pa 0.0005% RH (bhokisi regirovhosi), Raman spectroscopy ichiri kuratidza kuvepo kweinenge isina chikamu monolayer (Fig. 4B).Yechina monolayer pane planar silica inotendwa seye transitional layer, zvichireva kuti ichiri adsorbed uye inorambidzwa asi inogona kuve nekumwe kufamba.Kubva pachikamu chechishanu zvichienda mberi, mvura inova inofambisa uye yakaita semvura.Mvura-yakaita semvura icharatidza pahuwandu hwemafungu epamusoro muFTIR spectrum nekuda kweiyo yakaderera dhigirii yeH-bonding mumvura yemvura.Kune iyo nano-SCE yakafumurwa ku60% RH, iyo 3540-cm−1peak zvechokwadi inoratidza kumwe kuzunguzika kwakachinjirwa kune yakakwira mafungu manhamba nekuda kweyekuwedzera adsorbed mvura yemvura layer.Chinofadza panyaya iyi ndiko kuedza apo muenzaniso wakafumurwa 30% RH, sezvo pasina mvura mvura ichiri kutarisirwa silica panguva mwando ichi (fig. S2).Kune iyi sampuli, chete 3540 cm−1 peak yemvura yechando inoonekwa muFTIR.Mukuwedzera, hapana mvura yakasununguka yepamusoro yakaonekwa pa 1635 cm-1 kunyange mushure memazuva mana pa30% RH.Izvi zvinoreva kuti mvura haina kutorwa neiyo hygroscopic Li-TFSI yakanyungudutswa mu hydrophobic BMP-TFSI kana nano-SCE yakaomeswa nekugadziriswa kwevacuum.Naizvozvo, chero mvura yekuwedzera muSCE ichave yakashambadzirwa paOH-yakagadziriswa silica pamusoro.Nekudaro, kana iri planar silica, iyo SCE silica matrix iri mukuenzana nechikamu chekumanikidza kwemvura munzvimbo.

Kuti uedze iyi hypothesis zvakare, iyo ion conductivity ye nano-SCE (x = 1, 1.5, uye 2) yakayerwa pane zvakasiyana% RH;iyo samples yakaratidzirwa kune inodzorwa musanganiswa weiyo yakaoma uye yakanyoroveswa N2 gasi mubhokisi regirovhosi kwemazuva maviri kubvumira kuvharwa kwemvura adsorbed kusvika kuenzana (Fig. 3D).Kune mapoinzi pa ~ 0% RH, iyo conductivity yeyakaenzana nano-SCE mubhokisi regirovhosi yakatorwa.Zvinoshamisa, iyo ion conductivity maringe neRH (%) chimiro chakatevera maitiro aitarisirwa ekushambadza kwemvura pane planar silica (fig. S2).Pakati pe0 ne30% RH, iyo conductivity yakawedzera nekuwedzera RH.sezvinotarisirwa kuwedzera kwe adsorbed ice layer density uye ukobvu (zvichienderana neaizi imwe kusvika kumatatu akaturikidzana pane planar silica).Ziva kuti FTIR yakaratidza kuti hapana mvura yemahara yaivepo mu nano-SCE kwemazuva akati wandei pa30% RH.Shanduko inoonekwa yakatenderedza 50% RH, inoenderana nemamiriro ezvinhu apo inoshanduka adsorbed yemvura layer inotarisirwa kune planar silica.Pakupedzisira, kuwedzera kwakasiyana kwakasimukira kweion conductivity kunowanikwa ku60% uye humidity yakakwirira apo, mukufanana ne planar silica, ikozvino, zvakare mvura-yakaita semvura layer inogona kuumbwa pakusangana pakati pesilica neILE yakanyudzwa.NeFTIR, mvura yemvura yakadzika pane ice layer ikozvino yaonekwa nekuchinja kwe silanol / ice / mvura vibrational peak kune yakakwirira simba (Fig. 2A).Iko kucherechedzwa kushanduka mu conductivity kunodzoreredzwa;saka, iyo nano-SCE inogona kuita senge humidity sensor uye Li-ion electrolyte.Kubva mumufananidzo 3D, iyo ion conductivity ye nano-SCE pakarepo mushure mekuvhara anneal inopindirana ne equilibrium hydrated silica ye ~ 10% RH.Iyo ion conductivity yekuzara mumamiriro akaoma emukamuri (~ 0.5% RH) ingangoita 0.6 mS/cm (ye x = 2).Ichi chiedzo chinoratidza mhedzisiro yemvura yakatarisana pane iyo ion conductivity.Kune RH> 60%, iyo yepamusoro ion conductivity inogona kutsanangurwa nekukurumidza kupararira kweLi+ yakagadziriswa kuburikidza neiyo mvura-yakaita layer.Nekudaro, kana iri yeaizi yakasimba layer, iyo Li + ion diffusion ingave yakasimba-state mhando kupararira uye nekudaro inononoka kupfuura kuburikidza neiyo ionic fluid pachayo.Panzvimbo iyoyo, kukwidziridzwa kwacho kunokonzerwa nekuwedzera adsorption yeiyo organic anions uye cations yeLi-munyu uye ionic mvura mamorekuru, sezvakarongwa mumuenzaniso pazasi.

