Kev nce qib tsis ntev los no ntawm anode rau sulfide-based all-solid-state lithium roj teeb
—— Ntu 1Lithium hlau anode
Tus sau:
JIA Linan, DU Yibo, GUO Bangjun, ZHANG Xi
1. Tsev Kawm Ntawv ntawm Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200241, Suav
2. Shanghai Yili Tshiab Zog Technology Co., LTD. , Shanghai 201306, Suav teb
Abstract
All-solid-state lithium batteries (ASSLBs) muaj lub zog ntau dua thiab muaj kev nyab xeeb dua li cov roj teeb lithium tam sim no, uas yog cov kev tshawb fawb tseem ceeb rau cov khoom siv hluav taws xob txuas ntxiv mus. Piv nrog rau lwm cov khoom siv hauv lub xeev electrolytes, sulfide solid-state electrolytes (SSEs) muaj cov yam ntxwv ntawm ultra-high ionic conductivity, tsis tshua muaj hardness, yooj yim ua, thiab zoo interfacial kev sib cuag, uas yog ib qho ntawm feem pheej txoj kev kom paub tag nrho cov khoom. - lub xeev roj teeb. Txawm li cas los xij, muaj qee qhov teeb meem cuam tshuam ntawm anodes thiab SSEs uas txwv lawv cov ntawv thov xws li kev cuam tshuam sab nraud, kev sib cuag tsis zoo, thiab lithium dendrite. Txoj kev tshawb no qhia txog qhov kev nce qib tam sim no hauv cov ntaub ntawv anode siv rau sulfide-based ASSLBs, sau cov xwm txheej kev txhim kho, kev siv tau zoo, cov teeb meem cuam tshuam thiab cov tswv yim daws teeb meem ntawm cov khoom siv anode tseem ceeb suav nrog lithium hlau, lithium alloys, silicon anode rau sulfide-based ASSLBs, thiab muab cov lus qhia rau kev txhim kho tom ntej ntawm cov khoom siv anode thiab kev daws teeb meem ntawm kev sib tshuam.
Ntsiab lus: tag nrho cov khoom-lub xeev lithium roj teeb; sulfide electrolyte; lithium anode; hlau anode; anode/electrolyte interfaces
Taw qhia
Cov roj teeb lithium-ion tau siv dav hauv ntau yam khoom siv thauj khoom vim lawv qhov hluav taws xob siab thiab lub zog siab ceev. Lawv yog cov khoom lag luam tseem ceeb rau kev siv tsheb hluav taws xob thiab kev xa tawm ntawm lub zog cia hauv lub zej zog uas muaj cov pa roj carbon tsawg. Txawm li cas los xij, cov roj teeb lithium-ion ua kua siv graphite tsis zoo electrodes, organic kua electrolytes, thiab nws yog xim hlau lithium oxide zoo electrodes (xws li LiCoO2). Ntawm qhov tod tes, lub zog tshwj xeeb ntawm cov roj teeb sib dhos yog txwv rau qhov ntau ntawm 200 ~ 250 Wh·kg-1, ua rau nws nyuaj rau kev ua tiav cov kev sib tw ntxiv hauv lub zog tshwj xeeb. Ntawm qhov tod tes, cov organic electrolytes muaj qhov tsis zoo xws li thermal stability thiab flammability. Ntxiv mus, cov lithium dendrites tsim tawm thaum lub sij hawm lub roj teeb lub voj voog tseem yuav ua rau muaj kev pheej hmoo loj ntawm lub roj teeb luv luv lossis txawm tias tawg. Cov teeb meem no tau ua rau ntau tus kws tshawb fawb tau mob siab rau thiab xav txog kev nyab xeeb ntawm lithium-ion roj teeb. Hloov cov hluav taws xob hluav taws xob hluav taws xob hluav taws xob nrog cov khoom siv hluav taws xob tuaj yeem tiv thaiv thermal khiav tawm thiab daws cov teeb meem kev nyab xeeb los ntawm cov kua hluav taws xob hluav taws xob uas siv hauv cov roj teeb lithium-ion ua kua. Nyob rau tib lub sijhawm, cov khoom siv hluav taws xob siab ntawm cov khoom siv electrolytes tseem suav tias yog ib qho ntawm cov kev sib tw hauv inhibiting kev loj hlob ntawm lithium dendrites.
Tam sim no, cov khoom siv hluav taws xob tseem ceeb muaj xws li plaub yam: sulfide solid-state electrolyte, oxide solid-state electrolyte, polymer solid-state electrolyte thiab halide solid-state electrolyte. Ntawm lawv, oxide electrolytes muaj qhov zoo ntawm kev ruaj ntseg zoo thiab nruab nrab ionic conductivity, tab sis muaj kev sib cuag tsis zoo. Polymer electrolytes muaj kev ruaj ntseg zoo rau lithium hlau thiab muaj cov cuab yeej ua kom paub tab, tab sis tsis zoo thermal stability, nqaim electrochemical windows, thiab qis ionic conductivity txwv qhov kev thov. Raws li hom tshiab ntawm electrolyte, halide electrolytes tau txais kev saib xyuas thoob plaws vim lawv cov ionic conductivity siab. Txawm li cas los xij, cov ntsiab lus siab valence hlau hauv halide electrolytes txiav txim siab tias lawv tsis tuaj yeem tiv tauj lithium hlau ncaj qha los tsim cov anode ruaj khov. Kev tshawb fawb txog halide electrolytes yuav tsum tau tshawb nrhiav ntxiv. Sulfide electrolytes raug suav hais tias yog ib txoj hauv kev zoo tshaj plaws kom paub txog tag nrho cov khoom-lub xeev lithium roj teeb (ASSLBs) electrolytes vim lawv cov ionic conductivity siab, tsis tshua muaj hardness, ua tau yooj yim, formability zoo, thiab kev sib cuag zoo.
