Silica gel siri ike nanocomposite electrolytes nwere nkwado ihu igwe na-aga nke ọma karịa nnukwu Li-ion conductivity nke ionic mmiri mmiri electrolyte filler

Ntughari na batrị Li-ion siri ike ga-eme ka ọganihu ruo njupụta ike nke 1000 W·hour / lita na karịa.Achọpụtala ihe mejupụtara matriks mesoporous oxide nke jupụtara na ihe ndị na-adịghị agbanwe agbanwe ionic mmiri mmiri electrolyte dị ka nhọrọ electrolyte siri ike.Agbanyeghị, njide dị mfe nke ngwọta electrolyte n'ime pores nwere nha nanometer na-eduga na nrụpụta ion dị ala ka viscosity na-abawanye.N'ebe a, anyị na-egosi na Li-ion conductivity nke nanocomposites mejupụtara mesoporous silica monolith na ionic mmiri mmiri electrolyte filler nwere ike ịbụ ọtụtụ ugboro elu karịa nke dị ọcha ionic mmiri mmiri electrolyte site na ntinye nke interfacial ice oyi akwa.Mgbasa ozi siri ike na ịtụ nke ụmụ irighiri mmiri ionic na-eme ka ha ghara ịdị na-ebugharị ma sie ike-dị ka oyi akwa ice n'onwe ya.dipole n'elu adsorbate mesophase oyi akwa na-ebute ngwọta nke ions Li+ maka nkwalite nkwalite.Enwere ike itinye ụkpụrụ ion gosipụtara n'usoro ion dị iche iche.

A na-atụ anya na electrolytes steeti siri ike na-enye nkwalite ọzọ maka batrị Li-ion ka ọ gafere ụlọ bara uru nke 800 W·hour/liter ma ọ bụ 300 W·hour/kg etinyere na cathode na kemịkalụ anode dị ugbu a.Mmụba a na-atụ anya na njupụta ike maka batrị steeti siri ike na-abịa site n'ọtụtụ onyinye, ha niile na-ezubere ịbawanye pasentị olu nke ihe nọ n'ime cell.Nke kachasị mgbasa ozi bụ iwebata igwe lithium iji dochie graphite na graphite/silicon dị ka anode.Igwe lithium dị ọcha nwere njupụta ume kachasị elu enwere ike, yabụ ọ ga-achọ ohere kacha nta.Otú ọ dị, a ka kwesịrị idozi ọtụtụ okwu, dị ka mmeghachi omume na-apụghị ịgbagha agbagha (ma si otú a na-eri) nke lithium metal, nguzobe dendrite, mmụba nke njupụta dị irè ugbu a maka planar lithium foils tụnyere porous graphite (silicon) electrodes, na, ikpeazụ. ma ọ dịghị ihe ọzọ, "mpụpụ" nke lithium n'oge mwepu (deplating) na otú ọnwụ nke kọntaktị na siri ike electrolyte.Ọdịdị nke siri ike nke seramiiki siri ike electrolytes enweghị nrubeisi efu, na ọ dị mkpa itinye nrụgide dị ukwuu iji pịa lithium ahụ nke ọma megide akụkụ electrolyte siri ike.Ihe nrụgide dị iche iche na-ebelata ebe elu dị irè ọbụna karị, na-eduga n'ichepụta dendrite mpaghara na nkwụnye ego spongy.Polymer electrolytes na-ekwenyekarị n'ụzọ igwe mana ha egosipụtabeghị ịdị elu nke ionic conductivity na ụlọ okpomọkụ.Ihe ọhụrụ na-adọrọ mmasị na nke a bụ silica gel electrolytes, nke a na-akpọkwa ya dị ka "ionogels," ebe a na-ejikọta ionic liquid electrolyte (ILE) na matrix silica nanoporous (1).Ihe dị oke elu nke silica matrix (70 ruo 90%) na-enye ihe ndị a nanocomposite electrolyte ihe nkwekọ dị ka gel ma si otú a na-eme ka ha kwekọọ n'ụzọ usoro dịka polymer electrolytes.A na-egosi gels silica ndị a mgbe ụfọdụ dị ka ngwakọ siri ike electrolytes, ebe ha nwere mmiri mmiri.Otú ọ dị, maka silica nanocomposites, dị ka ndị a kọwara n'akwụkwọ a, ionic "mmiri mmiri" electrolyte na-aghọ ihe siri ike-dị ka mgbe ejiri ya n'ime iri iri nke nanometer ọwa ma site na mmụba nke viscosity na site na mgbasa ozi na mgbidi silica na-emechi emechi. ọwa.Ọ bụrụ na matriks silica ga-eme naanị dị ka onye na-ekesa porous, mgbe ahụ mmụba nke viscosity maka electrolyte mmiri na-ekpochi ga-eduga na mbelata nke ionic conductivity.Kama, mmekọrịta dị n'etiti ụmụ irighiri ihe ILE na mgbidi silica pore na-eme ka njirimara nke nanocomposite dị iche na nchikota nke ihe mejupụtara ya.Mgbakwunye nke mmiri mmiri ionic na oxides na nguzobe nke mesophase siri ike ruo nanometer ole na ole n'ogo ka egosiri n'elu mbara ala nke nwere microscopy atomiki (2).Nhọrọ nhọrọ nke ion mmiri mmiri ionic na cations n'elu oxide nwere ike iduga nkwalite Li+ n'akụkụ ndị a.N'ezie, nkwalite ahụ dị n'akụkụ oghere oxide ga-akwụ ụgwọ ma ọ bụ ọbụna gafere ngbanwe arụmọrụ site na ILE nke dị na isi nke pores.N'ihi ya, a na-achọ obere oghere na oke elu-na-olu.Ka ọ dị ugbu a, ionogels nwere ion conductivities na-abịaru nso nke ILE n'onwe ya ka egosipụtara site na njikarịcha nke usoro mesoporous (3).Nke a pụtara na nkwalite interface adịlarị mana ọ bụghị ruo n'ókè nke nrụtụ aka dị ukwuu.

Nkwadebe nke ionogels na-amalite site na ngwakọta mmiri na-ejikọta ọnụ, nke a na-agbakwunye ILE na ngwọta sol-gel precursor maka njikọ nke matrix oxide (4, 5).Na usoro a, ILE na matrix na-etolite ihe mejupụtara n'ụzọ "n'ọnọdụ": Ndị na-ebute ụzọ na ngwọta na-emeghachi omume iji mepụta matrix oxide gburugburu template mmiri mmiri ionic, na-ekpuchi ya na usoro ahụ.N'okpuru ọnọdụ njikọ ụfọdụ, ILE-SCE a kwadebere (mkpụrụkpụ electrolyte siri ike) nwere ike ịbụ n'ụdị monolith nke ILE na-etinye na netwọk mesoporous inorganic oxide na-aga n'ihu.Ka ọ dị ugbu a, ọtụtụ ILE-SCE nke silica akwadoro n'ụzọ dị otú a, ọ bụ ezie na e mekwara ihe atụ na alumina (6), titania (7), na ọbụna tin oxide (8).Ọtụtụ usoro sol-gel kọrọ nwere ILE, alkyl-silicate dị ka tetraethyl orthosilicate (TEOS) dị ka silica precursor, yana formic acid dị ka reagent na ihe mgbaze (9, 10).Dị ka usoro a tụrụ aro (11) maka usoro sol-gel a, a na-emepụta silica karịsịa site na mmeghachi omume dị n'etiti TEOS na formic acid, ọ bụ ezie na a na-emepụta mmiri n'oge usoro sol-gel.E wezụga ngwakọta nke "nonaqueous" ndị a nke formic acid, aqueous sol-gel formulations na HCl dị ka ihe na-akpali akpali na H2O dị ka reagent (gbakwunyere organic mgbaze) a kọwakwara, Otú ọ dị, na nke a kpọmkwem maka njikọ nke silica mejupụtara ya. Mmiri ionic naanị (12-15).

Dịka, ionogels na-egosi conductivity ion dị ala karịa nke ntụnyere ILE.Ọgbọ mbụ nke ionogels nwere njikwa okpomọkụ nke ime ụlọ na-abụkarị naanị ihe dị ka 30 ruo 50% nke nnukwu uru ILE, n'agbanyeghị ihe atụ ụfọdụ ruru 80% ka akọpụtala (9, 10, 16, 17).Mmetụta nke ọdịnaya ILE na nsonaazụ pore morphology na ionogel conductivity enyochalarị nke ọma (3);Otú ọ dị, ọ dịghị usoro ọmụmụ nke interface nkwalite mmetụta mara.Wu et al.(18) kọrọ n'oge na-adịbeghị anya banyere ionogel arụ ọrụ na ọnọdụ, nke nyekwara nkwalite conductivity ma e jiri ya tụnyere nnukwu ILE.Ekwuru na nkwalite ahụ sitere na mmekọrịta dị n'etiti anion na otu 3-glycidyloxypropyl na-arụ ọrụ n'elu silica.Nchọpụta a na-akwado echiche na ịrụ ọrụ elu nwere ike ịkwalite nkwalite njikwa interface.

N'ime ọrụ a, anyị na-egosipụta n'ọnọdụ nke nhazi mmiri oyi siri ike na silica na nkọwa zuru ezu usoro nke interfacial Li-ion conduction site na mmụba dipole mmekọrịta n'etiti elu ice arụ ọrụ oyi akwa na adsorbed ionic mmiri mmiri mesophase oyi akwa.Site na nchikota nke elu esịtidem elu na ok ice arụ ọrụ oyi akwa, siri ike nanocomposite electrolytes (nano-SCE) na 200% elu Li-ion conductivity karịa nnukwu ILE ntụaka nwetara.E gosiputara matriks silica nwere ezigbo usoro mesoporous monolithic nwere oke pore na mpaghara elu ruo 90% na 1400 m2/g, si otú a na-enye oke oke elu na oke olu na-enye ohere buru ibu nke nkwalite mmegharị n'akụkụ ndị a.Site na ịrụ ọrụ nke ọma nke elu silica jikọtara yana ịba ụba nke elu-to-olu, nano-SCE na ion conductivities nke karịrị 10 mS/cm nwere ike ịmezi ya ma si otú a mara mma nke ukwuu maka batrị ndị nwere nnukwu ike maka ngwa ụgbọ ala.

Ihe lekwasịrị anya n'akwụkwọ anyị bụ na usoro mmeghari ihu igwe na-abawanye site na imepụta oyi akwa mesophase nwere ihe akaebe sitere na Raman, Fourier transform infrared (FTIR), na resonance magnetik (NMR) spectroscopy.A na-egosipụta nkwụsi ike interface nke ihe nano-SCE anyị na voltaji dị elu site na iji electrodes lithium manganese oxide (LMO) dị obere.N'ụzọ dị otú a, na-elekwasị anya na-ekwusi ike na ihe onwunwe kama na electrode mwekota na cell mgbakọ okwu.N'otu aka ahụ, windo electrochemical na nkwụsi ike megide foils metal lithium bụ nke zuru oke.A na-egosipụta ọrụ na ntinye nke nano-SCE anyị site na mgbakọ na ule arụmọrụ nke lithium iron phosphate (LFP) na sel lithium titanate (LTO).E gosipụtara nkwụsi ike nke electrolyte anyị na enweghị ọrụ electrochemical nke mmiri ice site na ịgba ígwè ogologo oge nke mkpụrụ ndụ Li-SCE-Li symmetrical.Ịkwalite njupụta ume ike, arụmọrụ ọnụego, na ịrụ ọrụ ịgba ígwè nke sel agbakọtara n'ụzọ zuru ezu ga-abụ ihe na-elekwasị anya na akwụkwọ ndị na-esote (19, 20).