Isu tinokurudzira muenzaniso apo iyo ionic liquid molecules inoshambadzirwa pane silica pamusoro kuburikidza neH-mabhiriji ane immobile ice layer pamapoka e silanol (Fig. 4).Mamiriro emukati eiyo hydrolysis condensation reaction inopa yakanyanya silanol density (4 × 1014 kusvika 8 × 1014 cm-2, iyo inoenderana zvakanaka nekuwanda kweimwe monolayer yeaizi ine ~ 8 × 1014 mamorekuru emvura pa cm2) (34).Humbowo hwekudyidzana kwemamolecular pakati peO maatomu eTFSI anions uye silica inopihwa neFTIR, iyo inoratidza kupetwa kaviri kweiyo O═S═O peak kune ese nano-SCE kana ichienzaniswa neILE reference (Fig. 4A; yakazara spectra. muri S8).Kuchinja kweimwe peak neinenge −5 cm−1 kubva pa1231 cm−1 kunoratidza kubatana kwemapoka eO═S═O kana chikamu cheTFSI anions.Nokudaro, H-kusungirirwa kweTFSI anions pamvura yechando inofungidzirwa.Zvadaro, iyo hombe yehydrophobic BMP cations inobatana neyekutanga TFSI layer, ichipedzisa yekutanga adsorbed layer yeionic liquid mamorekuru.Kana iri ice layer, adsorbed BMP-TFSI mamorekuru anofungidzirwa kuti haafambike, nekudaro achitambanudza iyo yakasimba-senge ice layer pane silica pamusoro.Sezvo iyo TFSI anion ine symmetric O═S═O boka, atomu imwe yeokisijeni inogona kudyidzana neiyo hydroxylated silica pamusoro nepo imwe ichiumba mapoinzi ekunamira eBMP cations.Iyo TFSI anion zvakare ine maviri O═S═O mapoka, anovimbisa adsorption yakasimba uye dense kurongeka kweiyo anion monolayer.Adsorption inoshanda zvakanyanya kana iri dense ice layer ine yakanyanya density yeOH-mapoka sezvingangoita mapoinzi ekunamira.Muhupo hwemapoka e-silanol chete, kushambadza kunogona kunge kusina kusimba zvakakwana kuti iite inoenderera mberi adsorbate layer.Mukuwedzera, nhamba inowedzera yechando monolayers inozivikanwa kuwedzera simba rehydrogen bond (35).Ziva kuti kupindirana kwema molecular pakati peBMP cation uye yakarairwa TFSI monolayer ichave yakasiyana neiyo iri mumvura ionic umo TFSI anion ine rusununguko rwekutenderera uye isina polarization kubva pasi pevhu.Kuchaja kweiyo hombe BMP cation yakagovaniswa pamusoro peatomu mazhinji nekupolarization yemukati mabhondi uye nekudyidzana kwemamorekuru nenzvimbo yayo yemakemikari uye, kunyanya, yakashambadzirwa TFSI anion.Iyo H-bonding pakati peO-boka reTFSI anion uye OH-kugumiswa kweaizi layer ikozvino inounza dipole pamusoro pekutanga adsorbed layer, ichikonzera kumwe kurongeka kwemamorekuru nemubatanidzwa.Zvinotendwa kuti panguva ino, madiki eLi-TFSI mamorekuru adsorb pane molecular layer apo iyo TFSI anion ikozvino inotsiva yasara yakanaka dipolar charge yeimwe kana anopfuura eiyo BMP cations muyepamusoro layer, nekudaro ichisunungura kubatana kwayo neLi. ion.Nenzira iyi, iyo yemahara Li + inowedzerwa pane ino interface, inotungamira kune yakakwirira ion conductivity.Nekudaro, denser uye gobvu mazaya echando anobva aunza dipole hombe ine yakakwira yasara charge yekuripa, ichipa yakaenzana yakakwira yemahara Li + concentration uye nekudaro ion conductivity.

Pamusoro peiyo adsorbed ILE layer, ingave imwe ILE layer inogona adsorb yakafanana neaizi multilayers pane silica kana dipole kudhonza kweaizi layer haina kusimba uye ILE yakasungwa zvishoma iri pamusoro, iyo inogona kupa mvura-yakafanana conduction ye. iyo Li + ions yakaburitswa muzasi adsorbed layer (Fig. 4C).Shanduko yemahara Li + ion concentration yakatsigirwa neese NMR uye Raman spectroscopy zviyero.Zviyero zveRaman zvisina kunanga zvinoratidza kuti chikamu chikuru chemahara Li + ions chiripo zvechokwadi mu nano-SCE ine mamwe mazaya emvura echando akasungirirwa kune silica (Fig. 5).Iyo Raman inoyera kubatanidzwa kwe cation neTFSI nekuongorora kudedera kweN-boka reTFSI anion (36).Mune yakachena BMP-TFSI ionic fluid, chete peak imwe pa741 cm−1 inoonekwa.Panyaya yeILE yakachena, imwe yepamusoro inoonekwa pa 746 cm-1 apo maviri TFSI anions anowirirana neLi + ion imwe chete [ona density functional theory (DFT) kuverenga muZvishandiso uye Nzira].Kune ese nano-SCEs, iyo peak intensity pa746 cm−1 haina kusimba pane iyo yeILE, zvichiratidza chikamu chidiki cheLi-TFSI chakabatana uye, nekudaro, chikamu chikuru cheanobatanidzwa kana emahara Li + cations.Iyo peak inodzikira zvakanyanya kune iyo nano-SCE inoratidza yakanyanya conductivity yekusimudzira, kureva, avo vane gobvu rechando.Kune iyo nano-SCE pakuenzanisa mubhokisi regirovhosi, zvakadaro, chidimbu chemahara Li+ chinoyerwa kunyangwe chiri chidiki zvakanyanya pane chevacuum-annealed samples.Chiyero chepamusoro-soro che 746 pamusoro pe 741 cm−1 Raman inoshanduka ipapo chiyero chereshiyo yemahara kune TFSI-yakabatana Li-ions (Fig. 5B).Kuwedzera kwemutsara kwemahara Li+ ion chikamu chine x kukosha kunotevera maitiro ekusimudzira conductivity ne x kukosha muFig. 3B, zvese zvevacuum yakaomeswa nano-SCE (zuva 0) uye SCE pakuenzana nekuoma kwebhokisi regirovhosi (zuva 138).

