ʻO ka silica gel solid nanocomposite electrolytes me ka hoʻolaha ʻana i ka conductivity interfacial i ʻoi aku ma mua o ka nui o ka conductivity Li-ion o ka hoʻopiha wai electrolyte ionic.

ʻO ka hoʻololi ʻana i nā pākahi Li-ion solid-state e hiki ai ke holomua i ka density ikehu o 1000 W·hola/lita a ma waho.Ua ʻimi ʻia nā mea hui o ka mesoporous oxide matrix i hoʻopiha ʻia me ka nonvolatile ionic liquid electrolyte fillers ma ke ʻano he koho electrolyte paʻa.Eia nō naʻe, ʻo ka hoʻopaʻa maʻalahi o nā hoʻonā electrolyte i loko o nā pores nanometer-sized e alakaʻi i ka conductivity ion haʻahaʻa i ka piʻi ʻana o ka viscosity.Maʻaneʻi, hōʻike mākou i ka Li-ion conductivity o nā nanocomposites i loaʻa i kahi mesoporous silica monolith me kahi mea hoʻopiha wai electrolyte ionic hiki ke kiʻekiʻe i nā manawa he nui ma mua o ka electrolyte wai ionic maʻemaʻe ma o ka hoʻokomo ʻana i kahi papa hau interfacial.ʻO ka adsorption ikaika a me ka hoʻonohonoho ʻana i nā molekole wai ionic e hoʻoneʻe iā lākou a paʻa ʻole e like me ka papa hau interfacial ponoʻī.ʻO ka dipole ma luna o ka papa mesophase adsorbate ka hopena i ka hoʻonā ʻana o nā liona Li+ no ka hoʻonui ʻana.Hiki ke hoʻohana ʻia ke kumu i hōʻike ʻia o ka hoʻonui ʻana i ka ion conduction i nā ʻōnaehana ion like ʻole.

Manaʻo ʻia nā electrolytes solid-state e hāʻawi i ka hoʻoikaika hou ʻana no nā pā Li-ion e ʻoi aku ma mua o ke kaupaku kūpono o 800 W·hour/lita a i ʻole 300 W·hour/kg i kau ʻia ma luna o nā cathode a me nā anode chemistries i kēia manawa.ʻO ka piʻi ʻana o ka ikehu i manaʻo ʻia no nā ʻenekona solid-state e loaʻa mai i kekahi mau haʻawina, e ʻimi ana i ka hoʻonui ʻana i ka pākēneka o nā mea hana i loko o ke kelepona.ʻO ka mea i hoʻolaha nui ʻia ʻo ka hoʻokomo ʻana i ka metala lithium e pani i ka graphite a me ka graphite / silicon ma ke ʻano he anode.Loaʻa i ka metala lithium maʻemaʻe ka ikehu kiʻekiʻe loa a no laila e koi ʻia ka liʻiliʻi loa.Eia nō naʻe, he nui nā pilikia e pono e hoʻoholo ʻia, e like me ka hopena hiki ʻole ke hoʻololi ʻia (a pēlā ka hoʻohana ʻana) o ka metala lithium, ka hoʻokumu ʻana o dendrite, ka piʻi ʻana o ka nui o kēia manawa no nā pahu lithium planar i hoʻohālikelike ʻia i nā electrodes porous graphite (silicon), a, hope loa. akā ʻaʻole liʻiliʻi, ʻo ka "nalo" o ka lithium i ka wā o ka hoʻokuʻu ʻana (deplating) a pēlā e nalowale ai ka pilina me ka electrolyte paʻa.ʻO ke ʻano paʻa ʻole o ka mīkini paʻa paʻa electrolytes, ʻaʻole i hoʻokō pono ʻia, a pono e hoʻopili ʻia nā kaomi koʻikoʻi e kaomi paʻa i ka lithium i ka mea electrolyte paʻa.ʻOi aku ka nui o ka hoʻohaʻahaʻa ʻana i ka ʻili o ka ʻili, e alakaʻi ana i ka hana dendrite kūloko a me nā waihona spongy.ʻOi aku ka hoʻokō ʻana o nā electrolytes polymer akā ʻaʻole i hōʻike i ka nui o ka conductivity ionic i ka lumi wela.ʻO nā mea hou hoihoi loa e pili ana i kēia ʻano he silica gel electrolytes, i kapa ʻia hoʻi he "ionogels," kahi i hoʻopaʻa ʻia ai kahi ionic liquid electrolyte (ILE) i loko o kahi nanoporous silica matrix (1).ʻO ka porosity kiʻekiʻe loa o ka matrix silica (70 a 90%) hāʻawi i kēia mau mea electrolyte nanocomposite i ka like me ka gel a pēlā e hoʻokō ai i ka mechanically e like me nā electrolytes polymer.Hōʻike ʻia kēia mau silica gels i kekahi manawa ma ke ʻano he hybrid solid electrolytes, no ka mea he wai.Eia naʻe, no nā nanocomposites silica, e like me nā mea i wehewehe ʻia ma kēia pepa, lilo ka ionic "wai" electrolyte i mea paʻa i ka wā i hoʻopaʻa ʻia i loko o nā ʻumi o nā kaha nanometer-nui ma o ka hoʻonui ʻana i ka viscosity a me ka adsorption ma ka pā silica e hoʻopaʻa ana i ka. kaila.Inā hana wale ka silica matrix ma ke ʻano he mea hoʻokaʻawale porous, a laila ʻo ka piʻi ʻana o ka viscosity no ka electrolyte wai paʻa e alakaʻi i ka emi ʻana o ka conductivity ionic.Akā, ʻo ka pilina ma waena o nā molekala ILE a me ka pā silica pore e hoʻokaʻawale i nā waiwai o ka nanocomposite mai ka huina o kāna mau ʻāpana.Ua hōʻike ʻia ka hoʻopili ʻana o nā wai ionic ma luna o nā oxides me ka hoʻokumu ʻana i nā papa mesophase paʻa a hiki i kahi nanometer i ka mānoanoa ma nā papa planar me ka microscopy ikaika atomika (2).ʻO ka hoʻopili koho ʻana o nā anion wai ionic a me nā cations ma nā ʻili oxide hiki ke alakaʻi i ka hoʻonui Li + conductivity ma kēia mau pilina.ʻOiaʻiʻo, ʻo ka hoʻonui ʻana ma nā pilina oxide e uku a i ʻole ma mua o ka emi ʻana o ka conductivity ma o ka ILE i hoʻopaʻa ʻia i loko o ke kumu o nā pores.No laila, makemake ʻia ka nui o ka pore liʻiliʻi a me ka ratio kiʻekiʻe o ka ʻili-a-nui.I kēia manawa, ua hōʻike ʻia nā ionogels me nā conductivities ion e pili ana i ka ILE ponoʻī ma o ka hoʻonui ʻana i ke ʻano mesoporous (3).ʻO ia hoʻi, ua loaʻa mua ka hoʻonui ʻana i ka interface akā ʻaʻole i ka nui o ka conductivity bulk.

Hoʻomaka ka hoʻomākaukau ʻana o nā ionogels mai kahi hui wai homogeneous, kahi i hoʻohui ʻia ai kahi ILE i kahi solution sol-gel precursor no ka synthesis o ka matrix oxide (4, 5).Ma kēia ʻano, hoʻokumu ka ILE a me ka matrix i mea hoʻohui ma ke ʻano "in situ": Hoʻopili nā mea mua i ka hoʻonā e hana i kahi matrix oxide a puni ka template wai ionic, e hoʻopili ana iā ia i ke kaʻina hana.Ma lalo o kekahi mau kūlana synthesis, hiki i ka ILE-SCE i hoʻomākaukau ʻia (solid composite electrolyte) ma ke ʻano o kahi monolith me ka ILE i hoʻokomo ʻia i loko o kahi pūnaewele mesoporous inorganic oxide mau.I kēia manawa, ua hoʻomākaukau ʻia ka hapa nui o nā ILE-SCE ma muli o ka silica, ʻoiai ua hana ʻia nā laʻana me ka alumina (6), titania (7), a me ka tin oxide (8).ʻO ka hapa nui o nā hoʻoheheʻe sol-gel i hōʻike ʻia he ILE, he alkyl-silicate e like me tetraethyl orthosilicate (TEOS) ma ke ʻano he silica precursor, a me ka waika formic ma ke ʻano he reagent a me ka solvent (9, 10).E like me ka manaʻo i manaʻo ʻia (11) no kēia kaʻina hana sol-gel, hana nui ʻia ka silica e ka hopena ma waena o TEOS a me ka waika formic, ʻoiai ua hana ʻia ka wai i ka wā o ka hana sol-gel.Ma waho aʻe o kēia mau huihuʻi "nonaqueous" i hoʻokumu ʻia i ka waikawa formic, ua wehewehe pū ʻia nā hana sol-gel wai me ka HCl ma ke ʻano he catalyst a me H2O ma ke ʻano he reagent (me ka mea hoʻoheheʻe organik) ua wehewehe pū ʻia, akā naʻe, i kēia hihia no ka synthesis o kahi hui silica me. wai ionic wale nō (12–15).

ʻO ka maʻamau, hōʻike nā ionogels i ka conductivity ion ma lalo o ka hōʻike ILE.He 30 a 50% wale nō ka nui o ka waiwai ILE i ka hanauna mua o nā ionogel, ʻoiai ua hōʻike ʻia kekahi mau hiʻohiʻona a hiki i 80% (9, 10, 16, 17).Ua noiʻi ʻia ka hopena o ka ʻike ILE a me ka pore morphology i ka conductivity ionogel (3);akā naʻe, ʻaʻole ʻike ʻia kahi noiʻi ʻōnaehana o nā hopena hoʻonui interface.ʻO Wu et al.(18) i hōʻike koke ʻia ma kahi ionogel i hoʻohana ʻia i loko, kahi i hāʻawi i ka hoʻonui conductivity i hoʻohālikelike ʻia me ka ILE nui.Hoʻopili ʻia ka hoʻonui ʻana i ka pilina ma waena o ka anion a me ka hui hana 3-glycidyloxypropyl ma ka ʻili silica.Kākoʻo kēia ʻike i ka manaʻo e hiki ke hoʻoikaika ʻia ka hana ʻana o ka ʻili i ka hoʻolaha hoʻolaha.

Ma kēia hana, hōʻike mākou i ka hoʻokumu ʻia ʻana o kahi papa wai hau paʻa ma ka silica a kikoʻī i ke ʻano o ka hoʻokele Li-ion interfacial ma o ka hoʻonui ʻana i ka pilina dipole ma waena o ka papa hana hau hau a me ka adsorbed ionic liquid mesophase layer.Ma ka hui pū ʻana o ka ʻili kiʻekiʻe o loko a me ka papa hana hau nui, ua hoʻokō ʻia nā nanocomposite electrolytes paʻa (nano-SCE) me 200% kiʻekiʻe Li-ion conductivity ma mua o ka nui ILE kuhikuhi.Hōʻike ʻia ka matrix silica i kahi ʻano mesoporous monolithic maoli me ka nui o ka pore a me nā ʻāpana ʻili a hiki i 90% a me 1400 m2/g, no laila e hāʻawi ana i nā lakio o ka ʻili a me ka nui e ʻae i ka hāʻawi nui ʻana o ka hoʻonui conduction ma kēia mau pilina.Ma muli o ka hoʻohana pono ʻana o ka ʻili silica i hui pū ʻia me ka hoʻonui ʻana i ka ratio surface-to-volume, nano-SCE me nā conductivities ion i ʻoi aku ma mua o 10 mS/cm hiki ke hana ʻia a no laila he nani loa no nā ʻenekini mana nui no nā noi kaʻa.