Nkwalite ion conductivity nke ihu na sistemu ihe mejupụtara akụkụ abụọ amarala ihe fọrọ nke nta ka ọ bụrụ afọ 90 (21).Dịka ọmụmaatụ, ihe ruru iwu anọ nke mmụba na ionic conductivity ka egosiri maka ngwakọta nke nnu lithium dị mfe dị ka lithium iodide nwere ihe mesoporous oxide dị ka silica ma ọ bụ alumina ma e jiri ya tụnyere ion conductivity nke lithium salt electrolyte dị ọcha (22).Ion ndị dị na SCE ndị a nwere ike ịgbasa ngwa ngwa n'akụkụ Li ion-mebichara (ma ọ bụ ohere-ọgaranya) okpukpu abụọ eletrọnịkị kpụrụ na oxide/electrolyte interface.N'ụzọ dị mwute, ion conductivity enwetara n'ime ihe ndị a dị mfe akụkụ abụọ mejupụtara inorganic siri ike siri ike (1) agafebeghị 1-mS/cm2 ọnụ ụzọ achọrọ iji mechie anya narị ole na ole-micrometer n'etiti efere ndị na-anakọta ugbu a na batrị Li-ion. .Achọpụtakwara echiche nke doping dị iche iche na matrix oxide iji injinia ihe omume ionic maka polymer electrolytes (23) na ILEs (24), bụ ndị nwere ihe nrụpụta ion dị elu dị elu iji malite.Na mgbakwunye, kemịkalụ molekul (stereo) bara ụba nke akụkụ nke atọ na-emepe usoro ntụgharị ion ndị ọzọ, dịka ụmụ irighiri ihe mgbaze (di) polar nwere ike itinye aka na nhazi nke okpukpu abụọ eletrik.Ọ bụ ezie na ihe ngwọta nke otu ether dị na polyethylene oxide polymer electrolytes na-enye ihe omume ion siri ike nke ~ 10-6 S / cm maka LiClO4 ruo ~ 10-5 S / cm maka LiN (SO2CF3) 2, ihe mejupụtara ha na silica, alumina. , ma ọ bụ titania nanoparticles nwere ike n'ezie na-enye ihe karịrị 10-fold nkwalite na tụrụ ion conductivity (25), dị mwute ikwu, ka ọma n'okpuru ụlọ okpomọkụ ọnụ ụzọ nke 1 mS / cm.Ngwọta ILE bụ ngwakọta nke Li-salt solute na ihe mgbaze mmiri ionic, nke nwere ike nweelarị ụkpụrụ ionic dị elu n'etiti 0.1 na 10 mS / cm (26, 27).Emeela ọtụtụ mbọ iji kwalite conductivity ion site na ịgwakọta ma ọ bụ gelling ya na oxide nanoparticles ma ọ bụ ijichi ILE na microparticles mesoporous (9, 16, 28, 29).Otú ọ dị, ka ọ dị ugbu a, a hụbeghị nkwalite nke ion conductivity maka akụkụ atọ nke Li-salt / ionic liquid / oxide composites (fig. S1).Ọ bụ ezie na iji microparticles silica mesoporous mesoporous na-eme ka nrụpụta dị elu dị elu ma e jiri ya tụnyere ihe mgbagwoju anya nwere nanoparticles siri ike, ebe etiti ihu ihu na nkwalite ion ion ezughị oke iji gafere nnukwu ILE conductivity.

Mesoporous silica bụ ihe a ma ama nke ejiri na catalysis.A na-emekarị ya site na hydrothermal ma ọ bụ sol-gel njikọ dị mfe.Usoro hydrothermal na-edugakarị na ntụ ntụ mesoporous, mana site na iji nlezianya na-achịkwa usoro sol-gel nke ime ụlọ, a na-emepụtakwa nnukwu iko monoliths ma ọ bụ aerogels.A na-emepụta matrix silica site na hydrolysis na mmeghachi omume condensation nke tetra-alkyl orthosilicates (30).Isi ihe na-achịkwa ihe owuwu pore bụ iji ndebiri, dịka ọmụmaatụ, ụdị micelle nke surfactant, nke na-etolite matrix silica gburugburu.Mgbe agbakwunyere mmiri mmiri ionic dị ka ihe nlegharị anya, matriks silica hydrated na-emekọrịta ihe na mmiri mmiri ionic, na-akpụ gel, na mgbe ọ gwọchara na ihicha, mmiri mmiri ionic na-ejide n'ime matrix silica nanoporous siri ike (13).Mgbe agbakwunyere nnu lithium dị ka akụkụ nke atọ, ILE nke etinyere na matrix silica na-etolite silica gel electrolyte, nke akpọkwara ya dị ka ionogel (24).Otú ọ dị, ka ọ dị ugbu a, silica gel electrolytes na-egosi omume na-abịaru nso nke nnukwu ILE ma ọ bụghị karịa ya, ma e wezụga otu ikpe ebe silica na-arụ ọrụ nke ọma (lee Okwu Mmalite) (18).

N'ebe a, anyị na-egosi, nkwalite nhazi nke Li-ion conductivity nke nanocomposite nke ọma karịa nke ILE dị ọcha.A na-eji ihe atụ nke 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide (BMP-TFSI) mee ihe ebe a.A na-ekwupụta na mgbasa nke molecules mmiri mmiri ionic na elu silica kwụsịrị OH na-akwalite site na ọnụnọ nke oyi akwa mmiri ice interfacial.Njikọ hydrogen siri ike n'etiti mmiri ice na TFSI- anion na-ebute nhazi mkpụrụ ndụ nke mmiri ionic, dị ka ngalaba enyere iwu nke na-etolite na mberede na mmiri ionic (31).Isi ihe dị iche na ngalaba ndị a na-ahazi na-enweghị usoro na nnukwu ILE bụ na oyi akwa ice na-arụ ọrụ dị ka oyi akwa na-arụ ọrụ nke (i) na-eme ka usoro mkpụrụ ndụ dị n'elu oxide na (ii) na-ewebata H-bonding siri ike iji mee ka dipoles hapụ Li + n'efu. maka nkwalite conduction.Na-esote na-abawanye na free Li + ịta, anyị ga-egosi na ebighị ike maka mgbasa bụ ala tinyere ihe mejupụtara interface na adsorbed ILE oyi akwa na ice mmiri oyi akwa.

Igwe mmiri dị n'elu mmiri ole na ole monolayers na silica bụ oyi akwa siri ike, ebe ọ na-ejikọta ya na silanol dị iche iche site na H-bridges na ya mere a na-akpọkwa ya dị ka oyi akwa (32).Njupụta ya na ọkpụrụkpụ ya (nke a na-eme atụmatụ ruo atọ na anọ monolayers, na ~ 0.25 nm kwa ice monolayer) dị na thermodynamic equilibrium na akụkụ nke mmiri nrụgide (RH) na gburugburu ebe obibi (fig. S2).Anyị na-egosi na ion conductivity na-abawanye na ọkpụrụkpụ nke oyi akwa mmiri ice ka hydrogen bonding na adsorbed ionic n'ígwé na-abawanye.Igwe mmiri ice kwụsiri ike ka mmiri kristal dị na ogige kemịkal.Nke a dị nnọọ iche na super concentrated aqueous electrolytes ma ọ bụ ihe a na-akpọ mmiri na ngwakọta nnu, ebe windo electrochemical na-agbasawanye nke ukwuu mana, n'ikpeazụ, mmiri ahụ ka na-arụ ọrụ nke ọma (33).

Dị iche na ụdị formic acid-catalyzed ionogel Ezi ntụziaka, anyị na-eji a nwayọọ pH 5 ngwakọta na nnukwu ngafe nke mmiri na PGME (1-methoxy-2-propanol) tinye na TEOS precursor na Li-TFSI nnu na BMP-TFSI ionic mmiri mmiri.Na pH a, mmeghachi omume hydrolysis na-adị ngwa, ebe condensation dị mma (30).The Li ion na-kweere na-eme ihe dị ka ihe na-akpali maka hydrolysis mmeghachi omume, dị ka ọ dịghị gelation mere na-anọghị nke lithium nnu mgbe ha abụọ nwere otu pH nke 5. The molar ratio nke ionic mmiri mmiri na TEOS (na silica moieties) bụ. gosiri dị ka x uru ma dị iche n'etiti 0.25 na 2. Oke molar ruru nke BMP-TFSI na Li-TFSI ka edobere na 3 (dakọtara na 1 M Li-ion ngwọta).ihicha ngwa ngwa dị mkpa iji nọgide na-eguzosi ike n'ezi ihe nke usoro monolith (lee Ngwa na Ụzọ).Ọgụgụ 1A na-egosi foto nke pellet monolithic enwetara mgbe ihichachara agụụ.Nhicha oghere nke awa 72 zuru ezu iji wepụ mmiri niile ruo n'ókè ebe ewepụrụ mmiri niile na-efu ebe oyi akwa mmiri ice na-adaba na-adịgide adịgide, dịka FTIR kwadoro.Ọ dịghị vibrations maka free mmiri ahụrụ na 1635 cm-1 na nke ọ bụla n'ime sample mgbe agụụ ihicha nzọụkwụ (Fig. 2).Maka ntụnyere, FTIR ụdịdị dị iche iche maka ihe nlele nano-SCE (x = 1.5) echekwara maka izu 1 n'ime igbe mkpuchi N2 na 60% RH.N'okwu a, oke mmiri na-enweghị ihe ọ bụla na-apụta.Nlele niile, n'aka nke ọzọ, gosipụtara akara ngosi doro anya maka ịrụ ọrụ elu silanol (Si─OH na-ehulata n'etiti 950 na 980 cm-1) na oyi akwa mmiri ice adsorbed (O─H na-agbatị na ~ 3540 cm-1) jikọtara ya na ndị ─OH elu site na H-bonding (nkọwa ndị ọzọ n'okpuru).A na-atụba vial ndị ahụ tupu na mgbe usoro ihicha ahụ gasịrị iji tụọ mmiri ahụ edobere na nano-SCE (tebulu S1).Mgbe e mesịrị, anyị ga-agbakọọ ọnụ ọgụgụ nke monolayers kwekọrọ ekwekọ nke oyi akwa n'elu-agbụ mmiri n'elu site na ngafe ibu.A na-ebuba pellets ndị a mịrị amị n'ime igbe aka [<0.1-ppm (akụkụ kwa nde) H2O] ma chekwaa ya na vials mechiri emechi iji nọgide na-enwe ọdịnaya mmiri mbụ.E wepụrụ obere olu site na pellet maka njirimara ọzọ.