(A) Raman spectra yeionic liquid (IL; ine bhuruu mutsara) uye ILE referensi (ILE; dash-dotted mutsara) seyakagadzirirwa nano-SCE (vacuum yakaomeswa) ine x kukosha dze0.5 (girinhi), 1.5 (yero) , uye 2 (brown) uye ye nano-SCE (x = 1.5) yakawedzera yakaomeswa mubhokisi regirovhosi kwemazuva makumi matatu kana pedyo nekuzara pa0.0005% RH (tsvuku).Mitsetse yakatwasuka inotara kuchinjika kweRaman yeTFSI ine N centre yakarongedzwa kuLi+ (746 cm−1) uye isina kurongeka kuLi+ (741 cm−1), zvichiteerana.(B) Ratio yemahara kune yakarongeka Li + ye nano-SCE seyakagadzirwa (vacuum yakaomeswa, dema madenderedzwa) uye nekuwedzera yakaomeswa mumabhokisi egirovhosi ane 0.0005% RH kwemazuva makumi matatu (madhaimondi ebhuruu), anoenderana nechiyero cheiyo yakabatanidzwa kusimba kweiyo. Raman peaks (746 cm−1 pamusoro pe741 cm−1).(C) PFG-NMR-yakatorwa Li+ self diffusion coefficient ye nano-SCE (madhaimondi matsvuku) uye ILE ref.(black squares) sebasa renguva pakati pe gradient magnetic field pulses.Iwo epamusoro etioretical paRaman spectra akateedzerwa uchishandisa DFT kuverenga.

Kubva pane pulsed-field gradient NMR (PFG-NMR), iyo yekuzviparadzanisa-coefficient yemhando dzakasiyana siyana dzeLi-ion dzakatemerwa sebasa renguva pakati pegradient magnetic field pulses ∆ yeILE liquid reference uye nano- SCE (x = 1.5) ine imwechete ion conductivity ye 0.6 mS / cm (Fig. 5C).Iyo Li + yekuzviparadzanisa-yega coefficient muILE referensi yaingogara, zvichiratidza kuti imwe chete kana akawanda emhando dzeLi dzinenge dzakafanana kufamba dziripo mumvura.Kune iyo nano-SCE, iyo yekuzviparira coefficient yakasiyana ne ∆ uye yakapfuura iyo yeILE panguva pfupi ∆, ichiratidza kuvapo kwemarudzi anokurumidza kufamba anopindura chete munguva pfupi pakati pemagineti.Iyo gradient mu-self-diffusion coefficient inoratidza kuti padivi pekuwedzera kwemahara Li-ion concentration, seyakatorwa kubva kuRaman spectroscopy, iyo activation simba rekupararira inodzikiswa mumesophase interface layer zvakare.Izvi zvinotsigira conductivity yekusimudzira yakaunzwa neiyo (yakawanda) yemahara Li + ions mumesophase layer.Nekurebesa ∆, iyo yekuzviparadzira coefficient yaive yakaderera pane iyo yeILE referensi.Izvi zvinotsigira yakaderera ion conductivity yebhokisi regirovhosi-yakazara nano-SCE ichienzaniswa neILE.Iyo ILE yakavharirwa mukati meiyo mesopores ichave nepamusoro viscosity nekuda kwekurambidzwa kwema molecular kufamba.Nekudaro, iko kukwidziridzwa nekugadzira kwekukurumidza kuparadzira Li-ion pane silica/ice/ILE interface inofanirwa kuwedzeredza kudzikira kwekufambiswa kwepakati pe pore.Izvi zvinotsanangura kusavapo kwekusimudzira muzvikamu-zvakavakirwa masisitimu apo iyo interfaces isingapi yakakwana ion conduction kukurudzira (fig. S1).

Kugadzikana kwe electrochemical ye nano-SCE pamusoro pe lithium metal yakaedzwa uchishandisa matatu-electrode setup (schematic of setup inoratidzwa mufig. S7).Ikozvino-inogoneka hunhu hweLi / SCE (x = 1.5) uye Li / ILE hafu-sero inoratidzwa muFig. 6A.Kana iri hwindo re electrochemical muFig. 2, electrochemistry inogumira neILE filler.Reversible lithium plating uye kubvisa zvinoonekwa.Yakatsiga yakasimba electrolyte interphase (SEI) layer inoumbwa pametallic lithium ine RSEI inosvika 0.9 kilo-ohm·cm2, inokonzera kudonha kukuru kweIR muiU curve kumativi maviri ecathodic uye anodic.Iko kathodic ikozvino mune yakachena ILE mhinduro haina kuratidza chero hysteresis kusvika -2.5 mA / cm2.Nekudaro, iyo anodic dissolution yakaratidza passivation peak ine steady-state anodic ikozvino ye 0.06 mA/cm2 chete.Iro cathodic current branch pa-solid-solid Li/SCE interface yakaratidza hapana hysteresis ye cathodic currents isingasviki -0.5 mA/cm2.Kupokana kweSEI kwaive, zvisinei, kwakapetwa kaviri.Saizvozvo, iyo anodic peak yaive yakadzikira uye yakatsiga-mamiriro ikozvino mushure meanodic passivation peak yaive 0.03 mA/cm2, hafu chete yeiyo yakachena ILE mhinduro.Kuumbwa kweSEI uye passivation layers mumapores eSCE inomisa iripo palithium simbi.Ose ari maviri mavoltammograms eLi/ILE uye Li/SCE maelectrode aidzokororwa pamichinjiro yakawanda, zvichiratidza kuti anodic passivation layer uye kemikari SEI layer inodzorereka uye yakagadzikana.Iyo inononoka dissolution kinetics paLi/SCE interface inodzikamisa zvakanyanya kuita kwehafu-masero akagadzirwa neLi simbi anode pazasi.