ʻO ka manaʻo o kā mākou pepa e pili ana i ka hana o ka hoʻonui ʻana i ka conductivity interface ma o ka hoʻokumu ʻana i kahi papa mesophase me nā hōʻike mai Raman, Fourier transform infrared (FTIR), a me ka spectroscopy nuclear magnetic resonance (NMR).Hōʻike ʻia ka paʻa ʻana o kā mākou mea nano-SCE ma nā volta kiʻekiʻe me ka hoʻohana ʻana i nā electrodes lithium manganese oxide (LMO) kiʻiʻoniʻoni lahilahi.Ma kēia ala, hoʻomau ka nānā ʻana i ka mea ma mua o ka hoʻohui electrode a me nā pilikia hui pū.Pēlā nō, ʻike piha ʻia ka puka aniani electrochemical a me ke kūpaʻa e kūʻē i nā foil metala lithium.Hōʻike ʻia ka hana a me ka hoʻohui ʻana o kā mākou nano-SCE ma o ka hui ʻana a me ka helu ʻana i nā hoʻokolohua hana o ka lithium iron phosphate (LFP) a me ka lithium titanate (LTO).Ua hōʻike ʻia ke kūpaʻa o kā mākou electrolyte a me ka hana ʻole electrochemical o ka wai hau ma o ke kaʻa holo lōʻihi o nā pūnaewele Li-SCE-Li symmetric.ʻO ka hoʻonui ʻana i ka nui o ka ikehu, ka hoʻokō ʻana, a me ka hana kaʻa kaʻa o nā cell i hui piha ʻia ke kumu o nā pepa hahai (19, 20).

Ua ʻike ʻia ka hoʻolaha ʻana o ka ion conductivity interfacial i nā ʻōnaehana composite ʻelua-phase no kahi kokoke i 90 mau makahiki (21).No ka laʻana, ua hōʻike ʻia a hiki i ʻehā mau kauoha o ka hoʻonui ʻana i ka conductivity ionic no nā composites o ka paʻakai lithium maʻalahi e like me ka lithium iodide me nā ʻāpana mesoporous oxide e like me ka silica a i ʻole alumina i hoʻohālikelike ʻia i ka conductivity ion o ka electrolyte paʻakai lithium maʻemaʻe (22).Hiki i nā iona i loko o kēia mau SCE ke ho'opuehu wikiwiki loa ma ka papa lua uila i ho'emi 'ia i ka Li ion (a ha'aha'a ha'aha'a) i ho'okumu 'ia ma ka interface oxide/electrolyte.ʻO ka mea pōʻino, ʻaʻole i ʻoi aku ka mana o ka ion i loaʻa i kēia mau mea ʻelua ʻāpana paʻa paʻa paʻa (1) ma mua o ka paepae 1-mS/cm2 e pono ai e hoʻopaʻa i ka mamao liʻiliʻi ma waena o nā papa hōʻiliʻili o kēia manawa i ka pā Li-ion. .ʻO ka manaʻo o ka heterogeneous doping me ka oxide matrix e ʻenekinia i ka ionic conductivity ua ʻimi pū ʻia no nā polymer electrolytes (23) a me ILEs (24), ʻoi aku ka kiʻekiʻe o ka conductivity intrinsic ionic e hoʻomaka me.Eia hou, ua wehe ka molekele waiwai (stereo)kemika o ke kolu o ka mea i nā hana hoʻoheheʻe ion, no ka mea, hiki i nā (di) polar solvent-like mole ke komo i ka hana ʻana i ka papa pālua uila.ʻOiai ka hana hoʻoheheʻe ʻana o nā pūʻulu eter i loko o ka polyethylene oxide polymer electrolytes e hāʻawi i nā conductivities ion solid-state o ~10−6 S/cm no LiClO4 a i ~10−5 S/cm no LiN(SO2CF3)2, ko lākou hui pū me ka silica, alumina. , a i ole titania nanoparticles hiki io ke haawi i oi aku mamua o 10-fold enhancement i ana ion conductivity (25), aka, ma lalo o ka lumi wela paepae o 1 mS/cm.ʻO nā haʻina ILE nā hui pū ʻana o kahi solute Li-paʻakai a me kahi mea hoʻoheheʻe wai ionic, hiki ke loaʻa i nā conductivities intrinsic ionic kiʻekiʻe ma waena o 0.1 a me 10 mS/cm (26, 27).Ua hana ʻia kekahi mau hoʻāʻo e hoʻonui i ka conductivity ion ma o ka hui ʻana a i ʻole ka gelling me nā nanoparticles oxide a i ʻole e hoʻopaʻa i ka ILE i nā microparticles mesoporous (9, 16, 28, 29).Eia naʻe, a hiki i kēia manawa, ʻaʻole i ʻike ʻia ka hoʻonui ʻana i ka conductivity ion no nā mea hui ʻekolu Li-salt/ionic liquid/oxide (fig. S1).ʻOiai ʻo ka hoʻohana ʻana i nā microparticles silica mesoporous e hopena i ka conductivity kiʻekiʻe i ka hoʻohālikelike ʻia me nā composites me nā nanoparticles paʻa, ʻaʻole lawa ka ʻāpana o ka ʻili a me ka hoʻolaha ʻana o ka ion e ʻoi aku ma mua o ka conductivity ILE nui.

ʻO ka silica Mesoporous kahi mea kaulana i hoʻohana ʻia i ka catalysis.Hana ʻia ia e ka hydrothermal a i ʻole ka sol-gel synthesis maʻalahi.ʻO nā kaʻina hydrothermal ka mea maʻamau e alakaʻi i nā pauka mesoporous, akā me ka mālama pono ʻana i ke kaʻina hana sol-gel mahana, ua hana ʻia nā monoliths aniani porous nui a i ʻole aerogels.Hoʻokumu ʻia ka matrix silica ma o ka hydrolysis a me ka condensation reactions o tetra-alkyl orthosilicates (30).ʻO ka mea nui i ka mana o ka hoʻolālā pore ʻo ia ka hoʻohana ʻana i nā templates, no ka laʻana, he surfactant-type micelle, kahi i hoʻokumu ʻia ai ka matrix silica.Ke hoʻohui ʻia kahi wai ionic e like me ka mole e hoʻohālikelike ʻia, pili ka matrix silica hydrated me ka wai ionic, hana i gel, a ma hope o ka ho'ōla ʻana a me ka hoʻomaloʻo ʻana, hoʻopaʻa ʻia ka wai ionic i loko o ka matrix silica nanoporous paʻa (13).Ke hoʻohui ʻia ka paʻakai lithium ma ke ʻano he kolu o ka ʻāpana, ʻo ka ILE i hoʻopaʻa ʻia i loko o ka silica matrix e hana i kahi silica gel electrolyte, kahi i kapa ʻia ʻo ionogel (24).Eia nō naʻe, i kēia manawa, hōʻike kēia mau silica gel electrolytes i nā conductivities e pili ana i ka ILE nui akā ʻaʻole i ʻoi aku ma mua o ia, koe wale no kahi hihia kahi i hoʻohana ʻia ai ka silica (e nānā i ka Introduction) (18).

Maʻaneʻi, hōʻike mākou i ka hoʻolaha ʻōnaehana o ka conductivity Li-ion o ka nanocomposite ma mua o ka ILE maʻemaʻe.Hoʻohana ʻia ka laʻana o 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP-TFSI) maanei.Ua manaʻo ʻia ʻo ka adsorption o nā molekele wai ionic ma ka ʻili silica i hoʻopau ʻia e OH e hoʻoikaika ʻia e ke alo o kahi papa wai hau interfacial.ʻO ka hoʻopaʻa hydrogen ikaika ma waena o ka wai hau a me ka anion TFSI− hoʻoulu i ka hoʻonohonoho molekala o ka wai ionic, e like me nā kāʻei i kauoha ʻia i hoʻokumu ʻia i loko o nā wai ionic (31).ʻO ka ʻokoʻa koʻikoʻi me nā kāʻei kapu i hoʻokumu ʻia i ka ILE nui, ʻo ia ka hana ʻana o ka papa hau ma ke ʻano he papa hana e (i) hoʻoulu i ka hoʻonohonoho molekala ma ka ʻili oxide a (ii) hoʻokomo i ka ikaika H-bonding e hoʻoulu i nā dipoles e hoʻokuʻu iā Li+ manuahi. no ka hoʻonui ʻia ʻana.Ma hope o ka hoʻonui ʻana i ka manaʻo Li + manuahi, e hōʻike mākou i ka haʻahaʻa o ka ikehu hoʻāla no ka diffusion ma ka ʻaoʻao hui me ka papa ILE adsorbed a me ka papa wai hau.

ʻO ka papa wai ʻili liʻiliʻi-monolayers-mānoanoa ma luna o ka silica he papa paʻa like ia, no ka mea, ua hoʻopaʻa ikaika ʻia i nā hui silanol ma o nā alahaka H a no laila ua kapa ʻia ʻo ia he papa hau (32).ʻO kona mānoanoa a me ka mānoanoa (manaʻo ʻia a hiki i ʻekolu a ʻehā mau monolayers, me ~ 0.25 nm no ka hau monolayer) aia i ka thermodynamic equilibrium me ka ʻāpana wai kaomi [relative humidity (RH)] i loko o ke kaiapuni (fig. S2).Hōʻike mākou i ka piʻi ʻana o ka conductivity ion me ka mānoanoa o ka papa wai hau e like me ka hoʻopili ʻana o ka hydrogen me nā papa ionic adsorbed.Paʻa ka papa wai hau e like me ka wai aniani i loko o nā pūhui kemika.He ʻokoʻa loa kēia me nā electrolytes aqueous super concentrated a i ʻole i kapa ʻia he wai i loko o nā hui paʻakai, kahi i hoʻonui nui ʻia ka puka aniani electrochemical akā, i ka hopena, e hoʻoikaika mau ana ka wai (33).

ʻOkoʻa mai ka waika formic acid-catalyzed ionogel recipes, ua hoʻohana mākou i ka pH 5 haʻahaʻa me ka nui o ka wai a me ka PGME (1-methoxy-2-propanol) i hoʻohui ʻia i kahi precursor TEOS me ka paʻakai Li-TFSI a me ka wai ionic BMP-TFSI.Ma kēia pH, ua lohi nā hopena hydrolysis, ʻoiai ua maikaʻi ka condensation (30).Ua manaʻo ʻia nā Li ion e hana ma ke ʻano he catalyst no ka hopena hydrolysis, no ka mea, ʻaʻohe gelation i hana ʻia me ka loaʻa ʻole o ka paʻakai lithium i ka pH like o 5. ʻO ka ratio molar o ka wai ionic i TEOS (a pēlā nā moieties silica). i hōʻike ʻia e like me ka waiwai x a ua hoʻololi ʻia ma waena o 0.25 a me 2. Ua mālama ʻia ka ratio molar o BMP-TFSI i Li-TFSI ma 3 (e like me ka 1 M Li-ion solution).Pono ka maloʻo lohi no ka mālama ʻana i ka paʻa o ke ʻano o ka monolith (e ʻike i nā mea hana a me nā ʻano).Hōʻike ka Kiʻi 1A i ke kiʻi o kahi pellet monolithic i loaʻa ma hope o ka maloʻo ʻana.Ua lawa ka maloʻo maloʻo 72-hola e hoʻoneʻe i ka wai a hiki i kahi i hoʻoneʻe ʻia ai ka wai manuahi a pau ka pae wai hau i hoʻopaʻa ʻia, e like me ka hōʻoia ʻana e FTIR.ʻAʻole i ʻike ʻia nā haʻalulu no ka wai manuahi ma 1635 cm−1 i kekahi o nā laʻana ma hope o ke kaʻina hoʻomaloʻo maloʻo (Fig. 2).No ka hoʻohālikelike, hōʻike ʻia ka spectrum FTIR no kahi laʻana nano-SCE (x = 1.5) i mālama ʻia no 1 pule i loko o kahi pahu mīkina N2 ma 60% RH.I kēia hihia, ʻike ʻia kahi kiʻekiʻe wai manuahi.ʻO nā laʻana a pau, ma ka ʻaoʻao ʻē aʻe, ua hōʻike i kahi hōʻailona maopopo no ka hoʻohana ʻana o ka silanol surface functionalization (Si─OH e kulou ana ma waena o 950 a me 980 cm−1) a me kahi papa wai hau adsorbed (O─H e kau ana ma ~3540 cm−1) i hoʻopaʻa ʻia i nā hui ─OH ma o ka hoʻopaʻa ʻana H (nā kikoʻī hou aku ma lalo).Ua kaupaona ʻia nā hue ma mua a ma hope o ka hoʻomaloʻo ʻana e ana i ka wai i mālama ʻia ma ka nano-SCE (papa S1).Ma hope, e helu mākou i ka helu o nā monolayers pili o nā papa hau i hoʻopaʻa ʻia i ka ʻili mai ke kaumaha keu.Lawe ʻia nā pellet maloʻo maloʻo maloʻo i loko o ka pahu mīkina [<0.1-ppm (mau ʻāpana o ka miliona) H2O] a mālama ʻia i loko o nā hue i pani ʻia no ka mālama ʻana i ka wai maoli.Ua lawe ʻia kahi leo liʻiliʻi mai ka pellet no ka hōʻike hou ʻana.