(A) Foto nke pellet abụọ nano-SCE (aka ekpe) arụpụtara na vial;mgbe gelation gasịrị, a na-enweta pellet transperent.Rịba ama na pellet ahụ na-apụta ìhè nke ọma, ya mere e nyere ya agba anụnụ anụnụ maka visibiliti.Mgbe ewepụrụ ILE, pellet na-acha ọcha na-agbaji agbaji na-anọgide maka matriks silica nke nwere porous (n'aka nri).(B) Nyochaa ihe onyonyo eletrọnịkị (SEM) nke matrix SiO2 nke na-adịgide mgbe ewepụrụ ILE.(C) Mbugharị nke foto egosiri na (B) na-egosi ọdịdị mesoporous nke ihe matriks nwere ụfọdụ macropores.(D) Onyonyo microscopy eletrọn na-ebufe (TEM) na-egosi ngwungwu dị ukwuu nke 7- ruo 10-nm silica nanoparticles dị ka ihe mgbochi ụlọ nke matrix porous.(E) Ogo nke ihe owuwu matriks echere maka oke molar dị iche iche nke ILE gbasara SiO2 (x uru).Ahịrị a kwụsịrị na-enye porosity nke a na-ekpebi site na nha nha nke ILE na silica.Akpọkọrọ ihe nlele acetone (square ojii) akpọnwụwo n'ikuku, nke na-enye ọdịda akụkụ akụkụ nke ihe owuwu maka x> 0.5.CO2 dị oke egwu ihicha nke ethanol-rinsed nano-SCE (okirikiri akwụkwọ ndụ akwụkwọ ndụ) na-egbochi ịdaba ruo x = 2 maka iwepụ ngwa ngwa nke CO2 (oghere oghe).BET, Brunauer-Emmett-Teller.Ebe e si nweta foto: Fred Loosen, imec;Akihiko Sagara, Panasonic.

(A) IR ụdịdị nke nano-SCE dị ka akpọnwụwo na agụụ (ojii) na emesia ọzọ akpọnwụwo n'ime igbe uwe na 0.0005% RH maka ụbọchị 9 (acha anụnụ anụnụ) na kpughere 30% RH maka ụbọchị 4 (red) na 60. % RH maka ụbọchị 8 (akwụkwọ ndụ akwụkwọ ndụ), n'otu n'otu.au, nkeji aka ike.(B) voltammogram nke cyclic nke ngwugwu Li/SCE/TiN nwere ụkpụrụ x nke 1.0 (acha anụnụ anụnụ), 1.5 (akwụkwọ ndụ akwụkwọ ndụ), na 2.0 (red) na nke ILE (oji);ntinye na-egosi ihe dị ugbu a na ọnụ ọgụgụ logarithmic.(C) Voltammogram cyclic nke Li/SCE (x = 2)/40-nm TiO2 tojupụtara (acha uhie uhie), ILE (nwere ntụpọ ojii), na ILE spiked nwere 5 arọ % (wt %) H2O (ahịrị na-acha anụnụ anụnụ nwere ntụpọ);na (B) na (C), nha na ILE na ILE na H2O mere na nhazi electrode atọ na TiN dị ka electrode na-arụ ọrụ na Li dị ka counter na electrodes.Akpọchara SCE maka ụbọchị 2 n'ime igbe aka mgbe ihichachara agụụ.

The ionic conductivity (σi) nke anyị agụụ-annealed nano-SCE mụbara na olu ntakiri nke ILE (x uru) dị ka urughuru composites (fig. S1).Otú ọ dị, na nke a, ionic conductivity karịrị nke dị ọcha ILE n'onwe ya karịa 200% maka x kasị elu (Fig 3).Ọzọkwa, ndabere okpomọkụ nke nano-SCE na nkwalite ion conductivity gosipụtara omume dị iche karịa nke ILE dị ọcha: Ebe Li-TFSI dị na BMP-TFSI ILE na-egosi mgbanwe doro anya na conductivity na activation ike (mkpọda) gburugburu agbaze. ebe ngwakọta na 29 Celsius C, nano-SCE na-arụ ọrụ emelitere adịghị.Kama nke ahụ, ọ na-egosi mgbanwe na-aga n'ihu na σi na okpomọkụ, na-egosi na a na-emepụta ụdị nke oge ma ọ bụ mesophase nke a na-amabughị na mbụ, bụ nke na-ahụ maka nkwalite arụmọrụ.Ọzọkwa, ndị nta mkpọda ma si otú ala ebighị ike maka mgbasa maka nano-SCE tụnyere ILE na-egosi dị iche iche ihe Njirimara (fig. S3).A na-ekwupụta na mmekọrịta siri ike n'etiti ụmụ irighiri mmiri ionic na oyi akwa siri ike na silica scaffold bụ maka omume mesophase a hụrụ, dịka a ga-atụle ya na ihe atụ a tụrụ n'okpuru.

(A) Ndabere okpomọkụ nke conductivity nke nano-SCE akpọnwụwo maka ụbọchị 8 n'ime igbe uwe (GB) nwere ụkpụrụ x nke 2 (square ojii), 1.75 (orange okirikiri), 1.5 (triangles na-acha anụnụ anụnụ), na 1.0 (triangles green). ) na nke akwụkwọ ILE (oghere mepere emepe).(B) Nrụ ọrụ nke nano-SCE gbakwunyere na GB maka ụbọchị 0 (mgbara akwụkwọ ndụ akwụkwọ ndụ), ụbọchị 10 (triangles ojii), na ụbọchị 138 (triangles na-acha anụnụ anụnụ).(C) Conductivity megide square mgbọrọgwụ nke ihicha oge nke nano-SCE na x ụkpụrụ nke 2 (oji square), 1.5 (blue triangles), 1.0 (green triangles), na 0.5 (aja aja diamonds).(D) Nrụ ọrụ nke nano-SCE nwere x = 2 (mkpọsa ojii), 1.5 (triangles na-acha anụnụ anụnụ), na 1.0 (triangles green) kpughere n'ime ụlọ iru mmiri N2 jupụtara.

Igwe ikuku argon n'ime igbe mkpuchi nwere ihe na-erughị 0.1 ppm mmiri, nke kwekọrọ na 0.0005% RH, akụkụ mmiri nke 0.01 Pa, ma ọ bụ ebe igirigi -88 ° C.Dị ka ọnụ ọgụgụ nke adsorbed mmiri n'ígwé na silanol-akwụsị silica bụ nhata na ele mmadụ anya n'ihu mgbali nke mmiri (fig. S2), elu mmiri ga-eji nwayọọ nwayọọ na-agbasa na nano-SCE na sublimate na n'ọnụ ya.Ọgụgụ 3C na-egosi mgbanwe na conductivity maka 23 μl nke nano-SCE dị ka ọrụ nke oge obibi na igbe aka.Ion conductivity na-ebelata site na ihicha ruo mgbe ọ na-ejupụta na uru kwekọrọ na elu silica na nha nha na nrụgide akụkụ mmiri nke 0.01 Pa na igbe uwe.Ọbụna n'okpuru ọnọdụ akọrọ nke igbe mkpuchi, ọ dịkarịa ala, otu akụkụ monolayer nke mmiri adsorbed na silanol dị, dị ka Raman spectroscopy ka gosipụtara mgbaàmà na 3524 cm-1, nke bụ kpọmkwem maka monolayer mbụ nke mmiri adsorbed na silanol. (Fig 4B).Nrụgharị ion n'okpuru ọnọdụ zuru oke dị n'okpuru nke ILE nke ọ bụla n'ọnọdụ niile.N'ihi ya, nkwalite ahụ ezughi oke iji kwụọ ụgwọ maka mfu na ionic conductivity nke ILE kpọchiri akpọchi na isi nke pore.

(A) ụdịdị IR nke nano-SCE nwere uru x nke 1.5 (acha ọbara ọbara), ntụaka ILE (nwa), na SiO2 (acha anụnụ anụnụ), na-egosi na otu O═S═O (1231 cm-1) na-etinye aka na mmekorita ya na otu OH n'elu silica.(B) Raman spectra nke nano-SCE na x ụkpụrụ nke 2 (ojii), 1.5 (red), na 0.5 (acha anụnụ anụnụ), na-egosi ọnụnọ nke ice mmiri bonded na silanol-akwụsị silica ọbụna maka nano-SCE nso saturation (0.0005). % RH) n'ime igbe uwe (ụbọchị 30).(C) Nlereanya echere maka mmekọrịta interface na nano-SCE na nkesa Li-TFSI n'ime Li+ efu ka TFSI- anion na-ekerịta akụkụ nke ụgwọ ọjọọ ya na oyi akwa ice-TFSI-BMP;agba na-anọchi anya ihe dị iche iche na-acha odo odo (silicon), ọbara ọbara (lithium), ọchịchịrị odo (sulfur), oroma (oxygen), blue (nitrogen), ọcha (hydrogen), na akwụkwọ ndụ akwụkwọ ndụ (fluorine).Ahịrị ahịrị na-acha odo odo na-anọchi anya njikọ hydrogen dị n'etiti otu O═S nke TFSI anion na OH-otu nke elu silica hydroxylated.Ion Li+ nke dipole tọhapụrụ n'elu oyi akwa adsorbed nwere ike ịkwaga site na ekwentị mkpanaaka na-esote ma ọ bụ gbasaa n'ígwé mmiri ionic n'elu ọkwa interface.Rịba ama na dabere na ike nke njikọ hydrogen yana ụgwọ nhata na silica, enwere ike ịmepụta ọtụtụ oyi akwa adsorbed.Egosiri nleba anya zuru oke na fig.S8.

Ihe na-akpali chọpụtara bụ linear mmekọrịta na square mgbọrọgwụ nke ihicha oge dị ka e gosiri na Fig. 3C, na-egosi na conductivity mgbanwe bụ kpọmkwem nhata na mgbanwe ego nke adsorbed ice mmiri na silica na mwepụ nke a elu mmiri bụ. Diffusion Limited.Rịba ama na "ịkpọ nkụ" na-eme naanị n'ebe mepere emepe ebe RH dị ala karịa maka oyi akwa akpụrụ akpụ.Nhazi ahụ agbanweghị ama ama, dịka ọmụmaatụ, na mkpụrụ ndụ mkpụrụ ego mechiri emechi ejiri maka nha dabere na ọnọdụ okpomọkụ.

A tụrụ ndabere okpomọkụ nke nano-SCE maka oge dị iche iche nke ihicha n'ime igbe uwe.Dị ka conductivity nke akpọnwụ nano-SCE na-eru nso na nke ILE, na-aga n'ihu σi versus 1 / T profaịlụ maka mesophase conductivity ji nwayọọ nwayọọ gbanwee na profaịlụ maka ILE, ọzọ na-ekpughe na dobe gburugburu ya agbaze ebe (fig. S3).Nlebanya a na-akwado n'echiche na oyi akwa ice na-arụ ọrụ dị ka oyi akwa na-arụ ọrụ maka mmekọrịta mmekọrịta na ILE, na-ebute omume mesophase na nano-SCE.N'ihi ya, mgbe e wepụrụ oyi akwa na-arụ ọrụ, ILE na-abụ nanị ihe ejichiri na akpụkpọ anụ mesoporous oxide.