(A) Cyclic voltammogram ye nano-SCE (x = 1.5, seyakagadzirwa mushure mekuomeswa kwevacuum) (tsvuku) uye ILE referensi (dema) yakayerwa mumatatu-electrode configuration neLi sekushanda, counter, uye referensi magetsi (SEI kuramba kunofungidzirwa kubva IR kudonha pa cathodic current i 0.9 uye 1.8 kilo-ohm·cm2 yeILE ne SCE, zvichiteerana).(B) Galvanic charge / discharge curves yeLi / SCE (x = 1) / 100-nm yakaonda-firimu LiMn2O4 sero yezvikamu zvishanu paC-mazinga e1C, 5C, uye 20C.(C) Cyclic voltammograms yeLi / SCE / 40-μm Li4Ti5O12 uye Li / SCE / 30-μm LiFePO4 powder electrode masero (1 mV / s).(D) Galvanic charge/ discharge curves yeLi/SCE/40-μm Li4Ti5O12 poda electrode pa1C, 0.1C, 0.2C, uye 0.02C.(E) Galvanic charge / discharge curves yeLi/SCE/30-μm LiFePO4 poda electrode pa1C, 0.5C, 0.2C, 0.1C, 0.05C, uye 0.01C.(F) Kugona (madhaimondi akazadzwa e delithiation uye akazaruka masikweya e lithiation) maringe nenhamba yekutenderera yeLi/SCE/30-μm LiFePO4 poda electrode;ukobvu hweSCE mumaseru hunosvika 280 μm.Kuwanda kweLFP uye LTO cathode inenge 1.9 uye 11.0 mg / cm2, maererano.(G) Zvingangove zvichienzaniswa nenguva macurves eLi/SCE/Li stack yakatenderedzwa pazvino densities ye0.1, 0.2, 0.5, uye 0.1 mA/cm2.(H) The 1st, 10th, 125th, uye yekupedzisira polarization yeLi / SCE / Li stack yakasimbiswa pa 0.1 mA / cm2, inoratidzwa mu (G).Kune (G) uye (H), iyo SCE ine conductivity ye0. 34 mS/cm, uye ukobvu hweSCE pellet i0.152 cm.

A 100-nm LiMn2O4 (LMO) yakatetepa-firimu yakashandiswa semuenzaniso wakanaka electrode kuyedza kugadzikana kwenano-SCE uye emagetsi zvinhu uku ichibvisa zvingangoitika zvemukati maelectrode ecomposite (37).Kuita kwebhasikoro kweiyo yakaonda-firimu electrode / SCE stack inoratidza kugadzikana kweiyo interface pakati pe electrode uye electrolyte.Mumuenzaniso uyu mutete-firimu setup, imwe chete, yakanyatsotsanangurwa, uye planar interface yekubatana iripo pakati pe electrolyte ne electrode, kureva, ipuratifomu yakanaka yekudzidza electrochemistry ye electrolyte/electrode interface pasina nyaya dzekuchinja kwevhoriyamu. , nezvimwewo zvakare mukuedza uku, chiyero chekuita hachina kuganhurirwa neLi-foil counter electrode, sezvo density yemazuva ano (6 μA/cm2 ye1C) iri pazasi peiyo inotsiga-inodic ikozvino plateau ye lithium hafu-. sero (0.03 mA/cm2).Reproducible uye yakagadzika charge / discharge curves inowanikwa kune cutoff voltage pa4.3 V yeC-mitengo pakati pe1 ne20C kweanopfuura 20 cycles (Fig. 6B).LMO haina kugadzikana mune yemvura electrolyte yeLiB.Semuyenzaniso, kuderedzwa kwe50% kwehuwandu kwakaonekwa pa100-nm LMO bhaisikopo rechaji-yakaburitswa kwegumi muLiClO4/propylene carbonate electrolyte pa1C (37).Mhedzisiro yedu inoratidza kuti nano-SCE inonyanya kuenderana neLMO pane yakajairwa mvura electrolyte.

Kuti tiratidze kubatanidzwa kwe nano-SCE, takagadzirawo hafu-masero ane Li4Ti5O12 (LTO) uye LiFePO4 (LFP) poda electrodes.Mushonga weprecursor wakadonhedzwa-wakakandirwa musero remari kuti iise ma porous electrodes ndokusiiwa kuti iwedzere gelation isati yaomeswa uye vacuum-annealed zvakafanana neye nano-SCE pellets.Masero anoratidza maitiro lithiation / delithiation yemagetsi anoenderana (Fig. 6C).Iyo yakaderera peak currents yeLFP pane LTO inokonzerwa nemusiyano mukukobvu kwekuputira.Chiyero chekuita panguva yekuchajisa/kuburitsa kuyerwa zvino kwakaganhurwa neLi-foil counter electrode yakatsikirirwa pane nano-SCE layer yakaumbwa pamusoro pe30- kusvika 40-μm-makobvu emagetsi emagetsi (Fig. 6, D uye E).Iyo LTO / nano-SCE / Li sero yakasvika pakukwanisa kwayo kwe160 mA · awa / g chete paC-rate yakaderera ye0.02C (Fig. 6D).Kusvikika kwesimba kunodonha nekukurumidza neC-reti isingasviki 10% yeC-mazinga akakura kupfuura 0.1C.Saizvozvowo, LFP / SCE / Li sero yakasvika pakukwanisa kwayo kusvika 140 mA · awa / g pa 0.01C (Fig. 6E).Mufananidzo 6F unoratidza chiyero chekushanda kwehuwandu hwemakumi matatu ekutenderera, kuratidza kugadzikana kwesero configuration.Izvi zviedzo zvinoratidza kushanda kwenano-SCE seLi-ion electrolyte uye kugona kwekubatanidza mumasero eLi-ion.