Nyob rau hauv xyoo tas los no, muaj feem xyuam rau kev tshawb fawb ntawm sulfide electrolytes tau tsim ntxiv, thiab nws cov ionic conductivity tau mus txog qib piv rau cov kua organic electrolytes. Cov tshuaj sulfide electrolytes muaj xws li iav Li-PS sulfide (LPS) thiab derivative iav ceramics, nyiaj sulfide germanium ore (Li6PS5X, X= Cl, Br, I), thiab lithium sulfide ion superconductors (thio-lithium superionic conductor, thio -LISICONs), Li10GeP2S12 (LGPS) thiab cov khoom sib xws.
Ntawm cov khoom siv sulfide sib txawv, LGPS-hom electrolytes qhia txog qhov zoo tshaj plaws ionic conductivity. Hauv 2016, Kato et al. qhia txog superlithium ion conductor Li9.54Si1.74P1.44S11.7Cl0.3 (LSPSCl), uas nws ionic conductivity siab li 25 × 10-2 S·cm-1 ntawm chav tsev kub. LGPS kuj tseem muaj ultra-high ion conductivity ntawm 1.2 × 10-2 S·cm{19}} ntawm chav tsev kub. Qhov tsis muaj zog anisotropic ion conductivity ntawm ib leeg siv lead ua LGPS nyob rau hauv cov kev taw qhia (001) txawm mus txog 27 × 10-2 S·cm-1. Cov iav ceramics (Li7P3S11) thiab sulfide-germanite (Li6PS5Cl) tuaj yeem ua tiav siab ionic conductivities ntawm 10-3 S·cm-1. Cov roj teeb tag nrho-lub xeev sib txuas cov sulfide electrolytes nrog high-nickel txheej cathodes thiab high-zog anodes (xws li Si los yog metallic lithium) tuaj yeem pom lub zog tshwj xeeb ntawm 500 kW·h·kg-1. Txawm li cas los xij, daim ntawv thov ntawm sulfide electrolytes nyob rau hauv tag nrho cov-solid-state lithium roj teeb tseem muaj teeb meem xws li nqaim electrochemical qhov rais, tsis zoo electrode-electrolyte interface stability, tsis zoo huab cua stability, tsis muaj loj-scale manufacturing txoj kev, thiab tus nqi siab. Lub qhov rais nqaim electrochemical txiav txim siab tias qhov txo qis ntawm cov electrolyte yuav tshwm sim thaum lub zog sulfide electrolyte los rau hauv kev sib cuag nrog feem ntau cov electrodes tsis zoo, ua rau muaj kev cuam tshuam tsis ruaj khov, uas yog ib qho tseem ceeb hauv kev txwv txoj kev loj hlob ntawm tag nrho cov khoom-lub xeev lithium roj teeb. Qhov tsab xov xwm no tsuas yog sau cov ntsiab lus ntawm txoj kev loj hlob ntawm mainstream anode cov ntaub ntawv rau tag nrho cov-solid-state lithium roj teeb raws li sulfide electrolytes, thiab ntxiv summarizes lub interface teeb meem thiab daws cov tswv yim ntawm sulfide khoom electrolytes thiab anode cov ntaub ntawv. Muab cov lus qhia qhia rau kev txhim kho thiab kev lag luam daim ntawv thov ntawm tag nrho cov-solid-state lithium roj teeb raws li sulfide electrolytes.
1 Lithium hlau anode
Cov roj ntsha lithium yog ib qho tseem ceeb ntawm cov khoom siv sib tw kom paub txog cov tiam tom ntej ntawm lub zog siab ceev lithium roj teeb vim nws lub peev xwm theoretical siab (3860 mA·h·g-1) thiab tsis tshua muaj hluav taws xob muaj peev xwm (-3.040 V vs SHE). Lithium anodes muab roj teeb lub zog ceev 10 npaug siab dua li cov graphite anodes. Txawm li cas los xij, qhov tsis tshua muaj hluav taws xob hluav taws xob muaj peev xwm ntawm cov hlau lithium txiav txim siab nws cov tshuaj lom neeg muaj zog heev thiab ua haujlwm electrochemical. Yog li, kev sib cuag nrog ib qho electrolyte tuaj yeem yooj yim ua rau txo qis hauv cov electrolyte. Lub ntim expansion npaum li cas ntawm cov hlau lithium yog loj, lub interface impedance yog nce, lithium dendrites yog tsim, thiab nws thiaj li muaj ib tug luv luv Circuit Court tshwm sim. Txij li thaum tag nrho cov khoom siv-lub xeev lithium roj teeb pom muaj teeb meem xws li lub voj voog tsis zoo, kev cuam tshuam tsis ua haujlwm, thiab kev ua haujlwm qis thaum lub sijhawm ua haujlwm, nws tseem ceeb heev uas yuav tau tshawb xyuas cov teeb meem cuam tshuam ntawm cov hlau lithium anodes thiab cov khoom electrolytes. Feem ntau hais lus, feem ntau sulfide khoom electrolytes qhia thermodynamic thiab kinetic instability ntawm hlau lithium. Nyob rau tib lub sijhawm, cov qoob loo ciam teb thiab qhov tsis xws luag hauv cov khoom siv electrolyte yuav ua rau tsim cov lithium dendrites, uas tsis tuaj yeem daws cov teeb meem ntawm lithium dendrite kev loj hlob thiab roj teeb luv luv. . Nws yog ib nqi sau cia hais tias nyob rau hauv siab tam sim no ntom, lithium / sulfide electrolyte interface tsis ua hauj lwm teeb meem yog tshwj xeeb tshaj yog tseem ceeb, uas zoo heev txwv kev txhim kho lub zog ceev ntawm tag nrho cov-solid-state lithium roj teeb.