Ntụle nke windo nkwụsi ike nke electrochemical na-egosi na mmiri ice dị na nano-SCE kwụsiri ike, n'ihi na ọ dịghị ọnụ ọgụgụ kasị elu maka mbelata mmiri ma ọ bụ oxidization na-ahụ na inert TiN electrode (Fig 2) ma ọ bụ na TiO2 thin-film electrode, nke na-eme ihe ọzọ. dị ka ihe electro-eme ka mmiri belata.Kama nke ahụ, nkwụsi ike nke electrochemical nke nano-SCE yiri nke ILE ma si otú a na-ejedebe site na oxidation nke TFSI- na ikike electrode> 4.3 V na mbelata TFSI- na BMP + na ikike <1 V vesos Li +/ Li (33).Maka ntụnyere, a na-egosi voltammogram maka ILE nwere 5 arọ % (wt%) mmiri agbakwunyere (ọdịnaya yiri nke ụfọdụ nano-SCE; lee tebụl S1).N'okwu a, a na-atụ alaka cathodic maka mbelata mmiri ozugbo na-eso Li-intercalation elu nke anatase na 1.5 V vesos Li +/Li.

Nkwụsi ike kemịkalụ ọkụ na (electro) nke nano-SCE bụ nke ILE na-ekpebi nke ukwuu.Nyocha Thermogravimetric (TGA) gosipụtara nkwụsi ike nke okpomọkụ nke SCE na ILE ruo 320 ° C, n'agbanyeghị ILE-to-silica ratio (fig. S4).N'elu okpomoku a, Li-TFSI na BMP-TFSI na-emebi kpamkpam ka ọ bụrụ ihe na-agbanwe agbanwe, naanị matriks silica na-anọgide na 450ºC.Pasent uka nke fọdụrụ mgbe ire ere okpomọkụ dabara n'ezie nke ọma na ntakiri silica dị na SCE.

Nano-SCE gosiri na ọ dịghị ihe doro anya microstructure na scanning eletrọn microscopy (SEM) ma e wezụga maka ire ụtọ elu na ụfọdụ silica patches peeking si (fig. S5).Achọpụtara njupụta nke SCE na helium pycnometer ma dị gburugburu 1.5 g/cm3 maka ụkpụrụ x niile (tebụ S1).Ekpughere matriks silica zuru ezu site na mmịpụta na-agwụ ike nke ILE na ihe mgbaze (lee Ngwa na Ụzọ).Site na iji nlezianya kpochaa n'ebe dị oke egwu nke CO2, enwere ike nweta airgel monoliths na-adịghị mma dị ka nke egosiri na Fig. 1A.Nyocha SEM na-egosi ihe nkedo nke silica mesoporous nke nwere 10- ruo 30-nm pore dayameta, nke a na-agbanye gburugburu nnukwu macropores nke 100 ruo 150 nm, dị ka a pụrụ ịhụ na Fig. 1 (B na C).Mkpebi dị elu nnyefe eletrọnịkị microscopy (TEM) (Fig 1D) gara n'ihu kpughee microstructure nke mejupụtara silica nanoparticles chiri anya.Nkezi urughuru dayameta sitere na 7 ruo 14 nm maka ụkpụrụ x n'etiti 0.5 na 1.5.

Ebe a kapịrị ọnụ nke dị n'elu [Brunauer-Emmett-Teller (BET)], porosity, nkezi pore size, na nkesa pore ka ejiri N2 adsorption / desorption nha (tebụ S1 na fig. S6).Ndakpọ akụkụ nke ihe owuwu yana iwepụ ILE adsorbed ezughị ezu nwere ike ịkọwapụta ọnụọgụgụ ahụ.Mwepụta nke ọma nke mmiri mmiri ionic na ihicha ngwa ngwa site na iji CO2 supercritical nyere, agbanyeghị, nsonaazụ a pụrụ ịdabere na ya nso na porosity a na-atụ anya ya gbakọọ site na nha nha nke ILE ruo silica (Fig 1).Ebe elu BET dị n'etiti 800 na 1000 m2/g.Nha nha nke enwetara site na mkpọda nke isotherm dị n'etiti 7 na 16 nm.Tụkwasị na nke ahụ, a na-atụle obere akụkụ nke nnukwu pores ruo ihe dị ka 200 nm (fig. S6), dịka nyocha SEM.Dayameta nke pore dabara nke ọma na okpukpu abụọ nhata nke oyi akwa ILE enwetara site na mpempe olu ILE na mpaghara BET, nke pụtara na mesopores juputara na ILE.

Ebe elu BET a na-akọ bụ maka mesopores na macropores naanị.Maka matrix acetone rinsed, a tụrụkwa micropores (~ 0.6 nm).The micropores na-hụrụ n'etiti onye silica nanoparticles na-eme ka usoro dị ka ndị e gosiri na TEM oyiyi nke Fig. 1D.A na-eme atụmatụ na mpaghara agbakwunyere n'etiti 650 (x = 0.5) na 360 m2/g (x = 1.5) (tebụ S1).

Ma FTIR na Raman spectra na-egosi ihe akaebe doro anya maka otu silanol nwere mkpụrụ ndụ mmiri mmiri na-ekpo ọkụ na matrix silica porosity dị elu nke nwere oke elu dị elu karịa 1400 m2 / g mgbe ị na-eburu n'uche micropores, mesopores, na macropores.A na-eme atụmatụ n'etiti efu na atọ mmiri monolayers site na oke mmiri dị na nano-SCE maka x <1.75.Maka silica planar, a na-ewere monolayers atọ mbụ nke mmiri adsorbed n'ezie na ọ dịghị mkpagharị na nke siri ike dị ka n'ihi njikọ siri ike ha na hydrogen na elu OH kwụsịrị (32) (lee fig. S2).A na-ahụ mgbatị O─H nke jikọtara ya na silanol hydrogen jikọtara na oyi akwa mmiri ice na 3540 cm-1 na FTIR spectra.Nano-SCE niile na-egosi, n'ezie, ọnụ ọgụgụ dị iche iche na 3540 cm-1 maka mmiri mmiri mgbe ihicha ọkụ na mgbe ọ gachara ihicha na igbe uwe (Fig 2).Ọbụna maka nano-SCE equilibrated na 0.0005% RH (igbe uwe), Raman spectroscopy ka gosipụtara ọnụnọ nke ma ọ dịkarịa ala monolayer akụkụ (Fig 4B).A na-ekwenye na monolayer nke anọ na silica planar bụ oyi akwa mgbanwe, nke pụtara na ọ ka na-akwado ya ma kpachie ya mana ọ nwere ike ịnwe mmegharị.Site na oyi akwa nke ise gaa n'ihu, mmiri na-aghọ mkpanaka na mmiri mmiri.Mmiri mmiri dị ka mmiri ga-apụta na ọnụ ọgụgụ ebili mmiri dị elu na ụdị FTIR n'ihi ntakịrị ogo H-bonding na mmiri mmiri mmiri.Maka nano-SCE ekpughere na 60% RH, 3540-cm−1peak na-egosi n'ezie ịma jijiji agbakwunyere na ọnụọgụ ebili mmiri dị elu n'ihi oyi akwa mmiri mmiri na-agbakwunye.Ihe na-adọrọ mmasị na nke a bụ nnwale ebe ihe nlele ahụ gosipụtara na 30% RH, ebe ọ bụ na ọ dịghị mmiri mmiri ka a na-atụ anya na silica na iru mmiri a (fig. S2).Maka ihe atụ a, naanị 3540 cm-1 kacha elu maka mmiri ice ka a na-ahụ na FTIR.Tụkwasị na nke ahụ, a chọpụtaghị ọnụ mmiri kachasị elu na 1635 cm-1 ọbụna mgbe ụbọchị 4 gasịrị na 30% RH.Nke a pụtara na mmiri anaghị eburu mmiri site na hygroscopic Li-TFSI gbazere na hydrophobic BMP-TFSI ozugbo nano-SCE akpọnwụwo site na ọgwụgwọ agụụ.Ya mere, mmiri ọ bụla ọzọ dị na SCE ga-adaba n'elu silica nke OH kwụsịrị.N'ihi ya, n'ihe gbasara silica planar, SCE silica matrix nọ na nha anya na nrụgide akụkụ nke mmiri na gburugburu ebe obibi.

Iji nwalee echiche a n'ihu, ion conductivity nke nano-SCE (x = 1, 1.5, na 2) tụrụ na dị iche iche% RH;A na-ekpughe ihe nlele ahụ na ngwakọta a na-achịkwa nke akọrọ na mmiri N2 gas n'ime igbe uwe maka ụbọchị 2 iji mee ka mkpuchi mmiri adsorbed ruo nhata (Fig 3D).Maka isi ihe dị na ~ 0% RH, a na-ewere conductivity maka nano-SCE nhata n'ime igbe uwe.N'ụzọ dị ịtụnanya, ion conductivity megide RH (%) profaịlụ gbasoro omume a na-atụ anya ya maka mgbasa ozi mmiri na silica planar (fig. S2).N'etiti 0 na 30% RH, conductivity na-abawanye na RH na-abawanye.dị ka a na-atụ anya maka mmụba nke njupụta oyi akwa ice adsorbed na ọkpụrụkpụ (kwekọrọ na otu okpukpu atọ nke ice na planar silica).Rịba ama na FTIR gosiri na ọ dịghị mmiri efu dị na nano-SCE ruo ọtụtụ ụbọchị na 30% RH.A na-ahụ mgbanwe gburugburu 50% RH, kwekọrọ na ọnọdụ ebe a na-atụ anya oyi akwa mmiri na-agbanwe agbanwe maka silica planar.N'ikpeazụ, a na-ahụ mmụba dị iche iche na ion conductivity na 60% na iru mmiri dị elu ebe, dị ka planar silica, ugbu a, a pụkwara ịmepụta mmiri mmiri dị ka mmiri oyi na interface n'etiti silica na ILE agbakwunyere.Na FTIR, a na-achọpụta mmiri mmiri mmiri mmiri na oyi akwa ice site na ngbanwe nke silanol / ice / mmiri na-ama jijiji na ike dị elu (Fig 2A).The hụrụ mgbanwe conductivity bụ reversible;Ya mere, nano-SCE nwere ike ime dị ka ihe mmetụta iru mmiri na Li-ion electrolyte.Site na Fig. 3D, ion conductivity nke nano-SCE ozugbo mgbe agụụ anneal kwekọrọ na nha nha hydrated silica nke ~ 10% RH.Ihe omume ion maka saturation na ọnọdụ ụlọ akọrọ (~ 0.5% RH) ga-adị gburugburu 0.6 mS / cm (maka x = 2).Nnwale a gosipụtara n'ụzọ doro anya mmetụta nke mmiri interfacial na ion conductivity.Maka RH> 60%, enwere ike kọwapụta conductivity ion dị elu site na mgbasa ngwa ngwa nke Li+ gbazere site na oyi akwa dị ka mmiri mmiri.Otú ọ dị, n'ihe banyere oyi akwa ice siri ike, mgbasa ozi Li + ion ga-abụ ụdị mgbasa ozi siri ike ma si otú a dị nwayọọ karịa site na mmiri mmiri ionic n'onwe ya.Kama, a na-ekwu na nkwalite ahụ bụ mgbasawanye nke anions organic na cations nke mkpụrụ ndụ mmiri Li-nnu na ionic, dị ka atụpụtara na ihe nlereanya dị n'okpuru.