(A) Kiʻi o ʻelua nano-SCE pellets (hema) synthesized i loko o ka vial;ma hope o ka gelation, loaʻa kahi pellet transparent.E hoʻomanaʻo i ka ʻike piha ʻana o ka pellet a no laila ua hāʻawi ʻia i kahi hue polū no ka ʻike.Ke hoʻoneʻe ʻia ka ILE, waiho ʻia kahi pellet keʻokeʻo palupalu no ka matrix silica porous loa (akau).(B) E nānā ana i ke kiʻi electron microscopy (SEM) o ka matrix SiO2 i koe ma hope o ka wehe ʻia ʻana o ka ILE.(C) Zoom o ke kiʻi i hōʻike ʻia ma (B) e hōʻike ana i ke ʻano mesoporous o ka mea matrix me kekahi mau macropores.(D) Transmission electron microscopy (TEM) kiʻi e hōʻike ana i kahi paʻa paʻa o 7- a 10-nm silica nanoparticles ma ke ʻano he hale kūkulu o ka mea porous matrix.(E) ʻO ka porosity o ka hale matrix i hoʻolālā ʻia no nā lākiō molar like ʻole o ILE e pili ana iā SiO2 (waiwai x).Hāʻawi ka laina ʻokiʻoki i ka porosity theoretical i hoʻoholo ʻia mai ka hakina leo o ILE a me ka silica.Ua maloʻo nā ʻāpana acetone i holoi ʻia (nā ʻāpana ʻeleʻele) i ka ea, e hāʻawi ana i ka hāʻule hapa o ka hale no x > 0.5.ʻO ka hoʻomaloʻo nui CO2 o ka nano-SCE i holoi ʻia ethanol (nā pōʻai ʻōmaʻomaʻo) e pale i ka hāʻule ʻana a hiki i ka x = 2 no ka wehe lohi ʻana o ka CO2 (poʻe hāmama).BET, Brunauer-Emmett-Teller.Kiʻi kiʻi: Fred Loosen, imec;Akihiko Sagara, Panasonic.

(A) IR spectra o ka nano-SCE e like me ka maloʻo i loko o ka ʻeleʻele (ʻeleʻele) a ma hope o ka maloʻo ʻana i loko o kahi pahu mīkina lima me 0.0005% RH no 9 mau lā (uliuli) a hōʻike ʻia i 30% RH no 4 mau lā (ʻulaʻula) a me 60 % RH no 8 mau lā ('ōmaʻomaʻo), kēlā me kēia.ʻau, ʻokoʻa ʻokoʻa.(B) Nā voltammograms Cyclic o kahi waihona Li/SCE/TiN me nā helu x o 1.0 (uliuli), 1.5 ('ōmaʻomaʻo), a me 2.0 (ʻulaʻula) a me ka kuhikuhi ILE (ʻeleʻele);hōʻike ka inset i ke au i ka pālākiō logarithmic.(C) Cyclic voltammograms o Li/SCE (x = 2)/40-nm TiO2 ahu (ʻulaʻula), ILE (ʻeleʻele kiko), a me ILE spiked me 5 kaumaha % (wt %) H2O (dash-dotted blue line);ma (B) a me (C), ua hana ʻia nā ana me ILE a me ILE me H2O i ʻekolu-electrode hoʻonohonoho me TiN ma ke ʻano he electrode hana a me Li ma ke ʻano he counter a me nā electrodes kuhikuhi.Hoʻomaloʻo ʻia ka SCE no 2 mau lā i loko o ka pahu mīkina ma hope o ka maloʻo ʻana.

Ua hoʻonui ʻia ka conductivity ionic (σi) o kā mākou nano-SCE i hoʻopaʻa ʻia me ka hapa leo o ka ILE (waiwai x) e like me nā mea i hoʻohui ʻia (fig. S1).Eia naʻe, ma kēia hihia, ʻoi aku ka nui o ka conductivity ionic ma mua o ka ILE maʻemaʻe ponoʻī ma mua o 200% no nā koina x kiʻekiʻe loa (Fig. 3).Eia kekahi, ʻo ka hilinaʻi wela o ka nano-SCE me ka ion conductivity i hoʻonui ʻia i hōʻike i kahi ʻano ʻokoʻa ma mua o ka ILE maʻemaʻe: ʻOiai ʻo ka Li-TFSI ma BMP-TFSI ILE e hōʻike ana i kahi loli maopopo o ka conductivity a me ka ikehu hoʻāla (slope) a puni ka hoʻoheheʻe. ʻO ke kiko o ka hui ʻana ma 29°C, ʻaʻole ʻo ka nano-SCE me ka conductivity hoʻonui.Akā, hōʻike ia i ka hoʻololi mau ʻana i ka σi me ka mahana, e hōʻike ana ua hoʻokumu ʻia kahi ʻano i ʻike mua ʻole ʻia o ka pae a i ʻole mesophase, a laila ke kuleana o ka conductivity i hoʻonui ʻia.Eia kekahi, ʻo ka liʻiliʻi liʻiliʻi a no laila haʻahaʻa i ka ikehu hoʻāla no ka diffusion no ka nano-SCE i hoʻohālikelike ʻia me ka ILE e hōʻike ana i nā waiwai waiwai like ʻole (fig. S3).Manaʻo ʻia ʻo ka pilina ikaika ma waena o nā molekala wai ionic a me ka papa hau paʻa ma ka scaffold silica ke kuleana no ka hana mesophase i ʻike ʻia, e like me ke kūkākūkā ʻana me ke kumu hoʻohālike i manaʻo ʻia ma lalo nei.

(A) Hoʻomaloʻo ʻia ka wela o ka conductivity o nā nano-SCE no 8 mau lā i loko o ka pahu mīkina lima (GB) me nā helu x o 2 (nā ʻāpana ʻeleʻele), 1.75 (nā pōʻai ʻalani), 1.5 (nā huinakolu uliuli), a me 1.0 (nā huinakolu ʻōmaʻomaʻo. ) a me ka hōʻike ILE (nā huinahā hāmama).(B) Hoʻomaloʻo ʻia ka hana o nā nano-SCE i GB no 0 mau lā (nā ʻāpana ʻōmaʻomaʻo), 10 mau lā (nā huinakolu ʻeleʻele), a me 138 mau lā (nā huinakolu uliuli).(C) Conductivity versus kumu huinahalike o ka manawa maloʻo o nano-SCE me x waiwai o 2 (ʻeleʻele huinahalike), 1.5 (blue triangles), 1.0 ('ōmaʻomaʻo triangles), a me 0.5 (brown daimana).(D) Conductivity o nano-SCE me x = 2 (ʻeleʻele huinahalike), 1.5 (blue triangles), a me 1.0 ('ōmaʻomaʻo triangles) hōʻike 'ia i loko o ka N2-piha humidity keena.

Aia ka lewa argon i loko o ka pahu mīkina lima ma lalo o 0.1 ppm o ka wai, e pili ana i ka 0.0005% RH, kahi kaomi wai hapa o 0.01 Pa, a i ʻole kahi hau o −88°C.E like me ka helu o nā papa wai i hoʻopaʻa ʻia ma ka silica i hoʻopau ʻia i ka silanol i ke kaulike me ke kaomi ʻāpana o ka wai (fig. S2), e hoʻopuehu mālie ka wai ʻili mai ka nano-SCE a hoʻohaʻahaʻa i nā kihi.Hōʻike ka Figure 3C i ka loli o ka conductivity no 23 μl o nano-SCE ma ke ʻano he hana o ka manawa noho i loko o ka pahu mīkina.E emi ana ka hana o ka ion me ka maloʻo ʻana a hiki i ka hoʻopololei ʻana i kahi waiwai e pili ana i ka ʻili silica i ke kaulike me ke kaomi ʻāpana wai o 0.01 Pa i loko o ka pahu mīkina lima.ʻOiai ma lalo o nā kūlana maloʻo loa o ka pahu mīkina lima, ma ka liʻiliʻi loa, aia kahi monolayer ʻāpana o ka wai adsorbed ma ka silanol, ʻoiai ʻo Raman spectroscopy e hōʻike mau ana i kahi hōʻailona ma 3524 cm−1, kahi kikoʻī no ka monolayer mua o ka wai adsorbed ma ka silanol (Fig. 4B).ʻO ka conductivity ion ma lalo o nā kūlana saturated ʻoi aku ka maikaʻi ma lalo o kēlā me kēia ILE i nā hihia āpau.No laila, ʻaʻole lawa ka hoʻonui ʻana e hoʻopaʻi i ka nalowale o ka conductivity ionic o ka ILE i hoʻopaʻa ʻia i loko o ke kumu o ka pore.

(A) IR spectra o nano-SCE me ka x waiwai o 1.5 (ʻulaʻula), ILE kuhikuhi (ʻeleʻele), a me SiO2 (uliuli), e hōʻike ana i ka hui O═S═O (1231 cm−1) i loko o ka ka launa pū ʻana me nā pūʻulu OH ma ka ʻili silica.(B) Raman spectra o nano-SCE me nā helu x o 2 (ʻeleʻele), 1.5 (ʻulaʻula), a me 0.5 (uliuli), e hōʻike ana i ka hele ʻana o ka wai hau i hoʻopaʻa ʻia ma ka silica i hoʻopau ʻia ʻo silanol no ka nano-SCE kokoke i ka saturation (0.0005). % RH) i loko o kahi pahu mīkina lima (30 lā).(C) Ke kumu hoʻohālike i manaʻo ʻia no ka launa pū ʻana ma ka nano-SCE me ka wehe ʻana o Li-TFSI i ka Li+ manuahi ʻoiai ʻo ka TFSI− anion e puʻunaue ana i kahi ʻāpana o kāna uku ʻino me ka adsorbed ice-TFSI-BMP layer;Hōʻike nā kala i nā mea like ʻole me ka poni (silicon), ʻulaʻula (lithium), melemele ʻeleʻele (sulfur), ʻalani (oxygen), uliuli (nitrogen), keʻokeʻo (hydrogen), a me ka ʻōmaʻomaʻo (fluorine).Hōʻike nā laina poni poni i ka pilina hydrogen ma waena o ka pūʻulu O═S o ka anion TFSI a me nā pūʻulu OH o ka ʻili silica hydroxylated.Hiki i nā Li+ ion i hoʻokuʻu ʻia e ka dipole ma luna o ka papa adsorbed hiki ke neʻe aku ma o nā papa wai ionic ma hope aʻe a i ʻole ma luna o nā papa kuhikuhi.E hoʻomanaʻo, ma muli o ka ikaika o nā paʻa hydrogen a me ka uku like ma ka silica, hiki ke hana ʻia nā papa adsorbed lehulehu.Hōʻike ʻia ka spectra piha ma ka fig.S8.

ʻO kahi nānā hoihoi ʻo ia ka pilina laina me ke kumu huinahā o ka manawa maloʻo e like me ka mea i hōʻike ʻia ma ke kiʻi 3C, e hōʻike ana i ka hoʻololi pololei ʻana o ka conductivity i nā loli i ka nui o ka wai hau adsorbed ma luna o ka silica a ʻo ka wehe ʻana o kēia wai ili. palena palena.E hoʻomaopopo i ka "maloʻo" wale nō ma kahi ākea kahi i haʻahaʻa ai ka RH ma mua o ka papa hau equilibrium.ʻAʻole i loli ka conductivity, no ka laʻana, i loko o nā keʻena kālā pani i hoʻohana ʻia no nā ana e pili ana i ka mahana.

Ua ana ʻia ka hilinaʻi wela o ka nano-SCE no nā manawa like ʻole o ka maloʻo ʻana i ka pahu mīkina.I ka hoʻokokoke ʻana o ka conductivity o ka nano-SCE maloʻo i ka ILE, ua hoʻololi iki ʻia ka σi mau me 1/T profiles no ka conductivity mesophase i ka ʻaoʻao no ka ILE, e hōʻike hou ana i ka hāʻule a puni kona wahi heheʻe (fig. S3).Kākoʻo hou kēia ʻike i ka manaʻo e hana ana ka papa hau ma ke ʻano he papa hana no ka launa pū ʻana me ka ILE, e hāʻawi ana i ke ʻano mesophase i ka nano-SCE.No laila, ke wehe ʻia ka papa hana, hoʻopaʻa wale ʻia ka ILE i loko o kahi membrane mesoporous oxide.