Kugadzikana kana kutenderera kwenano-SCE kwakaedzwa uchishandisa Li/SCE/Li symmetric stack.Yakanga yakatenderedzwa kweanopfuura 120 kutenderera panguva ino density ye0.1 mA / cm2 kwemaawa 0.5 (Fig. 6G) pasina chero nyaya kana dendrite kuumbwa (Fig. 6H).Iyo polarization voltage yakava diki nekufamba kwenguva, zvichiratidza kuvandudzwa kwekusangana.Uyezve, sero yakasimbiswa kusvika kune ikozvino densities ye 0.5 mA / cm2, pasina chero kuumbwa kwe lithium dendrites kana zviratidzo zvekuora kwe nano-SCE kana iyo interface (Fig. 6G).Metallic lithium inozivikanwa kuumba inodzivirira interphase layer kana SEI pamusoro wayo muBMP-TFSI-based ILEs (27).Kuita uku kunoitikawo pa lithium/nano-SCE interface;sezvakakurukurwa pasi peMufananidzo 6A, SEI inogona kukura zvishoma mukati me pores, ichitsanangura iyo yakakwirira SEI kushorwa kwe nano-SCE kupfuura ILE (ona pamusoro).Uchapupu hweSEI layer yakawanikwa kubva kuIR spectra (fig. S9).Zvakafanana neSEI coating mu classical LiB, iyo inovheneka graphite electrode kubva mumvura electrolyte kudzivisa mamwe maitiro, isu tinotenda kuti SEI pano inodzivirirawo chando chemvura yechando kubva kune mamwe maitiro kubva kune esimbi lithium anode.Impedance spectra isati yasvika uye shure kwepolarization yeLi / nano-SCE (x = 1.5) kwemaawa gumi haina kuratidza chero shanduko muhuwandu hwekugadzirisa electrolyte.Zviyero zvekuita kwebhasikoro kwenguva refu zvinozodiwa kusabvisa kuomeswa zvishoma nezvishoma kwe nano-SCE nelithium simbi, asi mhedzisiro iyi yatoratidza kugona kwayo kwekugonesa kutenderera kweSCE mu lithium metal-based solid-state mabhatiri.Zvakangodaro, artificial interphase coatings anogona kutariswa kuvandudza iyo interface impedance zvachose.

Takaratidza kuti ion conduction promotion pa silica interfaces inogona kuwanikwa kuburikidza nekuunzwa kwechemisorbed water layer paOH-terminated silica surfaces.Iyo TFSI anions chemisorb pane iyi mvura inoshanda layer kuburikidza nehydrogen bonding neiyo symmetric O═S═O boka.Iyo yemvura yakaturikidzana haifambi uye nekudaro inonamira iyo adsorbed TFSI layer kumusoro.Iyo yakakura BMP cations inobatana neTFSI monolayer, nekudaro kuunza mamorekuru kurongeka kweTFSI-BMP pamusoro.Isu tinotenda kuti iyo inononoka gelation munzvimbo ine aqueous uye inononoka kuomeswa kunobatsira mukuumbwa kwakasanganiswa kweiyo inoshanda yemvura layer uye yakarongeka layer ye organic ions pamusoro payo.Sezvo yekutanga TFSI anion layer ichigovera chikamu chechaji yayo isina kunaka neiyo hydroxylated silica, iyo BMP cation layer iri pamusoro ichatsvaga kushamwaridzana neimwe TFSI anion, iyo yakawanda BMP inogona kugovera yavo isina kubhadharwa mhosva neTFSI imwe (zvichida matatu kune imwe semu chiyero cheIL kune Li-TFSI muILE).Sezvo Li-TFSI mamorekuru emunyu ane nzira yepedyo, maLi + ions anozopatsanura uye kusunungurwa kuti aendeswe nekukurumidza pamwe neiyi interface layer.Kuti uwedzere kufambisa, idzi dzemahara Li + mhando dzinoda imwe yekuwedzera ionic fluid layer kuti ifambe.Nechikonzero ichi, iyo nano-SCE ine yakaderera x kukosha kwe0.5 yakaratidza isina kukwidziridzwa conductivity, sezvo iyo ILE vhoriyamu / silica nzvimbo inokwana kune imwe chete yakavharwa monolayer.

Yakaratidzwa zvakare kuti mvura yakasimba-yakafanana nepamusoro pemvura kana ice layer haisi electrochemically inoshanda.Panguva ino, hatigone kusabvisa kuti mvura yechando inosangana zvakananga ne electrode surface haisi kuita.Zvisinei, takaratidza kuti kunze-kupararira kwemvura yepamusoro kunononoka uye nokudaro kinetically isina hanya kuti ionekwe.Isu tinoziva kuti kusvibiswa kwemvura, kunyangwe idiki, inogara ichinetsa, uye chete miyedzo yenguva refu yehupenyu inogona kupa mhinduro chaiyo yekuti mvura yakasungwa zvakakwana here.Nekudaro, mamwe maseru anoshanda epamusoro anopa zvakafanana kana kutokura kukwidziridzwa kwepamusoro anogona kuvandudzwa.Panyaya iyi, boka reLi rakatoratidza kukwanisa kweglycidyloxypropyl layer seboka rinoshanda (18).Mvura yechando inowanikwa kune silica uye saka yakanyatsokodzera kudzidza mhedzisiro yekushanda kwepamusoro pane ion conduction kukurudzira zvakarongeka, sezvakaratidzwa zvinobudirira pano.Pamusoro pezvo, iyo mesophase layer uye dipole yayo inotsamira pane oxide uye pane adsorbed organic mamorekuru uye nekudaro anogona kutariswa neaviri.Murabhoritari, takatoratidza misiyano mikuru mukusimudzira ion conduction kune zvakasiyana zvinwiwa zveionic.Uyezve, musimboti unoratidzwa ndeye generic kune ion conduction uye unogona zvakare kushandiswa kune akasiyana masisitimu eion akakodzera, semuenzaniso, kune sodium, magnesium, calcium, kana aluminium ion mabhatiri.Mukupedzisa, iyo nanocomposite electrolyte ine interface conduction inoratidzwa pano ipfungwa kwete chinhu chimwe chete, chinogona kuenderera mberi (nano) kugadzirwa kune inodiwa zvivakwa zveion conduction, nhamba yekufambisa, hwindo remagetsi emagetsi, chengetedzo, uye mutengo wezvizvarwa zvebhatiri masero. .