Anyị na-atụ aro a nlereanya ebe ionic mmiri mmiri ụmụ irighiri ihe na-adsorbed na silica elu site H-àkwà mmiri na-adịghị mobile oyi akwa na silanol iche iche (Fig. 4).Ọdịdị dị n'ime nke mmeghachi omume condensation hydrolysis na-enye njupụta silanol kachasị elu (4 × 1014 ruo 8 × 1014 cm−2, nke dabara nke ọma na njupụta nke otu monolayer ice na ~ 8 × 1014 mmiri mmiri kwa cm2) (34).Ihe akaebe maka mkparịta ụka molecular n'etiti O atọm nke TFSI anions na silica bụ nke FTIR na-enye, nke na-egosi okpukpu abụọ nke O═S═O elu maka nano-SCE niile ma e jiri ya tụnyere ntụaka ILE (Fig. 4A; nkọwa zuru ezu). na fig.Ngbanwe nke ọnụ ọgụgụ kachasị elu nke ihe dịka -5 cm−1 sitere na 1231 cm-1 na-egosi njikọ nke otu O═S═O maka opekata mpe akụkụ nke anions TFSI.Ya mere, a na-ewere H-bonding nke TFSI anions na oyi akwa mmiri mmiri.N'ikpeazụ, nnukwu hydrophobic BMP cations na-ejikọta na oyi akwa TFSI mbụ, na-emecha oyi akwa mbụ nke ion mmiri mmiri ionic.N'ihe banyere oyi akwa ice, a na-eche na ụmụ irighiri ihe BMP-TFSI na-anaghị agagharị agagharị, si otú a na-agbatị oyi akwa ice siri ike dị n'elu silica.Dị ka anion TFSI nwere otu O═S═O symmetrical, otu oxygen atom nwere ike imekọrịta ihe na elu silica hydroxylated ebe nke ọzọ na-etolite isi ihe na-arapara na BMP cations.Anion TFSI nwekwara otu O═S═O abụọ, na-emesi nkwenye siri ike na ịtụ oke nke anion monolayer.Adsorption na-arụ ọrụ nke ọma n'ihe gbasara oyi akwa ice nwere njupụta kachasị elu nke OH-otu dị ka ihe nwere ike ịrapagidesi ike.N'ihu naanị otu silanol, mgbasa ozi ahụ nwere ike ọ gaghị adị ike iji mepụta oyi akwa adsorbate na-aga n'ihu.Tụkwasị na nke ahụ, ọnụ ọgụgụ na-arịwanye elu nke ice monolayers mara na-eme ka ike nke njikọ hydrogen (35).Rịba ama na mmekọrịta molekụla n'etiti cation BMP na TFSI monolayer nyere iwu ga-adị iche na nke ahụ n'ime mmiri mmiri ionic ebe TFSI anion nwere nnwere onwe ntụgharị na enweghị polarization site na elu dị n'okpuru.A na-ekesa ụgwọ nke nnukwu cation BMP n'ezie n'ọtụtụ atom site na ijikọta njikọ dị n'ime ya na site na mmekọrịta molekụla na gburugburu kemịkal ya na, kpọmkwem, TFSI anion adsorbed.Njikọ H-n'etiti O-otu nke TFSI anion na OH-nkwụsị nke oyi akwa ice ugbu a na-ewebata a dipole n'elu nke mbụ adsorbed oyi akwa, na-akpali ọzọ molekụla ịtụ site mkpakọrịta.Ekwenyere na n'oge a, obere mkpụrụ ndụ Li-TFSI na-adaba na oyi akwa molekụla nke TFSI anion na-akwụ ụgwọ ụgwọ dipolar dị mma nke otu ma ọ bụ karịa nke BMP cations na elu elu, ya mere na-atọpụ njikọ ya na Li ya. ion.N'ụzọ dị otú a, ịta nke free Li + na-abawanye na interface a, na-eduga na elu ion conductivity.N'ihi ya, akwa akwa ice dị oke ma buru ibu wee webata dipole buru ibu yana ụgwọ mpụta dị elu iji kwụọ ụgwọ, na-enye ntinye uche Li + n'efu nke ukwuu wee si otú a na-eduzi ion.

N'elu oyi akwa ILE nke adsorbed, ma ọ bụ oyi akwa ILE ọzọ nwere ike adsorb dị ka ice multilayers na silica ma ọ bụ dipole ịdọrọ nke oyi oyi akwa adịghị ike na ILE na-ejighị ya kpọrọ ihe dị n'elu, nke nwere ike inye mmiri mmiri dị ka ntụziaka maka. ion Li + ewepụtara na ala adsorbed oyi akwa (Fig 4C).Mgbanwe na ntinye uche Li+ ion efu bụ nke NMR na nha spectroscopy Raman kwadoro.Ntụle Raman na-egosi n'ụzọ na-apụtaghị ìhè na ọnụ ọgụgụ buru ibu nke ion Li+ efu bụ n'ezie na nano-SCE nwere ọtụtụ mmiri mmiri ice jikọtara na silica (Fig 5).Raman na-atụle njikọ nke cation na TFSI site na nyocha nke ọma jijiji nke N-group nke TFSI anion (36).N'ime mmiri mmiri ionic BMP-TFSI dị ọcha, naanị otu ọnụ ọgụgụ kacha elu na 741 cm-1 ka a na-ahụ.N'ihe banyere ILE dị ọcha, a na-ahụ ọnụ ọgụgụ kachasị elu na 746 cm-1 ebe abụọ TFSI anions na-ejikọta ya na otu Li + ion [lee density functional theory (DFT) mgbakọ na mwepụ na ihe na ụzọ].Maka nano-SCE niile, ọnụ ọgụgụ kacha elu na 746 cm−1 adịghị ike karịa nke ahụ maka ILE, na-egosi obere akụkụ nke Li-TFSI jikọtara yana, ya mere, akụkụ buru ibu nke ndị na-enweghị njikọ ma ọ bụ nke Li+ n'efu.Ọnụ ọgụgụ kasị elu na-ebelata nke ukwuu maka nano-SCE ndị ahụ na-egosi nkwalite nrụpụta kachasị elu, ya bụ, ndị nwere oyi akwa ice kacha.Maka nano-SCE na nha nha n'ime igbe uwe aka, ka a na-atụ ntakịrị ntakịrị Li + n'efu n'agbanyeghị na ọ dị obere karịa maka ihe nlele ndị na-ekpo ọkụ.Ọnụọgụ ọnụ ọgụgụ kacha elu maka 746 n'elu 741 cm-1 Raman na-agbanwe mgbe ahụ bụ ihe nha nke free na TFSI metụtara Li-ions (Fig. 5B).Mmụba linear na ntakiri Li+ ion n'efu nwere uru x na-agbaso usoro nkwalite conductivity na uru x dị na Fig. 3B, ma maka oghere akpọnwụwo nano-SCE (ụbọchị 0) yana SCE na nha nha na igbe mkpuchi mkpuchi (ụbọchị). 138).

(A) Raman ụdịdị mmiri mmiri ionic (IL; ahịrị na-acha anụnụ anụnụ nwere ntụpọ) na ntụnye ILE (ILE; ahịrị nwere ntụpọ) nke nano-SCE a kwadebere (vacuum akpọnwụwo) yana ụkpụrụ x nke 0.5 (green), 1.5 (edo edo) , na 2 (aja aja) na nke nano-SCE (x = 1.5) gbakwunyere n'ime igbe uwe maka ụbọchị 30 ma ọ bụ nso saturation na 0.0005% RH (red).Ahịrị kwụ ọtọ na-edobe mgbanwe Raman maka TFSI yana etiti N ya na-ahazi na Li+ (746 cm−1) na anaghị ahazi ya na Li+ (741 cm−1), n'otu n'otu.(B) Ratio nke nnwere onwe iji hazie Li + nke nano-SCE dị ka synthesized (vacuum akpọnwụwo, okirikiri ojii) ma gbakwunyere n'ime igbe uwe nwere 0.0005% RH maka ụbọchị 30 (diamọnd na-acha anụnụ anụnụ), kwekọrọ na nha nke ike agbakwunyere. Oke Raman (746 cm-1 karịa 741 cm-1).(C) PFG-NMR – ewepụtara Li + ọnụọgụ mgbasa ozi onwe nke nano-SCE (ola edo uhie) na ILE ref.(oghere ojii) dị ka ọrụ nke etiti dị n'etiti oghere ndọta gradient.A na-eme ka ọnụ ọgụgụ dị elu nke usoro ihe omume dị na Raman spectra site na iji mgbako DFT.

Site na gradient pulsed-field NMR (PFG-NMR), ọnụọgụ mgbasa ozi nke ụdị Li-ion dị iche iche ka ekpebisiri ike dị ka ọrụ nke etiti dị n'etiti oghere ndọta gradient ∆ maka ntụnye mmiri ILE na maka nano- SCE (x = 1.5) na otu ion conductivity nke 0.6 mS / cm (Fig. 5C).Ọnụ ọgụgụ mgbasa ozi nke Li + na ntinye aka ILE na-adị mgbe niile, na-egosi na ọ bụ naanị otu ma ọ bụ ọtụtụ ụdị Li nwere mmegharị yiri ya dị na mmiri mmiri.Maka nano-SCE, ọnụọgụ mgbasa ozi nke onwe ya dịgasị iche na ∆ ma gafere nke ILE na mkpụmkpụ ∆, na-egosi ọnụnọ nke ụdị na-agba ọsọ na-anabata naanị na obere oge n'etiti oghere magnetik.The gradient na onwe mgbasa ọnụọgụgụ na-atụ aro na na-esote na-abawanye na free Li-ion ịta, dị ka e si na Raman spectroscopy, na ebighị ike maka mgbasa na-agbada na mesophase interface oyi akwa nakwa.Nke a na-akwado nkwalite conductivity nke ion Li+ efu webatara na oyi akwa mesophase.N'ogologo ∆, ọnụọgụ mgbasa ozi nke onwe dị ala karịa nke ntụnyere ILE.Nke a na-akwado arụmọrụ ion dị ala maka igbe uwe-nano-SCE juru eju ma e jiri ya tụnyere ILE.ILE nke etinyere na isi nke mesopores ga-enwe viscosity dị elu n'ihi mmachi nke mmegharị ahụ.N'ihi ya, nkwalite site na ịmepụta Li-ions na-agbasa ngwa ngwa na silica/ice/ILE interface ga-emerịrị mbelata nke conductivity na isi nke pore.Nke a na-akọwa enweghị nkwalite na urughuru dabeere na usoro ebe interfaces adịghị enye zuru ezu ion conduction nkwalite (fig. S1).