1.1 Lithium / sulfide electrolyte interface tshuaj stability
Raws li pom hauv daim duab 1, Wenzel li al. cais cov lithium/solid electrolyte interface hom los ntawm ib tug thermodynamic foundations rau hauv thermodynamically ruaj khov interfaces thiab thermodynamically unstable interfaces.
Fig.1 Hom kev sib cuam tshuam ntawm lithium hlau thiab cov khoom siv hauv lub xeev electrolyte
(1) Thermodynamically ruaj khov interface: Raws li pom nyob rau hauv daim duab 1(a), ob theem nyob rau hauv kev sib cuag yog nyob rau hauv lub xeev ntawm thermodynamic equilibrium. Cov hlau lithium tsis hnov mob txhua yam nrog cov electrolyte, tsim lub dav hlau ob sab, xws li LiF, Li3N thiab lwm yam lithium binary compounds.
(2) Thermodynamically unstable interface: Vim lub thermodynamically tsav tshuaj tshuaj tiv thaiv ntawm tus hu electrolyte thiab electrode, ib tug peb-dimensional interface txheej yuav tsim. Nyob ntawm seb cov txheej txheem sib txuas tsim los ntawm cov khoom siv tshuaj tiv thaiv puas muaj hluav taws xob thiab ionic conductivity txaus, nws tuaj yeem raug cais ntxiv rau hauv ob qhov txuas hauv qab no.
①Mixed conductive interface txheej: Thaum cov khoom muaj hluav taws xob txaus thiab ionic conductivity, txheej txheej txheej tuaj yeem ruaj khov rau hauv cov khoom electrolyte. Qhov tsim ntawm no hybrid conductive interlayer yuav kawg tso electron thauj mus los ntawm electrolyte, ua rau nws tus kheej tawm ntawm lub roj teeb [Daim duab 1(b)]. Lub interfacial instability ntawm sulfide khoom electrolytes ua rau lub cim ntawm interfacial sab tshua, uas yuav ua rau kom ceev attenuation ntawm roj teeb muaj peev xwm los yog txawm tsis ua hauj lwm. Wenzel et al. siv nyob rau hauv situ X-ray photoelectron spectroscopy (XPS) ua ke nrog lub sij hawm daws teeb meem electrochemical ntsuas. Cov ncauj lus kom ntxaws txog cov tshuaj tiv thaiv ntawm qhov sib cuam tshuam ntawm LGPS thiab nws yog xim hlau lithium yog muab, thiab nws tau txheeb xyuas tias qhov decomposition ntawm LGPS ua rau tsim cov khoom electrolyte interface theem ntawm Li3P, Li2S, thiab Li-Ge alloys. Ntawm lawv, Li3P thiab Li2S yog ionic conductors, thiab Li-Ge alloy yog hluav taws xob conductor. Cov txheej txheem sib xyaw ua ke sib xyaw ua ke yuav ua rau LGPS txuas ntxiv mus rau decompose, thiab qhov tsis zoo electrode interface impedance yuav nce ntxiv, nws thiaj li ua rau lub roj teeb tsis ua haujlwm.
②Metastable khoom electrolyte interface txheej: Yog hais tias cov tshuaj tiv thaiv cov khoom uas tsis yog-conductive los yog tsuas muaj tsawg hluav taws xob conductivity, lub interface txheej yuav raug txwv kom loj hlob mus rau hauv ib tug nyias nyias zaj duab xis, thiab ib tug ruaj khov-state electrolyte interphase, SEI, tej zaum yuav tsim. . Raws li pom nyob rau hauv daim duab 1(c), qhov kev ua tau zoo ntawm lub roj teeb no yuav nyob ntawm seb cov khoom siv ion conduction ntawm SEI. Cov sulfide-germanite hom electrolyte yog qhov ruaj khov, thiab nws cov khoom decomposition Li2S, Li3P thiab LiX (X=Cl, Br thiab I) muaj tsawg txaus hluav taws xob conductivity kom tsis txhob txuas ntxiv decomposition ntawm electrolyte thiab yooj yim tsim SEI ruaj khov. . Tib lub sijhawm, Li3P muaj ionic conductivity siab, ua kom muaj kev sib kis tau zoo ntawm lithium ions hauv cov roj teeb hauv lub xeev.
1.2 Kev tshawb fawb txog cov cuab yeej cuab tam ntawm lithium hlau
Cov khoom tam sim no-khoom sib txuas ntawm qhov tsis zoo ntawm cov electrode thiab cov khoom electrolyte yog ib qho kev sib chwv tsawg, uas yooj yim ua rau muaj kev cuam tshuam kev cuam tshuam. Txawm li cas los xij, cov khoom siv hluav taws xob ntawm cov hlau lithium, tshwj xeeb tshaj yog cov creep ntawm cov hlau lithium, yuav ua rau muaj kev cuam tshuam ntxiv rau kev sib cuag, ua rau muaj kev cuam tshuam ntawm cov voids thiab txawm tias tsis zoo electrode delamination ntawm qhov ceev tam sim no. Yog li ntawd, kev kawm cov khoom siv ntawm cov hlau lithium, tshwj xeeb tshaj yog cov cwj pwm ntawm cov hlau lithium, yog qhov tseem ceeb rau lub voj voog ruaj khov ntawm tag nrho cov khoom-lub xeev cov roj teeb.