Iyo nano-SCE yakagadzirwa uchishandisa sol-gel nzira.Lithium bis(trifluoromethylsulfonyl)imide Li-TFSI;Sigma-Aldrich;99.95%), 0.5 ml yeH2O deionized, 0.5 ml yeTEOS (Sigma-Aldrich; 99.0%), 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide (BMP-TFSI; Sigma-Aldrich; 9815%). ml yePGME yakasanganiswa mubhodhoro regirazi.The molar ratio, x, pakati pe [BMP][TFSI] neTEOS mumusanganiswa yakanga yakasiyana pakati pe 0.25 ne 2. Molar ratio yeLi [TFSI] uye [BMP][TFSI] yakagadziriswa pa 0.33: 1.Huwandu hweLi[TFSI] ne [BMP][TFSI] hwakatarwa kubva muzvikamu izvi.Semuenzaniso, apo x = 1, iyo yakawedzera [BMP][TFSI] uye Li[TFSI] mumhinduro yaive 0.97 uye 0.22 g, zvichiteerana.Misanganiswa yakazununguswa kwe1 min kuti iite monophasic solutions.Mishonga iyi yakabva yachengetwa mumabhodhoro akavharwa pasina kubvongodza kuumba gels mune tembiricha- uye humidity-controlled chamber (SH-641, ESPEC Corp.) ine tembiricha uye RH% yakaiswa pa25 ° C uye 50%, zvichiteerana.Zvichienderana ne x, misanganiswa yakatora, paavhareji, mazuva mashanu kusvika ku9 kugadzira gel rakajeka.Mushure mekuita gelation, mabhodhoro ane 2.4- kusvika 7.4-ml gel akatanga kuomeswa pa40 ° C kwemazuva mana akazara pane zvishoma zvishoma kuderedza (80 kPa) uye akazoendeswa muvheni yekutsvaira kwemaawa makumi manomwe nemaviri pa25 ° C.Sezvo hunyoro hwakasara hwakabviswa, iyo vacuum yakadzikira zvishoma nezvishoma kubva pakumanikidzwa kwekutanga kwakatenderedza 50 Pa kusvika kune yekupedzisira kudzvinyirira kwe5 Pa mushure mezuva rimwechete.Nekuda kwehuwandu hwemvura uye PGME yaifanira kubviswa, iyo yakaguma SCE pellets yakanga yaderera kubva ku20% (x = 0.5) kusvika ~ 50% (x = 2) yepakutanga gel volume.Huremu hwemajiro akabuda hwakayerwa nesemimicro balance (SM 1245Di-C, VWR).

TGA yakaitwa paQ5000 IR (TA Instruments, New Castle, DE, USA) pasi penitrogen.Munguva yekuyera, sampuli dzakapiswa kusvika ku700 ° C pamwero wekupisa we2 ° C / min.FTIR spectrometry yakaitwa uchishandisa Bruker Vertex 70 munhamba yemasaisai inotangira pa4000 kusvika 400 cm−1 mune yekufambisa nzira.Iye pycnometry yakaitwa uchishandisa Micromeritics AccuPyc II 1340.

Kuyera iyo ionic conductivity, vhoriyamu diki yeSCE yakatorwa kubva kuna mai vial mukati meAr-filled glove box (0.1-ppm H2O uye 0.1-ppm O2).Inenge 23 μl yeSCE yakazadzwa mu polytetrafluoroethylene (PTFE) mhete ine 4.34-mm mukati dhayamita uye 1.57-mm kureba, ichiita pellet.Pellet mumhete yakazoiswa pakati pemadhisiki maviri esimbi isina tsvina (SS) (0.2 mm gobvu; MTI).Zviyero zvekudzivirira zvakaitwa pachishandiswa PGSTAT302 (Metrohm), ine AC amplitude ye5 mV mune frequency renji kubva pa1 MHz kusvika 1 Hz.Iyo ion conductivity (σi) yakatemerwa kubva kune yakakwira-frequency intercept neiyo chaiyo axis muNyquist zvirongwa.Mushure mekuyerwa kweconductivity, iyo nano-SCE pellet yakabvumidzwa kuti iwedzere kuoma mubhokisi regirovhosi.Kuyera kutsamira kwetembiricha, iyo SS/SCE/SS stacks yakavharirwa musero remari.Mushure mekuisa chisimbiso, conductivity yakaramba isingagumi kwemazuva akawanda (ona fig. S3).Kupisa kwesero remari kunodzorwa nebhachi rinopisa rine bhati rinopisa rinoshandiswa neH2O/ethylene glycol sekushanda kwepakati.Masero acho akatanga atonhodzwa kusvika pa -15°C ndokuzopisa zvine hungwaru kusvika pa60°C.

Kubva pane yega nano-SCE pellet, ingangoita 23 μl yakaunzwa mumhete (4.34-mm yemukati dhayamita uye 1.57-mm kureba) yemagetsi zviyero zvakananga mukati meN2-yakazadzwa girovhosi bhokisi rine hunyoro hunodzorwa.Mhete ine SCE yakabva yaiswa sandwich pakati pemadhisiki maviri eSS (0.2 mm gobvu; MTI).Zviyero zvekudzivirira zvakaitwa pachishandiswa PGSTAT302 (Metrohm) ine AC amplitude ye5 mV uye frequency inotangira pa1 MHz kusvika 1 Hz inodzorwa kuburikidza neNova software.Iwo masampuli akachengetwa pane yega yega RH% kukosha kwemaawa makumi mana nemasere kusati kwaitwa conductivity ichitariswa kusvika kudzikamiswa.Iyo yakagadzikana ionic conductivity yeyakapihwa RH% kukosha (σi) yakatemerwa kubva kune yakakwirira-frequency kubatwa neiyo axis chaiyo muNyquist plots.

Iyo morphology yepellet ine uye isina Li[BMP][TFSI] ILE yakaongororwa neSEM ichishandisa Thermo Fisher Scientific Apreo chishandiso pa1.5 kusvika 2.0 kV iyo ichishanda mune mbiri-detector imaging mode uchishandisa T1 uye T2 detector yakafanana rarama-chifananidzo chekugadzirisa, uye T2 detector yakashandiswa kunyora mifananidzo yakaratidzwa SEM;sampuli yakagadziriswa pa carbon conductive tape.TEM yakaitwa pachishandiswa Tecnai inoshanda pa300 kV.