A nwalere nkwụsi ike nke electrochemical nke nano-SCE megide metal lithium site na iji nhazi atọ-electrode (atụmatụ nke nhazi ahụ gosipụtara na fig S7).A na-egosi njirimara nke Li/SCE dị ugbu a na ọkara cell na Li/ILE na Fig. 6A.N'ihe gbasara windo electrochemical na Fig. 2, electrochemistry na-ejedebe site na ILE filler.A na-ahụ ihe mkpuchi lithium na-agbanwe agbanwe na ịkwapụ.A na-emepụta oyi akwa siri ike electrolyte interphase (SEI) na lithium dara nwere RSEI nke ihe dịka 0.9 kilo-ohm·cm2, na-ahụ maka nnukwu IR dobe na iU curve n'akụkụ kathodic na anodic.Ụdị cathodic dị ugbu a na ngwọta ILE dị ọcha egosighi hysteresis ọ bụla ruo -2.5 mA/cm2.Otú ọ dị, mgbasa nke anodic gosipụtara ọnụ ọgụgụ kasị elu nke passivation nwere ọnọdụ anodic na-akwụ ụgwọ nke nanị 0.06 mA/cm2.Alaka cathodic dị ugbu a na interface Li/SCE siri ike egosighi hysteresis maka ikuku cathodic na-erughị -0.5 mA/cm2.Nguzogide nke SEI bụ, Otú ọ dị, ihe dị ka okpukpu abụọ.N'otu aka ahụ, ọnụ ọgụgụ anodic dị ala na ọnọdụ na-adị ugbu a mgbe ọnụ ọgụgụ anodic passivation bụ 0.03 mA/cm2, naanị ọkara nke ngwọta ILE dị ọcha.Nhazi nke SEI na passivation layers na pores nke SCE na-amachi ugbu a na lithium metal.Ma voltammogram maka Li/ILE na Li/SCE electrodes bụ nke a na-emegharị n'ọtụtụ okirikiri, na-egosi na oyi akwa passivation anodic na oyi akwa SEI kemịkalụ na-atụgharị ma kwụsie ike.Kinetics mgbasa ngwa ngwa na interface Li/SCE na-amachi arụmọrụ nke ọkara sel ejiri Li metal anodes mee n'okpuru.

(A) Cyclic voltammogram nke nano-SCE (x = 1.5, dị ka synthesized mgbe agụụ ihicha) (red) na ILE ntụaka (oji) tụrụ na atọ-electrode nhazi na Li dị ka ọrụ, counter, na akwụkwọ electrodes (SEI nguzogide atụmatụ si IR dobe na cathodic ugbu a bụ 0.9 na 1.8 kilo-ohm·cm2 maka ILE na SCE, n'otu n'otu).(B) Galvanic ụgwọ/mkpọsa usoro nke Li/SCE (x = 1)/ 100-nm mkpa ihe nkiri LiMn2O4 cell maka okirikiri ise na C-ọnụọgụ nke 1C, 5C, na 20C.(C) cyclic voltammogram nke Li/SCE/40-μm Li4Ti5O12 na Li/SCE/30-μm LiFePO4 uzuzu electrode sel (1 mV/s).(D) Galvanic ụgwọ / mwepu akụkụ nke Li/SCE/40-μm Li4Ti5O12 ntụ ntụ electrode na 1C, 0.1C, 0.2C, na 0.02C.(E) Galvanic ụgwọ / mwepu akụkụ nke Li/SCE/30-μm LiFePO4 ntụ ntụ electrode na 1C, 0.5C, 0.2C, 0.1C, 0.05C, na 0.01C.(F) Ikike (ola diamond jupụtara maka delithiation na oghere oghere maka lithiation) na ọnụọgụ okirikiri nke Li / SCE / 30-μm LiFePO4 ntụ ntụ;ọkpụrụkpụ nke SCE na sel bụ ihe dịka 280 μm.Njupụta nke LFP na LTO cathode bụ ihe dịka 1.9 na 11.0 mg/cm2, n'otu n'otu.(G) Ogologo oge na ogologo oge nke ngwugwu Li/SCE/Li gbagoro na njupụta ugbu a nke 0.1, 0.2, 0.5, na 0.1 mA/cm2.(H) Nke 1st, 10th, 125th, and last polarization of Li/SCE/Li stack mesiri ike na 0.1 mA/cm2, egosiri na (G).Maka (G) na (H), SCE nwere conductivity nke 0. 34 mS/cm, na ọkpụrụkpụ nke pellet SCE bụ 0.152 cm.

A na-eji ihe nkiri 100-nm LiMn2O4 (LMO) dị mkpa dị ka ihe nlereanya ziri ezi electrode iji nwalee ma nkwụsi ike nke nano-SCE na ihe electrode mgbe ọ na-ewepụ nsogbu ndị nwere ike ime na ihe ndị nwere ike ime na electrodes composite (37).Ọrụ ịgba ígwè nke igwe ihe nkiri dị mkpa / SCE stack na-egosipụta nkwụsi ike nke interface n'etiti electrode na electrolyte.Na nke a nlereanya mkpa-film setup, ọ bụ naanị otu otu, nke ọma-akọwara, na planar interface kọntaktị dị n'etiti electrolyte na electrode, ya bụ, ọ bụ ezigbo ikpo okwu na-amụ electrochemistry nke electrolyte / electrode interface na-enweghị mbipụta nke mgbanwe olu. , wdg Nakwa na nnwale a, arụmọrụ ọnụego anaghị ejedebe site na Li-foil counter electrode, dị ka njupụta dị ugbu a (6 μA / cm2 maka 1C) dị n'okpuru nke ala anodic dị ugbu a na-adịgide adịgide maka ọkara lithium. cell (0.03 mA / cm2).A na-enweta akụkụ ndị na-agbanwe agbanwe ma kwụsie ike maka ịgbanye ọkụ na 4.3 V maka ọnụego C n'etiti 1 na 20C maka ihe karịrị 20 okirikiri (Fig 6B).LMO anaghị eguzosi ike na electrolyte mmiri mmiri maka LiB.Dịka ọmụmaatụ, a hụrụ mbelata ikike 50% na ụgwọ ihe nkiri LMO 100-nm maka cycles 10 na LiClO4/propylene carbonate electrolyte na 1C (37).Nsonaazụ anyị na-egosi na nano-SCE dakọtara na LMO karịa igwe eletriki mmiri nkịtị.

Iji gosi njikọ nke nano-SCE, anyị mekwara ọkara sel na Li4Ti5O12 (LTO) na LiFePO4 (LFP) uzuzu electrodes.A tụbara ihe ngwọta nke mbụ n'ime mkpụrụ ego mkpụrụ ego iji tinye electrodes porous ma hapụ maka gelation ọzọ tupu akpọnwụọ ha ma kpochaa ya na-ekpo ọkụ n'otu aka ahụ maka pellets nano-SCE.Selụ na-egosi njirimara lithiation/delithiation nke electrodes kwekọrọ (Fig 6C).Igwe mmiri dị ala maka LFP karịa LTO bụ n'ihi ọdịiche dị na ọkpụrụkpụ mkpuchi.Arụmọrụ ọnụego n'oge nha/nha nha ka amachiri site na Li-foil counter electrode na-agbanye na nano-SCE oyi akwa nke kpụrụ n'elu 30- ruo 40-μm-oke electrode mkpuchi (Fig. 6, D na E).LTO / nano-SCE / Li cell ruru ikike kachasị elu nke 160 mA·hour / g naanị na obere C-ọnụego 0.02C (Fig. 6D).Ikike ịnweta na-agbada ngwa ngwa site na ọnụego C na-erughị 10% maka ọnụego C karịrị 0.1C.N'otu aka ahụ, LFP / SCE / Li cell ruru ikike kachasị elu nke ihe dịka 140 mA·hour / g na 0.01C (Fig. 6E).Ọgụgụ 6F na-egosi arụmọrụ ọnụego maka ngụkọta nke okirikiri 30, na-egosipụta nhazi cell kwụsiri ike.Nnwale ndị a na-egosipụta ọrụ nke nano-SCE dị ka Li-ion electrolyte na ohere maka ntinye na sel Li-ion.

A nwale nkwụsi ike ma ọ bụ cyclability nke nano-SCE site na iji nchịkọta Li/SCE/Li.A na-agbagharị ya maka ihe karịrị 120 cycles na njupụta ugbu a nke 0.1 mA / cm2 maka awa 0.5 (Fig 6G) na-enweghị nsogbu ọ bụla ma ọ bụ nhazi dendrite (Fig 6H).Voltaji nke polarization bịara dị ntakịrị ka oge na-aga, na-egosi mmụba nke kọntaktị.Ọzọkwa, a na-emesi cell ahụ ike ruo njupụta ugbu a nke 0.5 mA / cm2, na-enweghị nhazi nke lithium dendrites ma ọ bụ ihe ịrịba ama nke mmebi nke nano-SCE ma ọ bụ interface (Fig 6G).A maara lithium ọla ka ọ na-etolite oyi akwa interphase nchebe ma ọ bụ SEI n'elu ya na BMP-TFSI dabeere ILEs (27).Mmeghachi omume a na-emekwa na lithium/nano-SCE interface;dị ka a tụlere n'okpuru Fig. 6A, SEI nwere ike itolite ntakịrị n'ime pores, na-akọwa nguzogide SEI dị elu maka nano-SCE karịa ILE (lee n'elu).E nwetara ihe akaebe maka oyi akwa SEI site na IR spectra (fig. S9).Yiri mkpuchi SEI na oge gboo LiB, nke na-enyocha electrode graphite site na mmiri mmiri electrolyte na-ezere mmeghachi omume ọzọ, anyị kwenyere na SEI ebe a na-echebekwa oyi akwa mmiri mmiri site na mmeghachi omume ọzọ sitere na lithium anode dara.Ihe nlere anya nke impedance tupu na mgbe polarization nke Li/nano-SCE (x = 1.5) maka awa 10 egosighi mgbanwe ọ bụla na nguzogide electrolyte buru ibu.A ga-achọ nha arụmọrụ ịgba ígwè ogologo iji wepụ ngwa ngwa ihicha nke nano-SCE site na lithium metal, mana nsonaazụ ndị a egosilarị ikike ya maka ọmarịcha cyclability nke SCE na batrị lithium metal dabere na batrị steeti siri ike.Ka o sina dị, enwere ike ịtụle mkpuchi interphase artificial iji melite impedance interface kpamkpam.