Tian et al. ua kev tshawb fawb txog kev sib cuag mechanics thiab tsim cov qauv theoretical tsim nyog kom tau txais cov xwm txheej ntawm ciam teb uas cuam tshuam rau kev ntxhov siab faib ua haujlwm ntawm elastic, yas thiab viscous tiv tauj ntawm lithium hlau anode. Kwv yees qhov chaw sib cuag ntawm cov hlau lithium-sulfide khoom electrolyte interface thiab xam lub peev xwm poob los ntawm ion diffusion ntawm lub interface thiab poob ntawm qhov chaw sib cuag. Cov kev sim qhia tau hais tias ntawm qhov qis txiav tawm hluav taws xob (3.8 V), kev sib raug zoo ntawm qhov txo qis ntawm cov roj teeb muaj peev xwm thiab qhov poob ntawm qhov chaw sib cuag yog yuav luag linear, nrog txoj kab nqes ntawm 1. Thaum nyob ntawm qhov hluav taws xob ntau dua (4.{{ 6}} V), txoj kab nqes qis dua 1, thiab lub peev xwm poob qis nrog nce tus nqi tawm. Fincher et al. siv tensile thwmsim los ntsuam xyuas cov neeg kho tshuab cov teebmeem ntawm kev lag luam lithium ntawv nyiaj thiab pom tias lub zog ntawm cov hlau lithium lithium ranges ntawm 0.57 mus rau 1.26 MPa ntawm tus nqi strain ntawm 5 × 10-4 ~ 5 × {{ 15}} s-1. Rau qhov ntsuas indentation nrog lub hom phiaj ntawm 0.05 s–1, lub hardness poob qis heev los ntawm ze li ntawm 43. 0 MPa mus rau 7.5 MPa raws li qhov tob indentation nce los ntawm 25{{ 37}} nm rau 1 0 µm. Cov khoom yas ntsuas los ntawm cov kev ntsuam xyuas nanoindentation tau pom muaj zog strain rate dependence nrog kev ntxhov siab exponents ntawm 6.55 thiab 6.90 feem. Finite element tsom xam yog siv los txheeb xyuas qhov tob ntawm qhov ntsuas qhov ntev hauv cov ntawv thov roj teeb. Nws tuaj yeem muab cov lus qhia tseem ceeb rau kev ua kom zoo dua cov qauv ntawm lithium anodes thiab ua kom cov nqi thiab tawm kev ruaj ntseg, thiaj li txo qis qhov tsis sib xws ntawm lithium thaum lub sij hawm electrochemical cycles. Masias et al. systematically ntsuas lub elastic, yas thiab lub sij hawm-dependent mechanical zog ntawm polycrystalline lithium ntawm chav tsev kub. Nws cov Young's modulus, shear modulus thiab Poisson tus piv tau txiav txim siab yog 7.82 GPa, 2.83 GPa thiab 0.38 raws, thiab lub zog tawm los ntawm 0.73 thiab 0.81 GPa. Lub hwj chim-txoj cai creep dominates nyob rau hauv nruj, nrog ib tug kev nyuaj siab Performance index ntawm 6.56. Kev ntsuas compression tau ua nyob rau hauv cov roj teeb uas muaj kev ntxhov siab (0.8 ~ 2.4 MPa), thiab kev sib tw tseem ceeb thiab kev txo qis ntawm cov kab mob nrog lub sijhawm tau pom. Narayan et al. tsim cov qauv lus teb rau tag nrho cov khoom-lub xeev roj teeb lithium anode raws li qhov loj deformation txoj kev xav, simulating kev sib cuam tshuam ntawm lithium anode thiab sulfide khoom electrolyte hauv elastic-viscoplastic cov tshuaj tiv thaiv ntawm lithium. Nws qhia tau hais tias cov tshuaj tiv thaiv ntawm strain muaj feem xyuam rau lub ntim deformation ntawm lithium anode, uas yog lub ntsiab yog vim li cas rau tsis ua hauj lwm ntawm solid-state roj teeb. Los ntawm batch tensile thiab nanoindentation tests, lithium hlau qhia pom tseeb strain rate dependence thiab loj decay thaum creep. qhia tau hais tias kev nplua-tuning ntawm deformation mechanics tuaj yeem ua tiav los ntawm kev kho cov lithium deposits los txhim kho lub zog ntawm lithium anode thiab txo qis lithium kev loj hlob tsis ruaj khov thaum lub sij hawm electrochemical cycling.