Iyo ILE yakabviswa paSCE pellet nenzira mbiri dzakasiyana.Imwe sarudzo yekuwana iyo porous silica yakaitwa nekunyudza iyo SCE muacetone kwemaawa gumi nemaviri kubvisa Li[BMP][TFSI] ILE.Kusuka uku kwakadzokororwa katatu.Imwe sarudzo yaive yekunyudza iyo SCE mu ethanol.Muchiitiko ichi, ethanol yakabviswa nekushandisa mvura CO2 yakakosha point dryer.

Zvishandiso zviviri zvakasiyana zvakashandiswa pakuomeswa kwepamusoro-soro, zvinoti, Automegasamdri-916B, Tousimis (nzira 1) uye chishandiso-chakagadzirwa neJASCO Corporation (nzira 2).Pakushandisa chishandiso chekutanga, kutevedzana kwekuomesa kwakatanga nekudzikira kwekushisa kusvika ku8 ° C.Zvadaro, CO2 yakacheneswa kuburikidza nekamuri, ichiwedzera kumanikidza kusvika ku5.5 MPa.Muchikamu chinotevera, CO2 yakapisa kusvika ku41 ° C, ichiwedzera kudzvinyirira ku10 MPa, uye yakachengetwa yakadaro kwemaminitsi mashanu.Kupedzisa, mudanho rekubuda ropa, kumanikidzwa kwakaderedzwa pane imwe nguva ye10 min.Paunenge uchishandisa chigadziro chakavakwa, kutevedzana kwakafanana kwakateverwa.Zvisinei, nguva uye kumanikidzwa kwakasiyana zvikuru.Mushure mekuchenesa danho, kumanikidzwa kwakawedzerwa kusvika 12 MPa pakupisa kwe70 ° C uye yakaramba yakadaro kwemaawa mashanu kusvika ku6.Zvadaro, kudzvinyirira kwakaderedzwa muzvikamu kubva ku12 kusvika ku7 MPa, 7 kusvika ku3 MPa, uye 3 kusvika 0 MPa nekufamba kwenguva kwe10, 60, uye 10 min, maererano.

Nitrogen physisorption isotherms yakayerwa paT = 77 K uchishandisa Micromeritics 3Flex surface characterization analyzer.Iyo yakawanikwa porous silica yakabva yabuda kunze kwemaawa masere pa100 ° C pasi pe 0.1-mbar vacuum.Iyo porous silica inotorwa kubva mukuomeswa kwakanyanya yakaburitswa kwemaawa gumi nemasere pa120 ° C pasi pe 0.1-mbar vacuum.Pashure pacho, nitrogen physisorption isotherms yakayerwa paT = 77 K uchishandisa Micromeritics TriStar 3000 automated gas adsorption analyzer.

PFG-NMR kuyerwa kwakaitwa pachishandiswa JEOL JNM-ECX400.Iyo yakasimudzirwa echo pulse sequence yakashandiswa pachiyero chekupararira.Iyo yakajairika echo sign attenuation, E, inotsanangurwa muequation (38)E=exp(−γ2g2δ2D(Δ−δ/3)) (1) apo g ndiro simba rekupuruzira kwegradient, δ ndiyo nguva yegiradhenti. pulse, ∆ ndiyo nguva iri pakati pemicheto inotungamira ye gradient pulses, γ ndiyo reshiyo yemagnetogyric, uye D ndiyo yekuzviparadzanisa-siyana coefficient yemamorekuru.Iwo ega ega-diffusion coefficients akafungidzirwa nekukodzera echo masaini akawanikwa nekuchinja ∆ neEq.1. 7Li yakasarudzwa kuti ione kupararira kwekofi ye lithium ion.Zvose zviyero zvakaitwa pa30 ° C.

Iyo Raman spectroscopy setup yaive yakavakirwa kumba system ichishandisa argon ion inokwanisa kutariswa kune 458-nm laser excitation mwenje iyo yakasanganiswa kuita inverted Olympus IX71 microscope, uye mwenje wakapararira kumashure wakapfuudzwa kuburikidza neTriVista katatu spectrometer setup (Princeton Instruments). )Tichifunga nezve yakakwira optical absorbance paaya wavelengths, mashoma laser masimba akashandiswa kudzivirira kupisa kwelaser (<100 W · cm−2).

DFT yepasi-nyika geometry optimization uye analytical frequency kuverenga yakashandisa yakakurumbira B3LYP hybrid inoshanda uye 6-311++G** base base, ine Grimme's atomu-pairwise dispersion correction (39) neBecke-Johnson damping scheme (D3BJ), se yakaitwa muORCA 3.0.3 (40).Raman spectra yakaitwa ichishandisa ORCA, uye kuoneswa kwemamorekuru zvivakwa kwakawanikwa uchishandisa Avogadro software package (41) ine ORCA-inotsigirwa update.

Zvose zviyero zve electrochemical uye gadziriro yemuenzaniso yakabatana yakaitwa mubhokisi regirovhosi rakazadzwa neargon (PureLab, PL-HE-4GB-1800; <1-ppm O2 uye H2O mazinga) akatsaurirwa maitiro e electrochemical.Iyo SCE pellet yakaiswa paLi ribhoni (Sigma-Aldrich; 99.9%) yakatsigirwa pandiro yemhangura se counter electrode uye maviri akaboorwa kunze Li disks (5-mm dhayamita) akaiswa pamusoro pe SCE pellet kuti itariswe uye kushanda. electrodes.Iyo setup inoratidzwa mufig.S7.Pini dzegoridhe dzakashandiswa kubata iyo lithium referensi uye maelectrodes anoshanda.Cyclic voltammetry uye impedance zviyero zvakaitwa uchishandisa PGSTAT302 (Metrohm) inodzorwa kuburikidza neNova software.Cyclic voltammetry yakaitwa ine scan rate ye20 mV/s.Impedance zviyero zvakaitwa neAC amplitude ye5 mV uye frequency inotangira pa1 MHz kusvika 0.1 Hz.