Anyị egosila na enwere ike nweta nkwalite ion conduction na oghere silica site na iwebata oyi akwa mmiri chemisorbed na elu silica kwụsịrị OH.The TFSI anions chemisorb na mmiri a na-arụ ọrụ oyi akwa site hydrogen bonding na symmetric O═S═O otu.Igwe mmiri dị n'elu anaghị agagharị, yabụ na-atụnye oyi akwa TFSI nke etinyere n'elu.Nnukwu cations BMP na-ejikọta na monolayer TFSI, si otú a na-ewebata usoro ihe omimi nke TFSI-BMP n'elu.Anyị kwenyere na gelation na-adịghị ngwa na gburugburu ebe obibi mmiri na ihicha ngwa ngwa na-enyere aka n'ịmepụta nke na-arụ ọrụ mmiri oyi akwa na nhazi nhazi nke ion organic n'elu ya.Dị ka nke mbụ TFSI anion oyi akwa na-ekerịta akụkụ nke ụgwọ ọjọọ ya na silica hydroxylated, BMP cation Layer n'elu ga-achọ mkpakọrịta ya na anion TFSI ọzọ, nke ọtụtụ BMP nwere ike iji otu TFSI kesaa ụgwọ a na-akwụghị ụgwọ ha (ma eleghị anya, atọ na otu dị ka ọ dị na TFSI). oke nke IL na Li-TFSI na ILE).Dị ka ụmụ irighiri nnu Li-TFSI nwere ụzọ kacha nso, ion Li+ ga-ekewa ma hapụ ya ka ọ nwee ike ịgbasa ngwa ngwa n'akụkụ oyi akwa a.Maka nkwalite nkwalite, ụdị Li+ ndị a n'efu chọrọ opekata mpe otu akwa mmiri ionic ọzọ ka ọ gafere.N'ihi nke a, nano-SCE na ọnụ ala x dị ala nke 0.5 egosighi ihe nrụpụta emelitere, dịka ebe elu ILE / silica zuru ezu maka naanị otu monolayer mechiri emechi.

E gosikwara na mmiri dị n'elu siri ike dị ka oyi akwa ma ọ bụ oyi akwa anaghị arụ ọrụ nke ọma.N'ebe a, anyị enweghị ike iwepụ na mmiri ice na kọntaktị na elu electrode adịghị emeghachi omume.Otú ọ dị, anyị gosiri na mpụ-mgbasa nke elu mmiri na-adị nwayọọ ma si otú kinetically negligigible maka nchọpụta.Anyị na-aghọta na mmetọ mmiri, ọ bụrụgodị na ọ dị ntakịrị, ga-abụ ihe na-echegbu mgbe nile, na naanị ogologo oge ule ogologo ndụ nwere ike inye azịza doro anya ma mmiri ahụ ọ̀ bụ nke ọma.Otú ọ dị, ọkwa elu ndị ọzọ na-arụ ọrụ nke na-enye nkwalite elu nke yiri ya ma ọ bụ ọbụna karịa nwere ike ịmepụta ugbu a.N'akụkụ a, otu Li egosilarị ikike nke oyi akwa glycidyloxypropyl dị ka otu ọrụ (18).Mmiri ice sitere na silica, ya mere ọ dabara adaba iji mụọ mmetụta arụ ọrụ nke elu na nkwalite ion n'usoro n'usoro, dị ka egosiri nke ọma ebe a.Tụkwasị na nke ahụ, oyi akwa mesophase na dipole ya ga-adabere na oxide na n'elu ihe ndị na-emepụta ihe na-emepụta ihe na-edozi ahụ ma si otú a na-emegharị ha abụọ.N'ime ụlọ nyocha, anyị egosila nnukwu ọdịiche dị na nkwalite ion conduction maka mmiri mmiri ion dị iche iche.Ọzọkwa, ụkpụrụ egosipụtara bụ ọnụọgụ maka ion conduction ma nwee ike tinye ya maka sistemụ ion dị iche iche dabara adaba, dịka ọmụmaatụ, maka batrị sodium, magnesium, calcium, ma ọ bụ aluminom ion.N'ikpeazụ, nanocomposite electrolyte na interface conduction gosiri ebe a bụ echiche kama otu ihe, nke nwere ike ịbụ n'ihu (nano) engineered ka chọrọ Njirimara nke ion conduction, njem nọmba, electrochemical window, nchekwa, na-eri maka ọdịnihu batrị cell ọgbọ. .

A kwadebere nano-SCE site na iji usoro sol-gel.Lithium bis (trifluoromethylsulfonyl) imide Li-TFSI;Sigma-Aldrich;99.95%), 0.5 ml nke deionized H2O, 0.5 ml nke TEOS (Sigma-Aldrich; 99.0%), 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide (BMP-TFSI; Sigma-Aldrich; 98.5%), na 11. A gwakọtara ml nke PGME n'ime vial iko.Oke molar, x, n'etiti [BMP] [TFSI] na TEOS na ngwakọta dị iche iche n'etiti 0.25 na 2. Edobere oke nke Li[TFSI] na [BMP][TFSI] na 0.33: 1.Achọpụtara ọnụọgụ nke Li[TFSI] na [BMP][TFSI] site na oke ndị a.Dịka ọmụmaatụ, mgbe x = 1, agbakwunyere [BMP][TFSI] na Li[TFSI] na ngwọta bụ 0.97 na 0.22 g, n'otu n'otu.A na-ama jijiji nke ngwakọta maka 1 min iji mepụta ngwọta monophasic.A na-echekwa ihe ngwọta ndị a na vials mechiri emechi n'emeghị ka ọ bụrụ gels n'ime ụlọ na-achịkwa okpomọkụ na iru mmiri (SH-641, ESPEC Corp.) na okpomọkụ na RH% setịpụrụ na 25 ° C na 50%, n'otu n'otu.Dabere na x, ngwakọta ahụ were, na nkezi, 5 ruo 9 ụbọchị iji mepụta gel doro anya.Mgbe gelation gasịrị, a na-ebu ụzọ kpoo vial ndị nwere 2.4- ruo 7.4-ml gel na 40 ° C maka ụbọchị anọ zuru oke na nrụgide dị ntakịrị (80 kPa) wee banye n'ime oven na-ekpo ọkụ maka awa 72 na 25 ° C.Ka ewepụrụ mmiri fọdụrụnụ, oghere ahụ ji nwayọọ nwayọọ belata site na nrụgide mbụ gburugburu 50 Pa ruo nrụgide ikpeazụ nke 5 Pa mgbe ihe dị ka otu ụbọchị gasịrị.N'ihi nnukwu mmiri na PGME nke a ga-ewepụ, pellets SCE esitela na 20% (x = 0.5) ruo ~ 50% (x = 2) nke olu gel mbụ.A tụlere ịdị arọ nke gels ndị a na-esi na ya pụta na nguzozi semimicro (SM 1245Di-C, VWR).

Emere TGA na Q5000 IR (TA Instruments, New Castle, DE, USA) n'okpuru nitrogen.N'oge nha, ihe nlele na-ekpo ọkụ ruo 700 ° C na ọkụ ọkụ nke 2 ° C / min.Emere spectrometry FTIR site na iji Bruker Vertex 70 na ọnụọgụ ebili mmiri sitere na 4000 ruo 400 cm-1 n'ụdị nnyefe.Emere pycnometry ya site na iji Micromeritics AccuPyc II 1340.

Iji tụọ ihe omume ionic, a napụrụ obere olu SCE site na vial nne n'ime igbe mkpuchi Ar-jupụtara (0.1-ppm H2O na 0.1-ppm O2).Ihe dị ka 23 μl nke SCE juputara na mgbanaka polytetrafluoroethylene (PTFE) nke nwere dayameta dị n'ime 4.34-mm na ịdị elu 1.57-mm, na-akpụ pellet.A na-agbanye pellet dị na mgbanaka ahụ n'etiti diski igwe anaghị agba nchara (SS) abụọ (oke 0.2 mm; MTI).Emere nha ihe mgbochi site na iji PGSTAT302 (Metrohm), yana njupụta AC nke 5 mV n'ogo ugboro site na 1 MHz ruo 1 Hz.Ekpebiri ion conductivity (σi) site na nkwụsị nke ugboro ugboro na ezigbo axis na atụmatụ Nyquist.Mgbe nlele conductivity gasịrị, ekwenyere nano-SCE pellet ka ọ kpọnwụọ n'igbe aka.Maka nha dabere na ọnọdụ okpomọkụ, SS/SCE/SS kpọchiri akpọchi n'ime mkpụrụ ego mkpụrụ ego.Mgbe akara, conductivity nọgidere na-adịgide adịgide ruo ọtụtụ ụbọchị (lee fig. S3).A na-achịkwa okpomọkụ nke mkpụrụ ego mkpụrụ ego na jaket okpomọkụ na-eji ọkụ ọkụ na-eji H2O/ethylene glycol dị ka onye na-arụ ọrụ.A na-ebu ụzọ mee ka mkpụrụ ndụ dị jụụ ruo ihe dịka -15 Celsius C wee kpoo ya nke ọma ruo 60 Celsius.

Site na pellet nano-SCE nke ọ bụla, ihe dị ka 23 μl ka ewebatara n'ime mgbanaka (4.34-mm dayameta dị n'ime na ịdị elu 1.57-mm) maka nha eletrik ozugbo n'ime igbe uwe aka jupụtara N2 nwere iru mmiri na-achịkwa.A na-agbanye mgbanaka ahụ nwere SCE n'etiti diski SS abụọ (oke 0.2 mm; MTI).Emere nha impedance site na iji PGSTAT302 (Metrohm) nwere njupụta AC nke 5 mV yana ugboro sitere na 1 MHz ruo 1 Hz na-achịkwa site na ngwanrọ Nova.A na-edobe ihe nlele ahụ na uru RH% ọ bụla maka awa 48 tupu elele conductivity ruo mgbe nkwụsi ike.Achọpụtara arụmọrụ ionic kwụsiri ike maka uru RH% enyere (σi) site na nkwụchi ugboro dị elu yana ezigbo axis dị na atụmatụ Nyquist.

Emere nha eletrọkị niile na nkwadebe ihe nlele metụtara ya na igbe mkpuchi nke argon (PureLab, PL-HE-4GB-1800; <1-ppm O2 na H2O ọkwa) raara nye maka njirimara electrochemical.

A na-enyocha morphology nke pellet na na-enweghị Li [BMP] [TFSI] ILE na SEM site na iji ngwa Thermo Fisher Scientific Apreo na 1.5 ruo 2.0 kV wee na-arụ ọrụ n'ụdị ihe nleba anya abụọ na-eji T1 na T2 detector n'otu n'otu maka. mgbanwe oyiyi ndụ, na ihe nchọpụta T2 ejiri mee ihe maka ịdekọ ihe oyiyi SEM egosipụtara;A na-edozi ihe nlele ahụ na teepu conductive carbon.Emere TEM site na iji Tecnai na-arụ ọrụ na 300 kV.

E wepụrụ ILE na pellet SCE n'ụzọ abụọ dị iche iche.Otu nhọrọ iji nweta silica porous mere site n'itinye SCE na acetone maka awa iri na abụọ iji wepụ Li[BMP][TFSI] ILE.A na-emegharị ncha a ugboro atọ.Nhọrọ ọzọ bụ site na itinye SCE na ethanol.N'okwu a, e wepụrụ ethanol site na iji mmiri mmiri CO2 dị oke mkpa nkụ.