Ntxiv rau qhov kev kawm tag nrho ntawm cov hlau lithium, kev kawm ntawm nanomechanics muab qhov tseem ceeb heev thiab cov ncauj lus kom ntxaws heev thiab cov ntaub ntawv hauv zos ntawm cov nplai me. Nanoindentation thwmsim yog ib qho ntawm feem ntau siv cov cuab yeej tsom xam rau saum npoo thiab hauv zos yam ntxwv. Nanoindentation thwmsim ua nyob rau hauv cov roj inert muaj peev xwm soj ntsuam cov neeg kho tshuab, electrochemical, thiab morphological coupling tus cwj pwm ntawm metallic lithium. Herbert et al. tau ua ib tug series ntawm nanoindentation thwmsim ntawm high-purity evaporated lithium films thiab sau cov ntaub ntawv ntawm yas ntws yam ntxwv, nrog rau elastic modulus, hardness thiab yield zog. Cov evolution ntawm cov ntaub ntawv saum toj no nrog cov kev hloov pauv tseem ceeb xws li qhov ntev, qhov sib txawv, qhov kub thiab txias, crystallographic orientation thiab electrochemical cycling tau kawm, qhia tau hais tias cov yas ntws ntawm lithium feem ntau cuam tshuam nrog kev nkag mus tsis tu ncua nyob rau hauv tas li load lossis siab. Lub creep ntawm lithium thaum lub sij hawm electrochemical them thiab tso tawm tuaj yeem ua rau buckling ntawm lub interface thiab ua kom muaj kev ntxhov siab ntxiv. Nyob rau tib lub sijhawm, tus cwj pwm viscoplastic ntawm lithium yuav cuam tshuam ntxiv rau thaj chaw sib cuag, ua rau muaj kev cuam tshuam ntawm ion diffusion channel thiab kev cuam tshuam tsis ruaj khov. Txawm li cas los xij, tam sim no kev tshawb fawb nanomechanical ntawm cov hlau lithium tseem nyob hauv nws theem ua ntej, thiab kev tshawb fawb ntxiv tseem ceeb heev. Qee cov thev naus laus zis tshiab xws li nanocolumn compression thiab hauv-situ real-time kev soj ntsuam ntawm cov hlau lithium nanomechanics kuj tau raug npaj los tshuaj xyuas qhov sib txuas ntawm cov hlau lithium anode interface thiab muab cov ntaub ntawv siab ncaj ncees txog kev sib txuas kom nkag siab ntxiv txog kev sib txuas ntawm cov khoom siv hluav taws xob. nws yog xim hlau lithium, yog li muab qhov ua tau rau kev tsim ntawm nanoscale metallic lithium anodes.
1.3 Nucleation thiab kev loj hlob ntawm lithium dendrites
Lithium dendrites yog ib qho ntawm cov teeb meem tseem ceeb cuam tshuam rau kev ruaj ntseg thiab kev nyab xeeb ntawm lithium-ion roj teeb. Cov khoom electrolytes tau ntev tau suav hais tias yog ib qho kev daws teeb meem rau lithium dendrite kev loj hlob vim lawv lub zog txhua yam. Txawm li cas los xij, ntau qhov kev tshawb fawb tau pom tias qhov teeb meem ntawm lithium dendrites hauv cov khoom electrolytes tseem muaj, thiab tseem hnyav dua li cov roj teeb lithium. Hauv cov roj teeb uas muaj zog, muaj ntau yam laj thawj rau kev loj hlob ntawm lithium dendrites, nrog rau kev sib cuag tsis sib xws ntawm qhov sib cuam tshuam ntawm electrolyte thiab metallic lithium, qhov tsis xws luag, thaj tsam lis, voids hauv electrolyte, qhov chaw nqi, thiab lwm yam. Monroe li al. qhia txog kev loj hlob ntawm lithium dendrite qauv raws li nws yog xim hlau lithium anode thiab khoom electrolyte. Cov yam ntxwv xws li electrolyte elasticity, compression quab yuam, nto nro thiab deformation quab yuam tau txiav txim siab hauv cov qauv. Cov txiaj ntsig simulation qhia tau hais tias thaum lub shear modulus ntawm cov electrolyte yog sib npaug rau lithium, ib qho kev sib txuas ruaj khov yuav raug tsim. Thaum lub shear modulus ntawm cov electrolyte yog kwv yees li ob zaug ntawm lithium (4.8 GPa), tiam ntawm lithium dendrites yuav raug suppressed. Txawm li cas los xij, hauv kev tshawb fawb tag nrho-lub xeev lithium roj teeb, nws tau pom tias lithium dendrites tseem tsim nyob rau hauv cov khoom electrolytes nrog siab shear modulus [xws li Li7La3Zr2012 (LLZO), elastic modulus ≈ 100 GPa]. Yog li ntawd, cov qauv no tsuas yog siv tau rau qhov zoo tagnrho interfaces yam tsis muaj qhov tsis xws luag hauv microscopic thiab tsis sib xws. Porz et al. pom tias lub siab shear modulus ntawm cov electrolyte yuav ua rau siab kawg tam sim no ceev, inducing lub nucleation thiab loj hlob ntawm hlau lithium nyob rau hauv lub grain ciam teb thiab voids ntawm cov khoom electrolyte. Nagao et al. siv nyob rau hauv-situ scanning electron microscopy los soj ntsuam cov lithium deposition thiab dissolution txheej txheem ntawm qhov tsis zoo electrode interface nyob rau hauv tag nrho cov-solid-state lithium roj teeb, qhia txog cov kev hloov nyob rau hauv lub lithium deposition morphology nrog txawv thov tam sim no ntom. Thaum qhov ceev tam sim no tshaj 1 mA·cm-2, lithium deposition hauv zos yuav ua rau cov kab nrib pleb loj dua, uas ua rau txo qis ntawm cov lithium deposition thiab dissolution, thiab cov kab nrib pleb yuav ntxiv mus txog thaum lithium dendrites tsim. Ntawm qhov tod tes, cov lithium reversible thiab reversible lithium deposition thiab dissolution tuaj yeem ua tiav ntawm qhov ceev tam sim no ntawm 0.01 mA·cm-2, yuav luag tsis muaj kab nrib pleb. Yog li ntawd, tsuas yog tsom mus rau lub siab shear modulus ntawm electrolyte tsis tuaj yeem daws qhov teeb meem ntawm lithium dendrite kev loj hlob, thiab tuaj yeem txo cov ionic conductivity ntawm electrolyte thiab cuam tshuam rau lub zog ceev ntawm cov roj teeb hauv lub xeev.