ʻO nā ana o ka puka aniani paʻa electrochemical e hōʻoia i ka paʻa o ka wai hau i loko o ka nano-SCE, no ka mea, ʻaʻohe piko no ka hoʻemi ʻana i ka wai a i ʻole oxidization i ʻike ʻia ma ka inert TiN electrode (Fig. 2) ʻaʻole hoʻi ma kahi TiO2 thin-film electrode, i hana ʻole. ma ke ano he electro-catalyst no ka hoemi wai.Akā, ua like loa ke kūpaʻa electrochemical o ka nano-SCE me ka ILE a no laila ua kaupalena ʻia e ka hoʻonā ʻana o TFSI- ma nā electrode potentials> 4.3 V a me ka hōʻemi ʻana o TFSI- a me BMP + ma nā hiki <1 V versus Li+/Li (33).No ka hoʻohālikelike, hōʻike ʻia kahi voltammogram no kahi ILE me 5 paona % (wt%) wai i hoʻohui ʻia (maʻiʻo like me kekahi nano-SCE; e ʻike i ka papa S1).I kēia hihia, ana ʻia kahi lālā cathodic no ka hoʻemi wai ma hope koke o ka Li-intercalation peak o anatase ma 1.5 V versus Li+/Li.

Hoʻoholo nui ʻia ke kūpaʻa wela a me (electro) kemika o ka nano-SCE e ka mea hoʻopihapiha ILE.Ua hōʻike ʻo Thermogravimetric analysis (TGA) i ke kūpaʻa wela o ka SCE a me ka ILE a hiki i 320°C, me ka nānā ʻole i ka ratio ILE-to-silica (fig. S4).Ma luna aʻe o kēia mahana, hoʻoheheʻe ʻia ka Li-TFSI a me BMP-TFSI i nā mea hoʻoheheʻe, a ʻo ka silica matrix wale nō ke koe ma kahi o 450°C.ʻO ka pākēneka nui i koe ma hope o ka hoʻoheheʻe ʻana i ka wela ua pili pono loa me ka hakina silica i ka SCE.

ʻAʻole i hōʻike ʻia ka nano-SCE i kahi microstructure maʻemaʻe i loko o ka scanning electron microscopy (SEM) koe wale no kahi ʻili laulima me kekahi mau ʻāpana silica e nānā ana (fig. S5).Ua hoʻoholo ʻia ka mānoanoa kikoʻī o ka SCE me kahi pycnometer helium a ma kahi o 1.5 g/cm3 no nā helu x āpau (papa S1).Ua hōʻike ʻia ka matrix silica piha e ka ʻili ʻana o ka ILE i loko o kahi mea hoʻoheheʻe (e ʻike i nā Materials and Methods).Ma ka hoʻomaloʻo pono ʻana ma ka wahi koʻikoʻi o CO2, hiki ke loaʻa nā monolith airgel intact e like me ka mea i hōʻike ʻia ma ka Fig. 1A.Hōʻike ka nānā ʻana iā SEM i kahi scaffold o ka silica mesoporous me 10- a 30-nm pore anawaena, i uhi ʻia a puni nā macropores nui o 100 a 150 nm, e like me ka ʻike ʻia ma ka Fig. 1 (B a me C).Ua hōʻike hou ʻia kahi microstructure i haku ʻia me nā nanoparticles silica i hoʻopaʻa ʻia.ʻO ka awelika o ke anawaena pōpō mai ka 7 a 14 nm no nā waiwai x ma waena o 0.5 a me 1.5.

Ua hoʻoholo ʻia ka ʻāpana ili kikoʻī [Brunauer-Emmett-Teller (BET)], porosity, ka nui o ka pore awelika, a me ka puʻupuʻu pore me nā ana N2 adsorption/desorption (papa S1 a me ka fig. S6).ʻO ka hāʻule hapa o ka hale a me ka wehe ʻole ʻia ʻana o ka ILE i hoʻopili ʻia e hōʻike hewa paha i nā helu.ʻO ka unuhi pono ʻana o ka wai ionic a me ka maloʻo lohi me ka hoʻohana ʻana i ka supercritical CO2 i hāʻawi ʻia, akā naʻe, nā hopena hilinaʻi kokoke i ka porosity i manaʻo ʻia i helu ʻia mai ka hakina leo o ILE a i silica (Fig. 1).Aia ka ʻili o ka BET ma waena o 800 a me 1000 m2/g.ʻO ka mean pore nui i loaʻa mai ka pali o ka isotherm ma waena o 7 a me 16 nm.Eia kekahi, ua ana ʻia kahi hapa liʻiliʻi o nā pores nui a hiki i ka 200 nm (fig. S6), e like me ka nānā ʻana o SEM.Ua kūpono loa ke anawaena pore me ka pālua o ka mānoanoa like o ka papa ILE i loa'a mai ka hakina leo ILE a me ka ili BET, 'o ia ho'i, ua piha loa nā mesopores me ILE.

No nā mesopores a me macropores wale nō ka ʻāpana ili BET i hōʻike ʻia.No ka acetone-rinsed matrix, ua ana pū ʻia nā micropores (~ 0.6 nm).Loaʻa nā micropores ma waena o nā nanoparticles silica hoʻokahi i kūkulu i ka hale e like me nā mea i hōʻike ʻia ma ke kiʻi TEM o Fig. 1D.Ua manaʻo ʻia kahi ʻāpana ʻili nui ma waena o 650 (x = 0.5) a me 360 m2/g (x = 1.5) (papa S1).

Hōʻike ʻo FTIR a me Raman spectra i nā hōʻike maopopo no nā pūʻulu silanol me nā molekole wai hau adsorbed ma ka matrix silica porosity kiʻekiʻe me nā wahi ili kūpono loa ma mua o 1400 m2/g i ka wā e noʻonoʻo ai i nā micropores, mesopores, a me macropores.Ma waena o ka ʻole a me ʻekolu mau monolayers wai i manaʻo ʻia mai ka wai nui i loko o ka nano-SCE no x <1.75.No ka silica planar, ua mana'o 'ia nā 'ekolu monolayers mua o ka wai i ho'opili 'ia me ka 'ole a me ke 'ano pa'a ma muli o ka pa'a ikaika o ka hydrogen i ka ili i ho'opau 'ia (32) (e 'ike i ka fig. S2).Loaʻa ke kiko O─H pili me ka hydrogen silanol i hoʻopaʻa ʻia i kahi papa wai hau ma 3540 knm−1 i ka spectra FTIR.Hōʻike nā nano-SCE a pau, ʻoiaʻiʻo, he piko ʻokoʻa ma 3540 cm−1 no ka wai hau ma hope o ka maloʻo ʻana a ma hope o ka maloʻo hou ʻana i ka pahu mīkina lima (Fig. 2).ʻOiai no ka nano-SCE i hoʻohālikelike ʻia ma 0.0005% RH (pahu mīkina lima), ua hōʻike mau ʻia ka spectroscopy Raman i ke alo o kahi monolayer hapa liʻiliʻi (Fig. 4B).ʻO ka hā o ka monolayer ma ka planar silica ka mea i manaʻo ʻia he papa hoʻololi, ʻo ia hoʻi ke hoʻopili ʻia a kau ʻia akā hiki ke neʻe.Mai ka papa ʻelima ma luna, lilo ka wai me he wai lā.E hōʻike ʻia ana ka wai e like me ka wai ma nā helu nalu kiʻekiʻe ma ka spectrum FTIR ma muli o ka haʻahaʻa haʻahaʻa o ka paʻa-H i loko o ka wai wai.No ka nano-SCE i hōʻike ʻia i 60% RH, hōʻike maoli ka 3540-cm−1peak i nā haʻalulu hou i hoʻololi ʻia i nā helu nalu kiʻekiʻe ma muli o ka papa wai wai hoʻoheheʻe hou.ʻO ka hoihoi ma kēia ʻano ka hoʻokolohua kahi i hōʻike ʻia ai ka hāpana i 30% RH, no ka mea, ʻaʻohe wai wai i manaʻo ʻia ma ke silica ma kēia haʻahaʻa (fig. S2).No kēia laʻana, ʻike wale ʻia ka piko 3540 cm−1 no ka wai hau ma FTIR.Eia kekahi, ʻaʻole i ʻike ʻia kahi kiʻekiʻe wai manuahi ma 1635 cm−1 ma hope o 4 mau lā ma 30% RH.'O ia ho'i, 'a'ole lawe 'ia ka wai e ka Li-TFSI hygroscopic i ho'ohehe'e 'ia i loko o ka BMP-TFSI hydrophobic i ka manawa e malo'o ai ka nano-SCE ma ka ho'oma'ama'a 'ana.No laila, e hoʻopili ʻia kekahi wai hou i loko o ka SCE ma ka ʻili silica i hoʻopau ʻia e OH.No laila, no ka silica planar, aia ka SCE silica matrix i ke kaulike me ke kaomi hapa o ka wai i loko o ke kaiapuni.

No ka hoʻāʻo hou ʻana i kēia kuhiakau, ua ana ʻia ka conductivity ion o nano-SCE (x = 1, 1.5, a me 2) ma nā % RH ʻokoʻa;ua hōʻike ʻia nā laʻana i kahi hui hoʻomalu ʻia o ke kinoea N2 maloʻo a hoʻomaʻemaʻe ʻia i loko o ka pahu mīkina lima no nā lā 2 e hiki ai i ka uhi wai adsorbed ke hiki i ke kaulike (Fig. 3D).No nā kiko ma ~0% RH, ua lawe ʻia ka conductivity no ka nano-SCE i hoʻohālikelike ʻia i loko o ka pahu mīkina lima.ʻO ka mea kupanaha, ua hahai ka hana ion conductivity versus RH(%) i ka hana i manaʻo ʻia no ka adsorption wai ma ka silica planar (fig. S2).Ma waena o 0 a me 30% RH, hoʻonui ka conductivity me ka hoʻonui ʻana i ka RH.e like me ka mea i manaʻo ʻia no ka hoʻonui ʻana i ka nui a me ka mānoanoa o ka papa hau adsorbed (e like me hoʻokahi a ʻekolu mau papa hau ma ka silica planar).E hoʻomaopopo ua hōʻike ʻo FTIR ʻaʻohe wai manuahi i loko o ka nano-SCE no kekahi mau lā ma 30% RH.ʻIke ʻia kahi hoʻololi ma kahi o 50% RH, e pili ana me nā kūlana kahi e manaʻo ʻia ai kahi papa wai adsorbed hoʻololi no ka silica planar.ʻO ka hopena, ʻike ʻia kahi piʻi ʻokoʻa o ka conductivity ion ma kahi o 60% a me nā haʻahaʻa kiʻekiʻe kahi, ma ke ʻano like me ka silica planar, i kēia manawa, ua hoʻokumu ʻia kahi papa wai e like me ka wai ma ke kikowaena ma waena o ka silica a me ka ILE i hoʻopili ʻia.Me FTIR, ʻike ʻia kahi papa wai wai ma ka papa hau e ka hoʻololi ʻana o ka silanol/ice/water vibrational peak i nā ikehu kiʻekiʻe (Fig. 2A).Hiki ke hoʻololi i ka loli i ʻike ʻia i ka conductivity;no laila, hiki i ka nano-SCE ke hana ma ke ʻano he mea ʻike haʻahaʻa a me kahi electrolyte Li-ion.Mai ka Fig. 3D, ka ion conductivity o ka nano-SCE ma hope koke iho o ka vacuum anneal me ka equilibrium hydrated silica o ~10% RH.ʻO ka conductivity ion no ka saturation ma nā kūlana lumi maloʻo (~ 0.5% RH) ma kahi o 0.6 mS/cm (no x = 2).Hōʻike ʻia kēia hoʻokolohua i ka hopena o ka wai interfacial ma ka conductivity ion.No ka RH > 60%, hiki ke wehewehe ʻia ke kiʻekiʻe o ka ion conductivity e ka hoʻopuehu wikiwiki ʻana o Li+ i hoʻoheheʻe ʻia ma o ka papa wai-like.Eia naʻe, i ka hihia o kahi papa hau paʻa, ʻo ka Li+ ion diffusion he ʻano hoʻopuehu ʻano paʻa a no laila ʻoi aku ka lohi ma mua o ka wai ionic ponoʻī.Akā, ua pili ka hoʻonui ʻana i ka adsorption i hoʻonui ʻia o nā anion organik a me nā cations o ka Li-paʻakai a me nā molekele wai ionic, e like me ka mea i manaʻo ʻia ma ke kumu hoʻohālike ma lalo nei.