Eji ngwá ọrụ abụọ dị iche iche mee ihe maka ikpocha ihe dị elu, ya bụ, Automegasamdri-916B, Tousimis (Usoro 1) na ngwá ọrụ omenala nke JASCO Corporation wuru (usoro 2).Mgbe ị na-eji ngwá ọrụ mbụ, usoro ihicha malitere site na mbelata okpomọkụ ruo 8 Celsius.Mgbe nke ahụ gasịrị, a kpochapụrụ CO2 site na ụlọ ahụ, na-abawanye nrụgide ruo 5.5 MPa.Na usoro na-esote, a na-ekpo ọkụ CO2 na 41 ° C, na-abawanye nrụgide na 10 MPa, ma debe ya maka 5 min.Iji kwubie, na usoro ọbara ọgbụgba, a na-ebelata nrụgide n'ime oge nke 10 min.Mgbe ị na-eji ngwá ọrụ arụrụ arụrụ arụ, a gbasoro usoro yiri nke ahụ.Otú ọ dị, oge na nrụgide dịgasị iche iche.Mgbe usoro nchacha ahụ gasịrị, a na-abawanye nrụgide na 12 MPa na okpomọkụ nke 70 Celsius ma nọgide na-adị ka 5 ruo 6 awa.N'ikpeazụ, a na-ebelata nrụgide n'ime oge site na 12 ruo 7 MPa, 7 ruo 3 MPa, na 3 ruo 0 MPa n'ogologo oge nke 10, 60, na 10 min, n'otu n'otu.

Nitrogen physisorption isotherms tụrụ na T = 77 K site na iji Micromeritics 3Flex surface characterization analyzer.A na-ekpochapụ silica porous ahụ enwetara maka awa 8 na 100 Celsius n'okpuru oghere 0.1-mbar.A na-ekpochapụ silica porous nke sitere na ihicha dị elu maka awa 18 na 120 Celsius n'okpuru oghere 0.1-mbar.Mgbe nke ahụ gasịrị, a tụrụ nitrogen physisorption isotherms na T = 77 K site na iji Micromeritics TriStar 3000 gas adsorption analyzer.

Emere nha PFG-NMR site na iji JEOL JNM-ECX400.A na-eji usoro nrịbama nke echo pulse mee ihe maka nha mgbasa.A na-akọwa attenuation nrịbama mgbanaka nkịtị, E, na nha nha (38) E = exp (-γ2g2δ2D (Δ-δ/3)) (1) ebe g bụ ike nke gradient pulse, δ bụ ogologo oge nke gradient. pulse, ∆ bụ etiti dị n'etiti akụkụ ndị na-eduga nke mkpụrụ akụ gradient, γ bụ oke magnetogyric, na D bụ ọnụọgụ mgbasa ozi nke onwe nke ụmụ irighiri ihe.A na-eme atụmatụ ọnụọgụ mgbasa ozi nke onwe site n'itinye akara ngosi nke echo nwetara site n'ịgbanwe ∆ na Eq.1. 7Li ahọpụtara iji chọpụta ọnụọgụ mgbasa ozi nke ion lithium.A na-eme nha niile na 30 Celsius.

Ntọala spectroscopy nke Raman bụ usoro arụrụ n'ụlọ na-eji argon ion nke nwere ike na-emegharị ya na ọkụ ọkụ ọkụ laser 458-nm nke jikọtara n'ime microscope Olympus IX71 tụgharịrị, na ọkụ gbasasịrị azụ gafere site na TriVista triple spectrometer setup (Princeton Instruments). ), nke eji chụsasịa ngwa anya nke achọpụtara site na iji igwefoto ngwaọrụ ejikọ chajị oyi-ajụ oyi.N'iburu n'uche nnabata ngwa anya dị elu na ogologo oge ndị a, a na-eji ike laser dị ntakịrị iji zere ikpo ọkụ laser (<100 W · cm-2).

DFT njikarịcha geometry ala steeti na ngụkọ nyocha jiri ọrụ ngwakọ B3LYP na-ewu ewu yana ntọala ntọala 6-311++G** yana Grimme's atom-pairwise dispersion correction (39) na atụmatụ damping Becke-Johnson (D3BJ), dị ka etinyere na ORCA 3.0.3 (40).Ejiri ORCA simulated spectra nke Raman, wee nweta nleba anya nke ihe molekul site na iji ngwugwu ngwanrọ Avogadro (41) yana nwelite ORCA na-akwado.

Emere nha eletrọkị niile na nkwadebe ihe nlele metụtara ya na igbe mkpuchi nke argon (PureLab, PL-HE-4GB-1800; <1-ppm O2 na H2O ọkwa) raara nye maka njirimara electrochemical.A na-etinye SCE pellet na Li ribbon (Sigma-Aldrich; 99.9%) kwadoro na efere ọla kọpa ka eletrọd counter na pịpụtara Li disks abụọ (dayameta 5-mm) ka etinyere n'elu pellet SCE maka ntụnye aka na ịrụ ọrụ. electrodes.Egosiri ntọala na fig.S7.A na-eji ntụtụ ọla edo maka ịkpọtụrụ akwụkwọ ntụaka lithium na electrodes na-arụ ọrụ.Emere cyclic voltammetry na nha impedance site na iji PGSTAT302 (Metrohm) na-achịkwa site na ngwanrọ Nova.Emere voltammetry cyclic site na nyocha nyocha nke 20 mV / s.Emere nha impedance site na njupụta AC nke 5 mV yana ugboro sitere na 1 MHz ruo 0.1 Hz.

Etinyere 40-nm anatase TiO2 thin-film electrode site na ntinye ihe nrụnye atomic Layer (ALD) na wafer silicon 300-mm nwere 40-nm TiN underlayer nke ALD dokwara.Ọ bụ ihe dị mma ule electrode maka ngosipụta nke Li-ion conductivity site electrolytes, dị ka TiO2 adịghị ata ahụhụ site kemịkalụ mmebi ma ọ bụ n'ibu nrụgide (enweghị ịrịba olu mgbanwe) n'oge ịgba ígwè.Iji tụọ cell Li / SCE / TiO2, ILE-SCE jupụtara na mgbanaka PTFE na dayameta nke 4.3 mm na ọkpụrụkpụ nke 0.15 cm;mgbe ahụ, a na-agbanye mgbanaka ahụ n'etiti ihe nkiri Li na ihe nkiri TiO2.

Akpụpụtara Nano-SCE/ihe nkiri elektrọd dị obere, yana elektrọd LMO, site na ijikọ ihe nkiri nano-SCE na elektrọd.Ngụkọta 150 μl nke x = 1.5 ngwọta, agadi maka ụbọchị 2, ka etinyere na mgbanaka iko (dayameta, 1.3 mm) na-agbanye na ihe nkiri electrolyte.A na-eji parafilm mechie mgbanaka ahụ, a na-edobekwa ihe ngwọta ahụ n'ime akpa mkpuchi dị otú ahụ ka ọ bụrụ gel maka ụbọchị 4.Nchịkọta gel/electrode a kpụrụ dị ka akpọnwụwo ka ọ bụrụ nano-SCE/electrode stacks.Ọkpụrụkpụ nke nano-SCE, kpebisiri ike site na iji micrometer, bụ 300 μm.N'ikpeazụ, a pịnyere foil lithium (1.75 mm gbara ọkpụrụkpụ, 99.9%; Sigma-Aldrich) na nano-SCE/electrode tojupụtara dị ka anode.Edebere 100nm LiMn2O4 (LMO) nke dị mkpa ihe nkiri elektrọd site na ịgbasa ugboro redio n'okpuru Ar na-agba na wafer silicon nke ejiri 80-nm Pt (DC sputtering) / 10-nm TiN (ALD) kpuchie.E kpochapuru ngwugwu a maka nkeji 20 na 800 Celsius na ikuku oxygen.

LiFePO4 (LFP) ihe nkiri elektrọd ka ejiri mkpuchi agụba kwadebere.Nke mbụ, carbon ojii na LFP (2 ruo 3 μm) ka agbakwunyere na ngwọta mmiri nwere carboxymethylcellulose (CMC) iji mepụta ngwakọta nke emesịa ejikọta ya site na iji igwe igwe ụwa.Mgbe ahụ, a na-agwakọta ngwaahịa homogenized na mmiri deionized na fluorinated acrylic latex (JSR, TRD202A) na igwekota agụụ iji mepụta slurry maka mkpuchi electrode.A na-atụba slurry a kwadebere na foils aluminum iji tinye ihe nkiri electrode site na iji mkpuchi agụba.A na-ebunye electrodes mmiri mmiri ndị a dị ka mkpuchi ozugbo na oven ikuku ikuku na 70 Celsius C maka nkeji 10 wee kpochaa ya na 140 ° C maka awa 4 n'ime oven.Ihe nkiri elektrọd a mịrị amị gụnyere 91 wt% LiFePO4, 3 wt% carbon ojii, 2 wt% CMC, na 4 wt% TRD202A.Ọkpụrụkpụ ihe nkiri ahụ bụ 30 μm (ekpebisiri ike site na iji micrometer na nyocha microscope elektrọn).

Emere ihe nkiri electrode Li4Ti5O12 na foils ọla kọpa n'otu ụzọ ahụ.Ngwakọta nke electrodes a mịrị amị bụ 85 wt% Li4Ti5O12, 5 wt% carbon ojii, 5 wt% CMC, na 5 wt% fluorinated acrylic latex (TRD2001A).Ogologo ihe nkiri ahụ bụ 40 μm.

A tụbara ihe ngwọta nke SCE na ihe nkiri LFP dabeere na urughuru na LTO electrode.Nke mbụ, 100 μl x = 1.5 ngwọta, agadi maka ụbọchị 2, na-adaba na ihe nkiri electrode, nke nwere dayameta nke 15 mm, tinye n'ime mkpụrụ ego mkpụrụ ego (#2032, MTI).Mgbe SCE nke a na-etinye n'ime ahụ gasịrị, a kpochara ihe nkiri ahụ na 25 ° C maka awa 72 n'ime ọkụ ọkụ (<5 × 10-2 mbar) iji mee nano-SCE na electrode stack.Ọkpụrụkpụ nano-SCE bụ 380 μm.N'ikpeazụ, a pịara mpempe lithium n'elu SCE/electrode stacks dị ka anode, ma mechie cell mkpụrụ ego ahụ.Emere nha electrochemical site na iji Solartron 1470E potentiostat na ụlọ okpomọkụ.

Ihe mgbakwunye maka akụkọ a dị na http://advances.sciencemag.org/cgi/content/full/6/2/eaav3400/DC1

Tebụl S1.Njirimara arụrụ arụ nke silica matrix na nano-SCE maka mmụba molar nke mmiri mmiri ionic ruo silica (x uru) kpebisiri ike site na N2 adsorption/desorption ma ọ bụ nha BET na nlebanya TEM.

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

Oge nzipu: Jul-15-2020