Porz et al. tau kawm txog cov nucleation thiab kev loj hlob mechanism ntawm lithium dendrites nyob rau hauv ntau yam electrolytes thiab qhia tau hais tias qhov pib ntawm lithium nkag mus rau hauv lub nto morphology ntawm cov khoom electrolyte. Tshwj xeeb, qhov loj thiab qhov ntom ntawm qhov tsis xws luag, thiab qhov tso tawm ntawm lithium hauv qhov tsis xws luag tuaj yeem tsim cov kev ntxhov siab uas ua rau tawg tawg. Tsis tas li ntawd, qhov sib txawv ntawm qhov sib txawv ntawm cov nplej, cov ciam teb lossis cov kev sib tshuam kuj tuaj yeem ua rau cov tiam ntawm lithium dendrites. Yus et al. theoretically kawm lub zog, muaj pes tsawg leeg thiab thauj khoom ntawm peb lub zog qis symmetrically tilted grain ciam teb nyob rau hauv cov khoom electrolytes. Nws qhia tau hais tias kev thauj cov lithium ions ntawm cov ciam teb ntawm cov nplej yog qhov nyuaj dua li hauv cov nplej thiab muaj kev nkag siab rau qhov kub thiab txias ntawm cov kab lis kev cai. Raj et al. theoretically kawm cov nyhuv ntawm grain ciam teb tsis kam ntawm lub nucleation ntawm lithium dendrites ntawm cov khoom electrolyte / lithium interface. Lawv tau npaj siab tias qhov siab ionic resistivity ntawm cov ciam teb thiab lub cev tsis sib xws ntawm cov anode interface yuav ua rau muaj kev nce hauv cov khoom siv hluav taws xob hauv zos ntawm lithium, yog li txhawb kev tsim cov lithium dendrites. Yog li ntawd, piv nrog cov hmoov nplej siv lead ua, cov ciam teb nrog cov ion tiv thaiv siab muaj feem ntau yuav ua rau cov nucleation thiab kev loj hlob ntawm lithium dendrites. Kev loj hlob mechanism ntawm lithium dendrites nyob rau hauv tag nrho cov-solid-state roj teeb tau maj mam ua kom pom tseeb nrog kev tshawb fawb ntxiv. Txawm li cas los xij, tseem tsis muaj txoj hauv kev zoo los ua kom tag nrho cov lithium dendrites, thiab cov kev tshawb fawb ntsig txog yuav tsum tau ua kom qhov tob kom paub txog kev siv cov hlau lithium anodes hauv tag nrho cov roj teeb hauv lub xeev kom sai li sai tau.
1.4 Interface daws teeb meem cov tswv yim
Ntau txoj hauv kev tau raug npaj los daws cov teeb meem hauv daim ntawv thov ntawm lithium anodes, suav nrog kev siv lub zog sab nraud, siv SEI txheej, kev ua kom zoo ntawm electrolytes, thiab kev hloov kho ntawm cov hlau lithium. Qhov no txo qhov cuam tshuam ntawm lithium creep ntawm lub roj teeb, ua rau thaj chaw sib cuag ntawm cov khoom sib txuas ntawm cov khoom sib txuas, inhibits sab kev cuam tshuam ntawm kev sib tshuam ntawm sulfide khoom electrolyte thiab cov hlau lithium anode, txhim kho lithophilicity ntawm lub anode interface, thiab zam kev tsim thiab loj hlob ntawm lithium dendrites.
1.4.1 Siv lub zog sab nraud
Kev siv lub siab sab nraud tuaj yeem ua rau thaj chaw sib cuag ntawm cov khoom sib txuas, txo qhov kev puas tsuaj los ntawm kev nkag mus rau qhov tsis zoo electrode interface, thiab txhim kho lub voj voog ruaj khov ntawm lub roj teeb. Zhang et al. tau tshaj tawm ntau lub sijhawm peb-dimensional-dependent contact model los piav qhia txog kev hloov pauv ntawm cov khoom electrolyte / lithium anode interface nyob rau hauv pawg siab. Kev suav cov theoretical qhia tau hais tias cov pawg siab siab txog li 20 GPa zoo li cuam tshuam rau kev tsim cov voids, ib txoj hauv kev zoo los xyuas kom meej kev sib txuas lus sib txuas, muaj peev xwm ua tiav cov roj teeb ruaj khov. Cov pawg siab dua tsis muaj txiaj ntsig zoo rau kev ua haujlwm roj teeb. Cov pawg qis qis tsis tuaj yeem daws qhov teeb meem kev sib cuag ntawm qhov khoom-khoom interface. Cov pawg siab ntau dhau tuaj yeem tsim cov lithium dendrites tau yooj yim thiab ua rau luv luv hauv lub roj teeb. Wang et al. tau kawm txog cov nyhuv ntawm pawg siab ntawm kev ua haujlwm ntawm lithium / sulfide electrolyte roj teeb thiab pom tias thaum lub sij hawm lithium stripping txheej txheem, qhov siab tshaj plaws tso cai stripping tam sim no ceev yog proportional rau cov ntaub ntawv sab nraud. Thaum lub sij hawm deposition txheej txheem, siab dua thov yuav txo qhov siab tshaj plaws deposition tam sim no, uas yog, siab stacking siab yuav yooj yim ua rau cov tiam ntawm lithium dendrites (Daim duab 2).