Hāʻawi mākou i kahi hoʻohālike e hoʻopili ʻia ai nā molekala wai ionic ma ka ʻili silica ma o nā alahaka H me ka papa hau immobile ma nā hui silanol (Fig. 4).Hāʻawi ke ʻano intrinsic o ka hopena condensation hydrolysis i ka silanol density kiʻekiʻe loa (4 × 1014 a i 8 × 1014 cm−2, e pili pono ana me ka nui o hoʻokahi monolayer o ka hau me ~ 8 × 1014 mau mole wai ma ke cm2) (34).Hāʻawi ʻia nā hōʻike no ka pilina molekala ma waena o nā ʻātoma O o nā anion TFSI a me ka silica e FTIR, e hōʻike ana i ka pālua o ka piko O═S═O no nā nano-SCE a pau ke hoʻohālikelike ʻia me ka kuhikuhi ILE (Fig. 4A; spectra piha. ma ka fig. S8).ʻO ka hoʻololi ʻana o ka piko hou me kahi o −5 cm−1 mai 1231 cm−1 e hōʻike ana i ka hoʻopaʻa ʻana o nā pūʻulu O═S═O no ka liʻiliʻi loa o nā anion TFSI.No laila, manaʻo ʻia ka hoʻopaʻa ʻana o nā anion TFSI ma ka papa wai hau.A laila, pili ka nui hydrophobic BMP cations me ka papa TFSI mua, e hoʻopiha ana i ka papa adsorbed mua o nā molekele wai ionic.No ka papa hau, ua manaʻo ʻia ʻo nā molekala BMP-TFSI i hoʻopili ʻia i ka nui o ka neʻe ʻana, pēlā e hoʻonui ai i ka papa hau paʻa ma ka ʻili silica.No ka mea he hui O═S═O like ka anion TFSI, hiki i hoʻokahi atomo oxygen ke launa pū me ka ʻili silica hydroxylated a ʻo nā mea ʻē aʻe e hana i nā kiko pili no nā cation BMP.ʻElua pūʻulu O═S═O ka TFSI anion, e hōʻoiaʻiʻo ana i ka adsorption paʻa a me ke kauoha paʻa o ka monolayer anion.ʻOi aku ka maikaʻi o ka Adsorption i ka hihia o kahi papa hau me ka kiʻekiʻe kiʻekiʻe o nā pūʻulu OH e like me nā kiko pipili.Ma ke alo o nā pūʻulu silanol wale nō, ʻaʻole lawa ka ikaika o ka adsorption e hana i kahi papa adsorbate mau.Eia kekahi, ʻike ʻia ka piʻi ʻana o nā monolayers hau e hoʻonui i ka ikaika o ka paʻa hydrogen (35).E hoʻomaopopo he ʻokoʻa ka pilina molekala ma waena o ka cation BMP a me ka monolayer TFSI i kauoha ʻia mai ka wai ionic kahi i loaʻa ai i ka anion TFSI ke kūʻokoʻa rotational a ʻaʻohe polarization mai kahi ʻili lalo.Hoʻokaʻawale ʻia ka uku o ka cation BMP nui ma luna o nā ʻātoma he nui ma o ka polarization o nā paʻa intrinsic a me nā pilina molekala me kona wahi kemika a, ʻo ia hoʻi, ka adsorbed TFSI anion.ʻO ka hoʻopaʻa ʻana H ma waena o ka pūʻulu O o ka anion TFSI a me ka hoʻopau ʻana o ka OH o ka papa hau i kēia manawa e hoʻolauna i kahi dipole ma luna o ka papa adsorbed mua, e hoʻoulu ai i ka hoʻonohonoho ʻana i ka molekala e ka hui.Ua manaʻo ʻia i kēia manawa, hoʻopili nā molekele Li-TFSI liʻiliʻi ma ka papa molekika kahi e uku ai ka anion TFSI i ke koena o ka hoʻopiʻi dipolar maikaʻi o hoʻokahi a ʻoi aku paha o nā cation BMP ma ka papa luna, no laila e wehe ana i kona hui ʻana me kāna Li. ion.Ma kēia ala, hoʻonui ʻia ka manaʻo o Li + manuahi ma kēia interface, e alakaʻi ana i ka conductivity ion kiʻekiʻe.No laila, ʻoi aku ka ʻoi aʻe a me ka mānoanoa o nā papa hau a laila hoʻokomo i kahi dipole ʻoi aʻe me ka uku koena kiʻekiʻe e uku ai, e hāʻawi ana i ka ʻoi aku ka nui o ka liʻiliʻi liʻiliʻi liʻiliʻi liʻiliʻi a no laila ka conductivity ion.

Ma luna o ka papa ILE i hoʻopili ʻia, hiki i kekahi papa ILE ʻē aʻe ke hoʻopili e like me nā ʻāpana hau nui ma ke silica a i ʻole ka nawaliwali o ka huki dipole o ka papa hau a aia ka ILE i hoʻopaʻa māmā ʻia ma luna, a laila hiki ke hāʻawi i ka hoʻokele wai-like no. ua hoʻokuʻu ʻia nā liona Li+ i ka ʻāpana adsorbed haʻahaʻa (Fig. 4C).Ua hoʻopaʻa ʻia ka hoʻololi ʻana i ka manaʻo Li+ ion manuahi e nā ana spectroscopy NMR a me Raman.Hōʻike pololei ʻole nā ana Raman i ka hapa nui o nā liona Li+ manuahi i loko o ka nano-SCE me nā papa wai hau i hoʻopaʻa ʻia i ka silica (Fig. 5).Hoʻopili ka Raman i ka hui ʻana o ka cation me TFSI ma ka ʻimi ʻana i ka haʻalulu o ka hui N o ka anion TFSI (36).I loko o ka wai ionic BMP-TFSI maʻemaʻe, ʻike ʻia kahi piko hoʻokahi ma 741 cm−1.Ma ka hihia o ka ILE maʻemaʻe, ʻike ʻia kahi kiʻekiʻe hou ma 746 cm−1 kahi e hui pū ai ʻelua mau anion TFSI me hoʻokahi Li+ ion [e ʻike i ka helu ʻana o ka density functional theory (DFT) ma nā Mea Hana a me nā Hana].No nā nano-SCE a pau, ʻoi aku ka nāwaliwali o ka piko ma 746 cm−1 ma mua o kēlā no ILE, e hōʻike ana i kahi hapa liʻiliʻi o Li-TFSI pili a, no laila, ʻoi aku ka hapa nui o nā Li+ cations ʻole i hui pū ʻia.E emi loa ka piko no kēlā nano-SCE e hōʻike ana i ka hoʻonui conductivity kiʻekiʻe loa, ʻo ia hoʻi, ka poʻe me ka papa hau mānoanoa.No ka nano-SCE ma ke kaulike i loko o ka pahu mīkina lima, eia naʻe, ua ana ʻia kahi hakina o ka Li+ manuahi ʻoiai ʻoi aku ka liʻiliʻi ma mua o nā mea hoʻohālike i hoʻopili ʻia.ʻO ka lakio o ka ikaika kiʻekiʻe no ka 746 ma luna o 741 cm−1 Raman neʻe a laila he ana o ka ratio o ka manuahi me nā Li-iona pili TFSI (Fig. 5B).ʻO ka hoʻonui laina i ka hakina Li+ ion manuahi me ka waiwai x e hahai maikaʻi i ke ʻano o ka hoʻonui conductivity me ka waiwai x ma Fig. 3B, ʻelua no ka nano-SCE maloʻo maloʻo (lā 0) a me ka SCE ma ke kaulike me ka maloʻo o ka pahu mīkina lima (lā. 138).

(A) Raman spectra o ka ionic wai (IL; dotted blue line) and ILE reference (ILE; dash-dotted line) o ka nano-SCE i hoʻomākaukau ʻia (maloʻo maloʻo) me nā waiwai x o 0.5 ('ōmaʻomaʻo), 1.5 (melemele) , a me 2 (ʻeleʻele) a me ka nano-SCE (x = 1.5) i hoʻomaloʻo ʻia i loko o ka pahu mīkina lima no 30 lā a i ʻole kokoke i ka saturation ma 0.0005% RH (ʻulaʻula).Hoʻopili ʻia nā laina kū pololei i ka neʻe ʻana o Raman no TFSI me kona kikowaena N i hoʻonohonoho ʻia i Li+ (746 cm−1) a ʻaʻole i hoʻonohonoho ʻia i Li+ (741 cm−1).(B) ʻO ka ratio o ka Li+ i hui pū ʻia o nano-SCE e like me ka synthesized (maloʻo maloʻo, nā pōʻai ʻeleʻele) a hoʻomaloʻo ʻia i loko o nā pahu mīkina lima me 0.0005% RH no 30 mau lā (nā daimana uliuli), e pili ana i ka ratio o ka ikaika hoʻohui o ka Nā piko o Raman (746 knm−1 ma luna o 741 knm−1).(C) PFG-NMR i loaʻa iā Li+ ka helu hoʻopuehu ponoʻī o nano-SCE (nā daimana ʻulaʻula) a me ILE ref.(nā ʻāpana ʻeleʻele) ma ke ʻano he hana o ka wā ma waena o nā puʻupuʻu gradient magnetic field.Ua hoʻohālikelike ʻia nā kiʻekiʻe theoretical ma Raman spectra me ka hoʻohana ʻana i ka helu DFT.

Mai ka pulsed-field gradient NMR (PFG-NMR), ua hoʻoholo ʻia ka coefficient diffusion ponoʻī o nā ʻano Li-ion mobile like ʻole ma ke ʻano he hana o ka wā ma waena o ka gradient magnetic field pulses ∆ no ka ILE wai kuhikuhi a no kahi nano- SCE (x = 1.5) me ka ion conductivity like o 0.6 mS/cm (Fig. 5C).He mau ka Li+ hoʻohalahala ponoʻī ma ka ILE kuhikuhi, e hōʻike ana he hoʻokahi wale nō ʻano Li me ka neʻe like loa i loko o ka wai.No ka nano-SCE, ua ho'ololi 'ia ka coefficient diffusion pono'ī me ∆ a ua oi aku i ko ILE ma ka ∆ pōkole, e hōʻike ana i ka hele ʻana o nā ʻano ʻano wikiwiki e pane wale i nā manawa pōkole ma waena o nā pulses magnetic field.ʻO ka gradient i loko o ka hoʻoheheʻe ponoʻī e hōʻike ana e pili ana i ka piʻi ʻana o ka manaʻo Li-ion manuahi, e like me ka ʻike ʻia mai Raman spectroscopy, ua hoʻohaʻahaʻa ʻia ka ikehu hoʻāla no ka diffusion i ka papa interface mesophase pū kekahi.Kākoʻo kēia i ka hoʻonui conductivity i hoʻokomo ʻia e nā (ʻoi aku) manuahi Li+ ion i ka papa mesophase.I ka lōʻihi ∆, ʻoi aku ka haʻahaʻa o ka coefficient diffusion ponoʻī ma mua o ka hōʻike ILE.Hoʻopili kēia i ka haʻahaʻa haʻahaʻa haʻahaʻa no ka pahu mīkina lima-saturated nano-SCE i hoʻohālikelike ʻia me ILE.ʻO ka ILE i hoʻopaʻa ʻia i loko o ke kumu o nā mesopores e ʻoi aku ka viscosity kiʻekiʻe ma muli o ke kaohi ʻana o ka neʻe ʻana o ka molekala.No laila, ʻo ka hoʻonui ʻana ma o ka hoʻokumu ʻana i nā Li-ions hoʻolaha wikiwiki loa ma ka pilina silica/ice/ILE e hoʻonui i ka emi ʻana o ka conductivity i ke kumu o ka pore.Hōʻike kēia i ka loaʻa ʻole o ka hoʻomaikaʻi ʻana i nā ʻōnaehana kumu ʻāpana kahi i hāʻawi ʻole ai nā interface i ka hoʻolaha hoʻolaha ion conduction (fig. S1).