Iyo 40-nm anatase TiO2 yakaonda-firimu electrode yakaiswa neatomic layer deposition (ALD) pa300-mm silicon wafer ine 40-nm TiN underlayer zvakare yakaiswa neALD.Iyo yakanakisa test electrode yekuratidzira kweLi-ion conductivity kuburikidza ne electrolytes, sezvo TiO2 isingatambudzi nemakemikari degradation kana mechanical stress (hapana yakakosha vhoriyamu shanduko) panguva yebhasikoro.Kuyera Li/SCE/TiO2 sero, iyo ILE-SCEs yakazadzwa mumhete yePTFE ine dhayamita ye4.3 mm uye ukuru hwe 0.15 cm;ipapo, mhete yakaiswa pakati peLi foil neTiO2 firimu.

Nano-SCE/thin-film electrode half stacks, ine LMO electrode, yakagadzirwa nekugadzira nano-SCE firimu pamagetsi.Zvose zve 150 μl ye x = 1.5 mhinduro, yakakwegura kwemazuva maviri, yakadonhedzwa-yakakandwa mumhete yegirazi (diameter, 1.3 mm) yakaiswa pamafirimu e electrolyte.Mhete yacho yakabva yavharwa neparafilm, uye mhinduro yacho yaichengetwa mumudziyo wakavharwa wakadaro kuti uise gel kwemazuva mana.Iyo yakaumbwa gel/electrode stack yakadaro yakaomeswa kuita nano-SCE/electrode stacks.Ukobvu hwenano-SCE, hwakatemerwa kushandisa micrometer, hwaive 300 μm.Pakupedzisira, lithium foil (1.75 mm gobvu, 99.9%; Sigma-Aldrich) yakatsikirirwa pane nano-SCE/electrode stack seanode.Iyo 100-nm LiMn2O4 (LMO) yakatetepa-firimu electrode yakaiswa neredhiyo frequency sputtering pasi peAr flow pasilicon wafer yakavharwa ne80-nm Pt (DC sputtering)/10-nm TiN (ALD) underlayers.Iyi stack yakavharirwa kwemaminetsi makumi maviri pa800 ° C mumhepo yeokisijeni.

LiFePO4 (LFP) electrode mafirimu akagadzirwa neblade coating.Chekutanga, kabhoni dema uye LFP (2 kusvika 3 μm) yakawedzerwa kune aqueous solution ine carboxymethylcellulose (CMC) kuita musanganiswa wakazoitwa homogenized uchishandisa musanganiswa wepuraneti.Zvadaro, chigadzirwa chehomogenized chakasanganiswa nemvura yakasvibiswa uye fluorinated acrylic latex (JSR, TRD202A) mune vacuum mixer kuti iite slurry ye electrode coating.Iyo slurry yakagadzirwa yakakandwa paaluminium foil kuti iise maelectrode mafirimu uchishandisa blade coater.Aya ma-electrode akanyorova akaputirwa akaiswa muhovhoni yemuchadenga ine mhepo yakadzikama pa70 ° C kwemaminetsi gumi uye akaomeswazve pa140 ° C kwemaawa mana muovheni yevacuum.Mafirimu e electrode akaomeswa aisanganisira 91 wt % LiFePO4, 3 wt % carbon black, 2 wt % CMC, uye 4 wt % TRD202A.Ukobvu hwefirimu i30 μm (yakatemerwa uchishandisa micrometer uye scanning electron maikorosikopu).

Li4Ti5O12 (LTO) mafirimu emagetsi emagetsi akagadzirwa pamapuranga emhangura nenzira imwecheteyo.Kuumbwa kwema electrode akaomeswa ndeye 85 wt % Li4Ti5O12, 5 wt % kabhoni dema, 5 wt % CMC, uye 5 wt % fluorinated acrylic latex (TRD2001A).Ukobvu hwefirimu ndeye 40 μm.

Mhinduro yeSCE yakadonhedzwa-yakakandwa pane particle-based LFP uye LTO electrode film.Chekutanga, 100 μl ye x = 1.5 mhinduro, yakwegura kwemazuva maviri, yakadonhedzwa-yakandwa pafirimu re electrode, rine dhayamita ye15 mm, yakaiswa musero remari (#2032, MTI).Mushure mokunge SCE yakasvibiswa yakasvibiswa, firimu yakaomeswa pa25 ° C kwemaawa 72 muvheni yevhavha (<5 × 10-2 mbar) kuita nano-SCE uye electrode stack.Ukobvu hwenano-SCE hwaive 380 μm.Pakupedzisira, lithium foil yakatsikirirwa paSCE/electrode stacks seanode, uye sero remari rakavharwa.Izvo zviyero zve electrochemical zvakaitwa uchishandisa Solartron 1470E potentiostat patembiricha yekamuri.

Zvekuwedzera zvechinyorwa chino zvinowanikwa pa http://advances.sciencemag.org/cgi/content/full/6/2/eaav3400/DC1

Tafura S1.Zvimiro zvesilica matrix mu nano-SCE yekuwedzera molar chikamu cheionic mvura kune silica (x kukosha) yakatemwa kubva kuN2 adsorption/desorption kana BET zviyero uye TEM kuongorora.

Ichi chinyorwa chakavhurika chinogoverwa pasi pemitemo yeCreative Commons Attribution-NonCommercial rezinesi, iyo inobvumidza kushandiswa, kugovera, uye kubereka mune chero svikiro, chero mhedzisiro kushandiswa kusiri kwekutengesa bhizimusi uye kana basa rekutanga rakakodzera. quoted.

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NaXubin 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 Mées.

Nguva yekutumira: Jul-15-2020