Fig.2 Kev sib raug zoo ntawm qhov siab tshaj plaws tam sim no ceev (MACD) thiab sab nraud siab rau stripping thiab deposition hauv ASSLBs
1.4.2 Artificial khoom electrolyte interface txheej
Muab qhov ruaj khov SEI ntawm sulfide khoom electrolyte / lithium interface tuaj yeem zam kev sib cuag ncaj qha ntawm cov hlau lithium thiab sulfide khoom electrolyte, zoo inhibiting qhov tshwm sim ntawm kev cuam tshuam sab cuam tshuam thiab tsim thiab loj hlob ntawm lithium dendrites. Feem ntau, muaj ob txoj hauv kev tsim SEI: hauv-situ SEI thiab ex-situ SEI. Wang et al. tsim ib qho kev tiv thaiv nyob rau hauv-situ ion conductive txheej ntawm polished lithium hlau los ntawm spin txheej tshuab. Kev sib xyaw ntawm polyacrylonitrile (PAN) thiab fluoroethylene carbonate (FEC) yog siv los kos cov txheej txheem tiv thaiv kab mob (LiPFG) tsim los ntawm cov organic matrix ntawm inorganic Li3N thiab LiF ntawm lithium nto. Ua tau zoo txhawb nqa kev tso nyiaj ntawm lithium thiab txhim kho kev ruaj ntseg thiab kev sib raug zoo. Li et al. tsim ib qho in-situ polymerized interlayer ntawm 1, 3-dioxolane hauv lithium difluoro (oxalate) phosphate. Lub SEI tsim ntawm Li / LGPS interface muaj ob txheej txheej txheej. Sab saum toj txheej yog nplua nuj nyob rau hauv polymers thiab elastic, thiab cov txheej hauv qab yog tag nrho ntawm inorganic tshuaj los inhibit lub nucleation thiab loj hlob ntawm lithium dendrites. Nyob rau tib lub sijhawm, kev sib cuag tsis sib haum ntawm Li / LGPS interface tau ua tiav, uas txhawb nqa kev sib kis ntawm lithium ions thiab inhibits qhov tsis tu ncua ntawm LGPS. Cov roj teeb lithium symmetric nrog cov gel polymer txheej ua kom pom kev ruaj khov dua 500 h nyob rau hauv cov xwm txheej ntawm 0.5 mA·cm-2/0. 5 mAh·cm-2. Gao et al. qhia txog nanocomposite raws li organic elastic ntsev [LiO-(CH2O) n -Li] thiab inorganic nanoparticle ntsev (LiF, -NSO2-Li, Li2O), uas yuav siv tau raws li theem nrab los tiv thaiv LGPS. Cov khoom siv nanocomposite yog tsim nyob rau hauv qhov chaw ntawm Li los ntawm electrochemical decomposition ntawm cov kua electrolyte, uas txo cov interface kuj, muaj zoo tshuaj thiab electrochemical stability thiab interface compatibility, thiab zoo inhibits qhov tshwm sim ntawm LGPS txo cov tshuaj tiv thaiv. ruaj khov lithium deposition ntau tshaj 3000 h thiab lub neej voj voog ntawm 200 zaug tau ua tiav. Lub zog txhua yam ntawm SEI yog qhov tseem ceeb heev rau lub voj voog ruaj khov ntawm tag nrho cov khoom-lub xeev cov roj teeb. Yog hais tias lub zog txhua yam ntawm SEI tsawg dhau, dendrite nkag mus yuav tshwm sim. Yog tias SEI tsis tawv txaus, khoov tawg yuav tshwm sim [Daim duab. 3(a)] ib. Duan et al. npaj cov txheej txheem LiI los ntawm cov tshuaj iodine vapor deposition raws li ib qho khoom siv SEI ntawm cov hlau lithium thiab LPS [Daim duab 3(b)]. Lub LiI txheej tsim nyob rau hauv situ muaj ib tug tshwj xeeb, slender mov-zoo li tus LiI siv lead ua intertwined qauv, uas muab cov neeg kho tshuab siab zog thiab zoo heev toughness, thiab muaj peev xwm inhibit qhov kev loj hlob ntawm lithium dendrites. thiab yoog tau zoo rau cov kev hloov pauv hauv lithium ntim, yog li tuav lub zog Li/LGPS interface [Daim duab 3(c)]. Nyob rau tib lub sijhawm, LiI txheej no muaj cov ionic conductivity siab thiab qee yam tshuaj inertness, thiab qhia tau tias muaj kev ruaj ntseg siab rau ob qho tib si lithium thiab LGPS. Lub roj teeb Li/LiI/LGPS/S npaj tau pom tias muaj peev xwm ntawm 1400 mA·h·g{30}} ntawm 0.1 C, thiab pom tias muaj peev xwm tuav tau ntawm 80.6% tom qab 150 cycles ntawm chav tsev kub. Txawm tias nyob rau hauv qhov hnyav ntawm 1.35 mA·h·cm-1 thiab 90 degree, nws tseem muaj peev xwm ntawm 1500 mA·h·g-1 thiab ruaj khov zoo rau 100 cycles. Qhia nws lub peev xwm zoo hauv ntau yam kev thov. Raws li txoj kev daws teeb meem, Liang et al. synthesized Li x SiS y txheej nyob rau hauv qhov chaw ntawm cov xim hlau lithium li SEI kom stabilize Li/Li3PS4 interface. Li x SiS y txheej no yog huab cua ruaj khov thiab tuaj yeem tiv thaiv kev cuam tshuam sab ntawm lithium thiab ib puag ncig ib puag ncig. Nws tuaj yeem nyob ruaj khov rau ntau tshaj 2000 teev hauv lub roj teeb symmetrical. Pab pawg kuj tau tshaj tawm cov tswv yim daws teeb meem siv polyacrylonitrile-sulfur composites (PCE) raws li ex-situ dag SEI. Siv PCE ua cov txheej txheem nruab nrab ntawm qhov sib txuas ntawm lithium hlau thiab LPS ua rau muaj kev cuam tshuam cuam tshuam ntawm kev sib cuam tshuam ntawm LPS thiab Li hlau. Cov roj teeb uas sib sau ua ke tag nrho-lub xeev muaj peev xwm ua tau zoo. 148 mAh·g-1 ntawm 0.1 C tus nqi. Nws yog 131 mA·h·g-1 ntawm 0.5 C tus nqi. Lub peev xwm tseem tshuav 122 mA·h·g-1 tom qab 120 cycles ntawm 0.5 C tus nqi. Qhia tau zoo heev.