Ua ho'āʻoʻia ke kūpaʻa electrochemical o ka nano-SCE e kū'ē i ka metala lithium me ka hoʻohanaʻana i kahi hoʻonohonohoʻekolu-electrode (hōʻikeʻia ka schematic o ka hoʻonohonoho i ka fig. S7).Hōʻike ʻia ke ʻano o kēia manawa o Li/SCE (x = 1.5) a me Li/ILE ma ke kiʻi 6A.No ka puka aniani uila ma Fig. 2, ua kaupalena ʻia ka electrochemistry e ka mea hoʻopiha ILE.ʻIke ʻia ka hoʻololi ʻana o ka lithium plating a me ka wehe ʻana.Hoʻokumu ʻia kahi papa electrolyte interphase paʻa paʻa (SEI) ma ka lithium metala me kahi RSEI ma kahi o 0.9 kilo-ohm·cm2, kuleana no ka hāʻule nui o ka IR ma ka pihi iU ma nā ʻaoʻao cathodic a me nā ʻaoʻao anodic.ʻAʻole i hōʻike ʻia ka hysteresis a hiki i ka −2.5 mA/cm2 ke ʻano cathodic i loko o nā haʻina ILE maʻemaʻe.Eia naʻe, ua hōʻike ka hoʻoheheʻe anodic i kahi kiʻekiʻe passivation me kahi ʻano anodic kūpaʻa o 0.06 mA / cm2 wale nō.ʻAʻole hōʻike ka lālā cathodic i kēia manawa ma ke kikowaena Li/SCE paʻa paʻa i ka hysteresis no nā au cathodic ma lalo o −0.5 mA/cm2.ʻO ke kūʻē ʻana o ka SEI, ma kahi o pālua.Pēlā nō, ʻoi aku ka haʻahaʻa o ka piko anodic a ʻo ke ʻano kūpaʻa ma hope o ke kiʻekiʻe passivation anodic he 0.03 mA/cm2, ʻo ka hapalua wale nō o ka hopena ILE maʻemaʻe.ʻO ka hoʻokumu ʻana o SEI a me nā papa passivation i loko o nā pores o ka SCE e kaupalena ana i kēia manawa ma ka metala lithium.Hiki ke hana hou ʻia nā voltammograms ʻelua no nā electrodes Li/ILE a me Li/SCE ma nā pōʻai he nui, e hōʻike ana he hiki ke hoʻohuli a paʻa ka papa anodic passivation a me ka papa SEI kemikala.ʻO nā kinetics hoʻoheheʻe lohi ma ka pānaʻi Li / SCE e kaupalena nui i ka hana o nā ʻāpana hapa i hana ʻia me nā anodes me Li ma lalo.

(A) Voltammogram Cyclic o nano-SCE (x = 1.5, e like me ka synthesized ma hope o ka maloʻo maloʻo) (ʻulaʻula) a me ka ILE kuhikuhi (ʻeleʻele) i ana i loko o ʻekolu-electrode hoʻonohonoho me Li e like me ka hana, counter, a me nā electrodes kuhikuhi (SEI kū'ē i manaʻo ʻia mai ʻO ka hāʻule ʻana o IR ma ke au cathodic he 0.9 a me 1.8 kilo-ohm·cm2 no ILE a me SCE, kēlā me kēia).(B) ʻO nā ʻōpuni hoʻoili / hoʻokuʻu Galvanic o Li/SCE (x = 1)/100-nm kiʻiʻoniʻoni lahilahi LiMn2O4 cell no nā pōʻai ʻelima ma C-rate o 1C, 5C, a me 20C.(C) Cyclic voltammograms o ka Li / SCE / 40-μm Li4Ti5O12 a me Li / SCE / 30-μm LiFePO4 pauka electrode cell (1 mV / s).(D) Galvanic uku / hoʻokuʻu ʻia o Li / SCE / 40-μm Li4Ti5O12 pauka electrode ma 1C, 0.1C, 0.2C, a me 0.02C.(E) Galvanic charge/discharge curves o ka Li/SCE/30-μm LiFePO4 pauka electrode ma 1C, 0.5C, 0.2C, 0.1C, 0.05C, a me 0.01C.(F) Ka nui (nā daimana piha no ka delithiation a me nā ʻāpana hāmama no ka lithiation) me ka helu pōʻai o ka Li/SCE/30-μm LiFePO4 pauka electrode;ʻO ka mānoanoa o ka SCE i loko o nā pūnaewele ma kahi o 280 μm.ʻO ka mānoanoa o ka LFP a me ka LTO cathode ma kahi o 1.9 a me 11.0 mg/cm2.(G) Hiki ke hoʻohālikelike i nā pihi manawa o kahi waihona Li/SCE/Li i hoʻokele ʻia ma nā mānoanoa o kēia manawa o 0.1, 0.2, 0.5, a me 0.1 mA/cm2.(H) ʻO ka 1st, 10th, 125th, a me ka polarization hope loa o ka waihona Li / SCE / Li i koʻikoʻi ma 0.1 mA / cm2, i hōʻike ʻia ma (G).No (G) a me (H), he conductivity o ka SCE he 0. 34 mS/cm, a he 0.152 knm ka manoanoa o ka pellet SCE.

Ua hoʻohana ʻia kahi kiʻiʻoniʻoni liʻiliʻi 100-nm LiMn2O4 (LMO) ma ke ʻano he electrode maikaʻi e hoʻāʻo ai i ka paʻa o ka nano-SCE a me ka mea electrode oiai e hoʻopau ana i nā pilikia pili pili i nā electrodes composite particle (37).ʻO ka hana kaʻa kaʻa o ke kiʻi ʻoniʻoni ʻoniʻoni ʻoniʻoni / SCE e hōʻike ana i ka paʻa o ka pilina ma waena o ka electrode a me ka electrolyte.I loko o kēia ʻano hoʻonohonoho kiʻiʻoniʻoni lahilahi, hoʻokahi wale nō, wehewehe maikaʻi ʻia, a me ka hoʻopili ʻana i ka papa kuhikuhi ma waena o ka electrolyte a me ka electrode, ʻo ia hoʻi, he kahua kūpono ia e aʻo ai i ka electrochemistry o ka electrolyte/electrode interface me ka pilikia ʻole o ka hoʻololi leo. , etc. Eia kekahi, ma keia hoao ana, aole i kaupalena ia ka hana ana e ka Li-foil counter electrode, no ka mea, o ka nui o keia manawa (6 μA/cm2 no 1C) aia ma lalo o ka pa'a anodic anodic no ka hapalua o ka lithium. kelepona (0.03 mA/cm2).Loaʻa nā ʻōkuhi hoʻopiʻi hou a paʻa no ka ʻoki ʻoki ʻana ma 4.3 V no nā C-rate ma waena o 1 a me 20C no nā pōʻai he 20 (Fig. 6B).ʻAʻole paʻa ʻo LMO i kahi electrolyte wai no LiB.No ka laʻana, ua ʻike ʻia he 50% hiki ke hoʻemi ʻia ma kahi kiʻiʻoniʻoni LMO 100-nm i hoʻokuʻu ʻia no 10 mau pōʻai i loko o kahi LiClO4/propylene carbonate electrolyte ma 1C (37).Hōʻike kā mākou mau hopena i ka ʻoi aku o ka nano-SCE me ka LMO ma mua o kahi electrolyte wai maʻamau.

No ka hōʻike ʻana i ka hoʻohui ʻana o ka nano-SCE, ua hana pū mākou i nā ʻāpana hapalua me nā electrodes pauka Li4Ti5O12 (LTO) a me LiFePO4 (LFP).Ua hoʻolei ʻia ka hoʻonā precursor i loko o ke keʻena kālā e hoʻokomo i nā electrodes porous a waiho ʻia no ka gelation hou aʻe ma mua o ka hoʻomaloʻo ʻana a hoʻoheheʻe ʻia e like me nā pellets nano-SCE.Hōʻike nā pūnaewele i ka lithiation / delithiation o nā electrodes pili (Fig. 6C).ʻO nā kaha kiʻekiʻe haʻahaʻa no LFP ma mua o LTO ma muli o ka ʻokoʻa o ka mānoanoa uhi.ʻO ka hana maʻamau i ka wā o ka hoʻouka / hoʻokuʻu ʻana ua kaupalena ʻia e ka Li-foil counter electrode i kaomi ʻia ma ka papa nano-SCE i hana ʻia ma luna o ka 30- a 40-μm-mānoanoa electrode coatings (Fig. 6, D a me E).ʻO ka LTO / nano-SCE / Li pūnaewele i hiki i kona mana kiʻekiʻe loa o 160 mA · hola / g wale nō ma ka haʻahaʻa C-rate o 0.02C (Fig. 6D).E hāʻule koke ka hiki ke hiki me ka C-rate me ka liʻiliʻi ma lalo o 10% no nā C-rate ʻoi aku ka nui ma mua o 0.1C.Pēlā nō, hiki i ka LFP / SCE / Li cell i kona mana kiʻekiʻe ma kahi o 140 mA · hola / g ma 0.01C (Fig 6E).Hōʻike ka Figure 6F i ka hana pākēneka no ka huina o 30 pōʻai, e hōʻike ana i ka hoʻonohonoho hoʻonohonoho paʻa.Hōʻike kēia mau hoʻokolohua i ka hana o ka nano-SCE e like me Li-ion electrolyte a me ka hiki ke hoʻohui ʻia i nā cell Li-ion.

Ua ho'āʻo ʻia ke kūpaʻa a i ʻole ka cyclability o ka nano-SCE me ka hoʻohana ʻana i ka Li/SCE/Li symmetric stack.Ua hoʻokele ʻia ʻo ia ma mua o 120 cycles ma kahi ʻano nui o 0.1 mA/cm2 i kēia manawa no nā hola 0.5 (Fig. 6G) me ka ʻole o nā pilikia a i ʻole ka hoʻokumu dendrite (Fig. 6H).Ua liʻiliʻi ka voltage polarization i ka manawa, e hōʻike ana i ka hoʻomaikaʻi ʻana o ka pilina.Eia kekahi, ua hoʻokūpaʻaʻia ke kelepona i nā densities o kēia manawa o 0.5 mA / cm2, me kaʻole o ka hoʻokumuʻiaʻana o nā lithium dendrites a iʻole nā hōʻailona o ka hōʻinoʻana o ka nano-SCE a iʻole ka interface (Fig. 6G).ʻIke ʻia ka lithium metallic e hana i kahi papa interphase pale a i ʻole SEI ma kona ʻili ma BMP-TFSI-based ILEs (27).Hiki pū kēia hopena ma ka pānaehana lithium/nano-SCE;e like me ka mea i kūkākūkā ʻia ma lalo o ka Fig. 6A, hiki i ka SEI ke ulu iki i loko o nā pores, e wehewehe ana i ke kūpaʻa SEI kiʻekiʻe no ka nano-SCE ma mua o ILE (e ʻike i luna).Loaʻa ka hōʻoia no kahi papa SEI mai ka IR spectra (fig. S9).E like me ka uhi SEI i ka LiB maʻamau, nāna e pale i ka graphite electrode mai ka wai electrolyte e pale aku ai i ka hopena hou aʻe, ke manaʻoʻiʻo nei mākou e pale pū ka SEI ma ʻaneʻi i ka papa wai hau mai ka hopena hou mai ka anode lithium metallic.Impedance spectra ma mua a ma hope o ka polarization o ka Li / nano-SCE (x = 1.5) no 10 hola 'aʻole i hōʻike i kekahi loli i ka bulk electrolyte kū'ē.Pono nā ana hana kaʻa kaʻa lōʻihi e kāpae i ka maloʻo lohi o ka nano-SCE me ka metala lithium, akā ua hōʻike mua kēia mau hopena i kona hiki ke hiki i ka cyclability maikaʻi loa o ka SCE i loko o nā pā paʻa paʻa paʻa lithium metala.Eia nō naʻe, hiki ke noʻonoʻo ʻia nā uhi interphase artificial e hoʻomaikaʻi i ka impedance interface.

Ua hōʻike mākou e hiki ke hoʻokō ʻia ka hoʻolaha ʻana o ka ion conduction ma nā pilina silica ma o ka hoʻokomo ʻana i kahi papa wai chemisorbed ma nā ʻili silica i hoʻopau ʻia e OH.Hoʻomohu nā anion TFSI i kēia papa hana wai ma o ka hoʻopaʻa ʻana i ka hydrogen me ka hui likemmetric O═S═O.ʻAʻole naʻe ka ʻili o ka wai a no laila ke hoʻopaʻa nei i ka papa TFSI adsorbed i ka ʻili.Hoʻopili ʻia nā cations BMP nui i ka monolayer TFSI, no laila e hoʻokomo ana i ke kauoha molekala o ka TFSI-BMP ma ka ʻili.Ke manaʻoʻiʻo nei mākou ʻo ka lohi lohi i ka wai a me ka maloʻo maloʻo e kōkua i ka hoʻokumu ʻana o ka papa wai hana a me ka papa o nā ion organik ma luna.Ke kaʻana like ʻana o ka papa anion TFSI mua i ka ʻāpana o kāna uku maikaʻi ʻole me ka silica hydroxylated, ʻo ka BMP cation layer ma luna e ʻimi i ka hui ʻana me kahi anion TFSI ʻē aʻe, kahi e hiki ai i nā BMP he nui ke kaʻana like i kā lākou uku uku ʻole me hoʻokahi TFSI (ʻekolu paha a hoʻokahi e like me ka ratio o IL i Li-TFSI ma ka ILE).I ka loaʻa ʻana o kahi kokoke loa o nā molekala paʻakai Li-TFSI, e hoʻokaʻawale ʻia nā liona Li+ a hoʻokuʻu ʻia no ka hoʻopuehu wikiwiki ʻana ma kēia papa kuhikuhi.No ka hoʻonui ʻana, pono kēia mau ʻano Li+ manuahi i hoʻokahi ʻāpana wai ionic hou e neʻe ai.No kēia kumu, ʻaʻole i hōʻike ka nano-SCE me ka waiwai haʻahaʻa x o 0.5, ʻaʻole i hoʻonui ʻia ka conductivity, no ka mea, lawa ka nui o ka ILE/silica surface area no hoʻokahi monolayer paʻa.

Ua hōʻike hou ʻia ʻaʻole hana electrochemical ka wai o ka ʻili paʻa a i ʻole ka papa hau.I kēia manawa, ʻaʻole hiki iā mākou ke hoʻokaʻawale ʻaʻole i pane ka wai hau e pili pono ana me ka ʻili electrode.Eia naʻe, ua hōʻike mākou he lohi ka hoʻopuehu ʻana o ka wai i waho a no laila hiki ʻole ke ʻike ʻia.ʻIke mākou i ka hoʻohaumia ʻana i ka wai, ʻoiai he liʻiliʻi paha, e hopohopo mau ana, a ʻo nā hoʻokolohua lōʻihi o ke ola holoʻokoʻa hiki ke hāʻawi i kahi pane maopopo i ka lawa ʻana o ka wai.Eia nō naʻe, hiki ke hoʻomohala ʻia nā papa papa hana ʻē aʻe e hāʻawi i ka hoʻolaha ʻana like a ʻoi aku paha.Ma kēiaʻano, ua hōʻike mua ka hui o Li i ka hiki o kahi papa glycidyloxypropyl ma keʻano he hui hana (18).ʻO ka wai hau no ka silica a no laila ua kūpono ke aʻo ʻana i ka hopena o ka hoʻohana ʻana i ka ʻili i ka hoʻolaha ʻana o ka ion conduction ma ka ʻōnaehana, e like me ka mea i hōʻike maikaʻi ʻia ma aneʻi.Eia kekahi, e pili ana ka papa mesophase a me kona dipole i ka oxide a me nā molekole organik adsorbed a no laila hiki ke hoʻolohe ʻia e nā mea ʻelua.I loko o ka hale hana, ua hōʻike mua mākou i nā ʻokoʻa nui i ka hoʻolaha ʻana i ka ion conduction no nā wai ionic like ʻole.Eia kekahi, ʻo ke kumukānāwai i hōʻike ʻia he maʻamau i ka conduction ion a hiki ke hoʻohana ʻia no nā ʻōnaehana ion ʻokoʻa i kūpono, no ka laʻana, no nā pāpaʻi sodium, magnesium, calcium, a i ʻole alumini ion.I ka hopena, ʻo ka nanocomposite electrolyte me ka conduction interface i hōʻike ʻia ma ʻaneʻi he manaʻo ma mua o kahi mea hoʻokahi, hiki ke hana hou ʻia (nano) i nā waiwai i makemake ʻia o ka conduction ion, ka helu lawe, puka aniani uila, palekana, a me ke kumu kūʻai no nā hanauna kelepona e hiki mai ana. .

Ua hoʻomākaukau ʻia ka nano-SCE me ka hoʻohana ʻana i ke ʻano sol-gel.Lithium bis(trifluoromethylsulfonyl)imide Li-TFSI;Sigma-Aldrich;99.95%), 0.5 ml o ka H2O deionized, 0.5 ml o TEOS (Sigma-Aldrich; 99.0%), 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP-TFSI; Sigma-Aldrich; 98.5%), a me 1 Ua hui ʻia ka ml o PGME i loko o kahi hue aniani.Ua hoʻololi ʻia ka ratio molar, x, ma waena o [BMP][TFSI] a me TEOS i ka hui ʻana ma waena o 0.25 a me 2. Ua hoʻopaʻa ʻia ka ratio molar o Li[TFSI] a me [BMP][TFSI] ma 0.33:1.Ua hoʻoholo ʻia ka nui o Li[TFSI] a me [BMP][TFSI] mai kēia mau lakio.No ka laʻana, inā x = 1, ʻo ka [BMP][TFSI] a me Li[TFSI] i hoʻohui ʻia i loko o ka hopena he 0.97 a me 0.22 g.Hoʻoluliluli ʻia nā hui ʻana no 1 min e hana i nā hoʻonā monophasic.A laila ua mālama ʻia kēia mau mea hoʻonā i loko o nā hue i pani ʻia me ka hoʻoulu ʻole ʻana e hana i nā gels i loko o kahi keʻena mālama ʻia i ka mahana a me ka haʻahaʻa (SH-641, ESPEC Corp.) me ka mahana a me ka RH% i hoʻonohonoho ʻia ma 25 ° C a me 50%, kēlā me kēia.Ma muli o ka x, ua lawe nā hui, ma ka awelika, 5 a 9 mau lā e hana ai i kahi gel maʻemaʻe.Ma hope o ka hoʻomaloʻo ʻana, ua hoʻomaloʻo mua ʻia nā hue me 2.4- a i ka 7.4-ml gel ma 40 ° C no nā lā piha ʻehā ma ka hoʻemi iki ʻana o ke kaomi (80 kPa) a laila hoʻoneʻe ʻia i loko o kahi umu ʻūhā no 72 mau hola ma 25 ° C.I ka lawe ʻia ʻana o ke koena o ka wai, ua emi mālie ka ʻūhā mai kahi kaomi mua ma kahi o 50 Pa a i kahi kaomi mau hope o 5 Pa ma hope o 1 lā.Ma muli o ka nui o ka wai a me ka PGME i pono e wehe ʻia, ua emi iho nā pellets SCE i loaʻa mai ka 20% (x = 0.5) a hiki i ka ~ 50% (x = 2) o ka nui gel kumu.Ua anaʻia ke kaumaha o nā gels i loaʻa me kahi kaulike semimicro (SM 1245Di-C, VWR).

Ua hana ʻia ʻo TGA ma kahi Q5000 IR (TA Instruments, New Castle, DE, USA) ma lalo o ka nitrogen.I ka wā o ke ana ʻana, ua hoʻomehana ʻia nā laʻana i ka 700 ° C ma ka 2 ° C / min.Ua hana ʻia ka spectrometry FTIR me ka Bruker Vertex 70 ma ka helu nalu mai 4000 a 400 cm−1 ma ke ʻano hoʻoili.Ua hana ʻia ʻo ia ka pycnometry me ka Micromeritics AccuPyc II 1340.

No ke ana ʻana i ka conductivity ionic, ua lawe ʻia kahi puʻupuʻu liʻiliʻi o ka SCE mai ka hue makuahine i loko o kahi pahu mīkina lima piha Ar (0.1-ppm H2O a me 0.1-ppm O2).Ma kahi o 23 μl o SCE i hoʻopiha ʻia i loko o ke apo polytetrafluoroethylene (PTFE) me ka 4.34-mm anawaena o loko a me 1.57-mm kiʻekiʻe, e hana ana i kahi pellet.Hoʻopili ʻia ka pellet i loko o ke apo ma waena o ʻelua diski kila (SS) (0.2 mm mānoanoa; MTI).Ua hana ʻia nā ana impedance me ka hoʻohana ʻana i ka PGSTAT302 (Metrohm), me kahi amplitude AC o 5 mV ma kahi alapine mai 1 MHz a i 1 Hz.Ua hoʻoholo ʻia ka conductivity ion (σi) mai ka intercept kiʻekiʻe me ka axis maoli ma nā ʻāpana Nyquist.Ma hope o ke ana conductivity, ua ʻae ʻia ka pellet nano-SCE e maloʻo hou i loko o ka pahu mīkina lima.No ke ana ʻana i ke ana wela, ua hoʻopaʻa ʻia nā pūʻulu SS/SCE/SS i loko o kahi pūnae kālā.Ma hope o ka sila ʻana, ua mau ka conductivity no kekahi mau lā (e nānā i ka fig. S3).Hoʻomalu ʻia ka mahana o ka cell coin me kahi ʻaʻahu wela me kahi ʻauʻau wela me ka hoʻohana ʻana i ka H2O/ethylene glycol ma ke ʻano hana.Hoʻomaʻalili mua ʻia nā keʻena a hiki i ka -15 ° C a laila hoʻomehana ʻia i ka 60 ° C.

Mai kēlā me kēia nano-SCE pellet, ma kahi o 23 μl i lawe ʻia i loko o ke apo (4.34-mm anawaena o loko a me 1.57-mm kiʻekiʻe) no nā ana uila i loko pono o ka pahu mīkina lima piha N2 me ka haʻahaʻa hoʻomalu.A laila ua hoʻopaʻa ʻia ke apo me ka SCE ma waena o ʻelua mau pā SS (0.2 mm mānoanoa; MTI).Ua hana ʻia nā ana impedance me ka hoʻohana ʻana iā PGSTAT302 (Metrohm) me kahi amplitude AC o 5 mV a me ke alapine mai ka 1 MHz a i ka 1 Hz i hoʻomalu ʻia ma o ka polokalamu Nova.Ua mālama ʻia nā laʻana ma kēlā me kēia waiwai RH% no nā hola 48 ma mua o ka nānā ʻia ʻana o ka conductivity a hiki i ka stabilization.Ua hoʻoholo ʻia ka conductivity ionic i hoʻopaʻa ʻia no kahi waiwai RH% i hāʻawi ʻia (σi) mai ke alapine kiʻekiʻe me ka axis maoli ma nā ʻāpana Nyquist.

Ua nānā ʻia ka morphology o ka pellet me Li[BMP][TFSI] ILE me ka SEM me ka hoʻohana ʻana i kahi hāmeʻa Thermo Fisher Scientific Apreo ma 1.5 a i 2.0 kV kahi e hana ai i kahi ʻano kiʻi kiʻi pālua me ka hoʻohana ʻana i ka mea ʻike T1 a me T2 i ka like no ka. nā hoʻololi kiʻi ola, a ua hoʻohana ʻia ka mea ʻike T2 no ka hoʻopaʻa ʻana i nā kiʻi SEM i hōʻike ʻia;ua hoʻopaʻa ʻia ka hāpana ma ka lipine conductive carbon.Ua hana ʻia ʻo TEM me kahi Tecnai e hana ana ma 300 kV.

Wehe ʻia ka ILE mai ka SCE pellet ma ʻelua ala like ʻole.Hoʻokahi koho no ka loaʻa ʻana o ka silica porous i hana ʻia ma ka hoʻokomo ʻana i ka SCE i loko o ka acetone no 12 mau hola e unuhi i ka Li[BMP][TFSI] ILE.Ua hana hou ʻia kēia holoi ʻana i ʻekolu manawa.ʻO ke koho ʻē aʻe ma ka hoʻoinu ʻana i ka SCE i ka ethanol.I kēia hihia, ua wehe ʻia ka ethanol ma o ka hoʻohana ʻana i kahi mea hoʻomaloʻo koʻikoʻi CO2 wai.

ʻElua mau mea hana like ʻole i hoʻohana ʻia no ka hoʻomaloʻo supercritical, ʻo ia hoʻi, ʻo Automegasamdri-916B, Tousimis (ʻano 1) a me kahi mea hana maʻamau e JASCO Corporation (ʻano 2).I ka hoʻohana ʻana i ka mea hana mua, hoʻomaka ke kaʻina maloʻo me ka emi ʻana o ka mahana a hiki i 8 ° C.A laila, hoʻomaʻemaʻe ʻia ka CO2 ma o ke keʻena, e hoʻonui ana i ke kaomi i 5.5 MPa.Ma ka hana aʻe, ua wela ka CO2 i 41 ° C, e hoʻonui ana i ke kaomi i 10 MPa, a mālama ʻia e like me 5 min.No ka hoʻopau ʻana, i ka pae koko, ua hoʻohaʻahaʻa ʻia ke kaomi ma luna o kahi manawa o 10 min.I ka hoʻohana ʻana i ka mea hana maʻamau, ua hahai ʻia kahi ʻano like.Eia naʻe, ʻokoʻa loa ka manawa a me nā pilikia.Ma hope o ka hoʻomaʻemaʻe ʻana, ua hoʻonui ʻia ke kaomi i 12 MPa ma kahi mahana o 70 ° C a noho mau no 5 a 6 mau hola.Ma hope mai, ua ho'ēmiʻia ke kaomi i nā manawa mai 12 a 7 MPa, 7 a 3 MPa, a me 3 a 0 MPa i ka manawa o 10, 60, a me 10 min.

Ua ana ʻia nā isotherms physisorption Nitrogen ma T = 77 K me ka hoʻohana ʻana i kahi Micromeritics 3Flex surface characterization analyzer.Ua hoʻokuʻu ʻia ka silica porous i loaʻa no 8 mau hola ma 100 ° C ma lalo o kahi 0.1-mbar vacuum.ʻO ka silica porous i loaʻa mai ka maloʻo supercritical ua hoʻopau ʻia no 18 mau hola ma 120 ° C ma lalo o kahi 0.1-mbar vacuum.Ma hope iho, ua ana ʻia nā isotherms physisorption nitrogen ma T = 77 K me ka Micromeritics TriStar 3000 automated gas adsorption analyzer.

Hana ʻia nā ana PFG-NMR me kahi JEOL JNM-ECX400.Ua hoʻohana ʻia ke kaʻina o ka echo pulse i hoʻoulu ʻia no nā ana diffusion.ʻO ka hōʻailona hōʻailona echo maʻamau, E, ua wehewehe ʻia ma ka hoohalike (38)E=exp(−γ2g2δ2D(Δ−δ/3))(1) kahi g ka ikaika o ka gradient pulse, δ ka lōʻihi o ka gradient. ʻO ka pulse, ∆ ka wā ma waena o nā ʻaoʻao alakaʻi o nā pulu gradient, γ ka ratio magnetogyric, a ʻo D ka coefficient diffusion ponoʻī o nā mole.Ua helu ʻia nā coefficients diffusion ponoʻī ma ka hoʻopili ʻana i nā hōʻailona echo i loaʻa ma ka hoʻololi ʻana i ka ∆ me Eq.1. Ua koho ʻia ʻo 7Li e hoʻoholo i ka diffusion coefficient o ka lithium ion.Hana ʻia nā ana a pau ma 30 ° C.

ʻO ka Raman spectroscopy setup he ʻōnaehana home me ka hoʻohana ʻana i kahi argon ion hiki ke hoʻopaʻa ʻia i kahi kukui laser excitation 458-nm i hoʻohui ʻia i loko o kahi microscope Olympus IX71 i hoʻohuli ʻia, a ua hāʻawi ʻia ke kukui hoʻopuehu i hope ma o kahi TriVista triple spectrometer setup (Princeton Instruments. ), ka mea i hoʻohana ʻia no ka hoʻopuehu ʻana i nā hōʻailona optical i ʻike ʻia me ka hoʻohana ʻana i kahi kāmeʻa hāmeʻa i hoʻohui pū ʻia me ka wai.Ma muli o ke kiʻekiʻe o ka optical absorbance i kēia mau nalu, ua hoʻohana ʻia nā mana laser haʻahaʻa e pale i ka hoʻomehana laser (<100 W·cm−2).

Ua hoʻohana ka DFT ground-state geometry optimization a me analytical frequency calculations i ka B3LYP hybrid functional functional a me 6-311++G** kumu hoʻonohonoho, me ka hoʻoponopono hoʻopuehu ʻana o ka atom-pairwise a Grimme (39) me ka Becke-Johnson damping scheme (D3BJ), e like me hoʻokō ʻia ma ORCA 3.0.3 (40).Ua hoʻohālikelike ʻia ʻo Raman spectra me ka hoʻohana ʻana i ka ORCA, a ua hoʻokō ʻia ka hiʻohiʻona o nā waiwai molekala me ka hoʻohana ʻana i ka polokalamu polokalamu Avogadro (41) me ka hoʻopiʻi kākoʻo ORCA.

ʻO nā ana electrochemical a pau a me ka hoʻomākaukau laʻana pili i hana ʻia i loko o kahi pahu mīkina lima piha argon (PureLab, PL-HE-4GB-1800; <1-ppm O2 a me H2O pae) i hoʻolaʻa ʻia no ka hōʻike ʻana i ka electrochemical.Ua kau ʻia ka pellet SCE ma luna o kahi lipine Li (Sigma-Aldrich; 99.9%) i kākoʻo ʻia ma kahi pā keleawe ʻoiai ua kau ʻia ka electrode counter a me ʻelua mau pahu Li i kuʻi ʻia (5-mm diameter) ma luna o ka pellet SCE no ka ʻike a me ka hana. nā electrodes.Hōʻike ʻia ka hoʻonohonoho ma ka fig.S7.Ua hoʻohana ʻia nā pine gula no ka hoʻopili ʻana i ka reference lithium a me nā electrodes hana.Hana ʻia ka voltammetry cyclic a me nā ana impedance me ka hoʻohana ʻana iā PGSTAT302 (Metrohm) i hoʻomalu ʻia ma o ka polokalamu Nova.Ua hana ʻia ka voltammetry cyclic me ka helu scan o 20 mV/s.Ua hana ʻia nā ana impedance me kahi amplitude AC o 5 mV a me ke alapine mai ka 1 MHz a i ka 0.1 Hz.

He 40-nm anatase TiO2 thin-film electrode i waiho ʻia e ka atomic layer deposition (ALD) ma kahi 300-mm silicon wafer me kahi 40-nm TiN underlayer i waiho pū ʻia e ALD.He electrode ho'āʻo maikaʻi loa ia no ka hōʻike ʻana i ka conductivity Li-ion ma o nā electrolytes, no ka mea, ʻaʻole ʻeha ʻo TiO2 i ka hoʻohaʻahaʻa kemika a i ʻole ke koʻikoʻi mechanical (ʻaʻohe loli nui) i ka wā kaʻa.No ke anaʻana i ka pūnaewele Li / SCE / TiO2, ua hoʻopihaʻia nā ILE-SCE i ke apo PTFE me ke anawaena o 4.3 mm a me ka mānoanoa o 0.15 cm;a laila, ua hoʻopaʻa ʻia ke apo ma waena o kahi pahu Li a me ke kiʻi ʻoniʻoni TiO2.

ʻO Nano-SCE / thin-film electrode half stacks, me ka LMO electrode, ua hana ʻia ma ka synthesizing i ka nano-SCE film ma nā electrodes.ʻO ka huina o 150 μl o x = 1.5 solution, ʻelemakule no nā lā 2, ua hoʻolei ʻia i loko o kahi apo aniani (diameter, 1.3 mm) i kau ʻia ma nā kiʻi electrolyte.Hoʻopaʻa ʻia ke apo me ka parafilm, a mālama ʻia ka hopena i loko o kahi pahu i hoʻopaʻa ʻia e gel no 4 mau lā.Ua hoʻomaloʻo ʻia ka pahu gel/electrode i hoʻokumu ʻia e hana i nā pūʻulu nano-SCE/electrode.ʻO ka mānoanoa o ka nano-SCE, i hoʻoholo ʻia me ka micrometer, he 300 μm.ʻO ka hope, ua kaomi ʻia kahi pahu lithium (1.75 mm mānoanoa, 99.9%; Sigma-Aldrich) ma ka nano-SCE/electrode stack e like me ka anode.Ua waiho ʻia ka electrode kiʻiʻoniʻoni lahilahi 100-nm LiMn2O4 (LMO) e ka lele ʻana o ka lekiō ma lalo o ke kahe Ar ma kahi wafer silika i uhi ʻia me 80-nm Pt (DC sputtering)/10-nm TiN (ALD) underlayers.Hoʻopili ʻia kēia waihona no 20 min ma 800 ° C i ka lewa oxygen.

Ua hoʻomākaukau ʻia nā kiʻi ʻoniʻoni electrode LiFePO4 (LFP) e ka uhi ʻana o ka lau.ʻO ka mua, ua hoʻohui ʻia ke kalapona ʻeleʻele a me ka LFP (2 a i ka 3 μm) i kahi hoʻonā wai i loaʻa i ka carboxymethylcellulose (CMC) e hana i ka hui ʻana i hoʻohui ʻia ma hope me ka hoʻohana ʻana i kahi hui honua.A laila, ua hui pū ʻia ka huahana homogenized me ka wai deionized a me ka fluorinated acrylic latex (JSR, TRD202A) i loko o kahi mea hoʻohui ʻia e hana i kahi slurry no ka uhi electrode.Hoʻolei ʻia ka slurry i hoʻomākaukau ʻia ma luna o nā pahu alumini e waiho ai i nā kiʻi electrode me ka hoʻohana ʻana i kahi uhi ʻili.Ua hoʻomaloʻo koke ʻia kēia mau electrodes pulu i uhi ʻia i loko o ka umu lewa me ka ea stagnant ma 70 ° C no 10 min a ua hoʻomaloʻo hou ʻia ma 140 ° C no 4 mau hola i loko o ka umu.ʻO nā kiʻiʻoniʻoni electrode maloʻo he 91 wt % LiFePO4, 3 wt % carbon black, 2 wt % CMC, a me 4 wt % TRD202A.ʻO 30 μm ka mānoanoa o ke kiʻiʻoniʻoni (hoʻoholo ʻia me ka micrometer a me ka scanning electron microscope).

Ua hana ʻia nā kiʻi ʻoniʻoni electrode Li4Ti5O12 (LTO) ma ke ʻano like.ʻO ka hui o nā electrodes maloʻo he 85 wt % Li4Ti5O12, 5 wt % carbon black, 5 wt % CMC, a me 5 wt % fluorinated acrylic latex (TRD2001A).ʻO 40 μm ka mānoanoa kiʻiʻoniʻoni.

Hoʻokuʻu ʻia ka hopena o SCE ma luna o ke kiʻi ʻoniʻoni electrode LFP a me LTO.ʻO ka mua, 100 μl o x = 1.5 solution, kahiko no nā lā 2, ua hoʻolei ʻia ma luna o kahi kiʻi electrode, me ke anawaena o 15 mm, waiho ʻia i loko o kahi pūnae kālā (#2032, MTI).Ma hope o ka gelled o ka SCE impregnated, ua maloʻo ke kiʻi ma 25 ° C no nā hola 72 i loko o ka umu (<5 × 10−2 mbar) e hana i ka nano-SCE a me ka hoʻopaʻa electrode.ʻO 380 μm ka mānoanoa nano-SCE.ʻO ka hope, ua paʻi ʻia kahi pahu lithium ma nā SCE / electrode stacks e like me ka anode, a ua hoʻopaʻa ʻia ka cell coin.Ua hana ʻia nā ana electrochemical me ka Solartron 1470E potentiostat ma ka lumi wela.

Loaʻa nā mea hoʻohui no kēia ʻatikala ma http://advances.sciencemag.org/cgi/content/full/6/2/eaav3400/DC1

Papa S1.Nā waiwai o ka silica matrix i loko o ka nano-SCE no ka hoʻonui ʻana i ka hakina molar o ka wai ionic i ka silica (waiwai x) i hoʻoholo ʻia mai ka N2 adsorption/desorption a i ʻole nā ana BET a me nā ʻike TEM.

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Na 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. Vereecken

Ka manawa hoʻouna: Iulai-15-2020