Fig.3 Schematic daim duab interface ntawm LGPS thiab Li anode
1.4.3 Electrolyte optimization
Electrolyte optimization tuaj yeem tsis tsuas yog txhim kho ionic conductivity ntawm sulfide electrolyte, tab sis kuj zam los yog txo cov electrolyte los ntawm lithium anode rau qee yam. Ntawm lawv, siv cov khoom tsim nyog hloov pauv yog lub tswv yim zoo los txhim kho ionic conductivity thiab stabilize lub anode interface. Kev sim los ntawm Sun et al. qhia tias oxygen doping tuaj yeem nce ion conductivity (Li10GeP2S11.7O0.3: 8.43 × 10-2 S·cm-1; LGPS: 1.12 × {{12} } S·cm-1). Nyob rau tib lub sijhawm, kev cuam tshuam ntawm kev sib tshuam yog tiv thaiv, yog li txhim kho kev ruaj ntseg ntawm lithium / sulfide electrolyte interface. Ntxiv rau cov pa oxygen, hlau sulfide doping tuaj yeem txo qhov impedance ntawm lithium / sulfide electrolyte interface. Piv txwv li, Li7P2.9S10.85Mo0. Li3.06P0.98Zn0. Lub peev xwm tuav tau ntawm 81%, liab qab Li3PS4 tsuas yog 35%). Txawm hais tias tsim nyog hloov pauv tau pom cov txiaj ntsig zoo rau lithium / sulfide electrolyte interface. Txawm li cas los xij, cov kev hloov kho no tseem muaj teeb meem xws li qhov tshwm sim ntawm kev cuam tshuam sab thiab tsim cov lithium dendrites thaum lub sij hawm ntev. Cov kev txwv sab saud ntawm lub luag haujlwm ntawm kinetics ntawm cov teeb meem cuam tshuam yuav tsum tau lees paub ntxiv, thiab lwm cov tswv yim yuav tsum tau ua ke los txhim kho cov tshuaj lom neeg ruaj khov ntawm lithium / sulfide electrolyte interface. Tus qauv tsim electrolyte tuaj yeem cuam tshuam qhov tshwm sim ntawm cov kev cuam tshuam sab nraud thiab tiv thaiv cov nucleation thiab kev loj hlob ntawm lithium dendrites. Ye et al. tau npaj ib qho kev tsim qauv zoo ntawm cov txheej txheem sandwich-structured electrolyte [Daim duab 4(a)]. Sandwiching cov electrolyte tsis ruaj khov ntawm cov electrolytes ruaj khov dua tsis txhob sib cuag ncaj qha los ntawm qhov zoo hauv zos decomposition hauv txheej ntawm cov electrolyte tsis ruaj khov. Nws tuaj yeem tiv thaiv kev loj hlob ntawm lithium dendrites thiab sau cov kab nrib pleb uas tsim tawm. Lub tswv yim nthuav dav zoo li no ua tiav lub voj voog ruaj khov ntawm cov hlau lithium anode ua ke nrog LiNi0.8Mn0.1Co0.1O2 cathode [raws li qhia hauv daim duab 4(b), lub peev xwm tuav tau yog 82% tom qab 10,000 cycles ntawm 20 C]. Qhov tseem ceeb tshaj, txoj haujlwm no tsis txwv rau cov khoom tshwj xeeb. Lub voj voog ruaj khov tuaj yeem pom tau siv LGPS, LSPSCl, Li9.54 Si1.74P0.94S11.7Cl0.3 (LSPS), Li3YCl6, thiab lwm yam raws li cov ntaub ntawv hauv nruab nrab. Nws muab txoj kev tsim qauv siv tau los txhim kho kev ruaj ntseg ntawm lithium anode / sulfide electrolyte interface.
Fig.4 Schematic daim duab ntawm cov khoom siv hluav taws xob tsim hluav taws xob thiab lub voj voog ntev electrochemical kev ua haujlwm nkhaus
1.4.4 Lithium anode hloov kho
Kev hloov kho ntawm lithium anode tuaj yeem txo lossis zam qhov tshwm sim ntawm electrolyte cov kab nrib pleb tshwm sim los ntawm tus cwj pwm ntawm cov hlau lithium thaum caij tsheb kauj vab, yog li inhibiting qhov tsim ntawm lithium dendrites. Raws li pom hauv daim duab 5, Su et al. siv cov graphite zaj duab xis los tiv thaiv lithium tsis zoo electrode, cais cov LPS electrolyte txheej ntawm lithium hlau, thiab inhibit qhov decomposition ntawm LGPS. Raws li cov neeg kho tshuab shrinkage mechanism, sab nraud siab ntawm 100 ~ 250 GPa yog siv rau lub roj teeb system. Qhov kev txwv sab nraud no ua kom zoo dua qhov kev sib cuag ntawm cov khoom siv hluav taws xob thiab nruab nrab ntawm txheej electrolyte thiab Li / G anode. All-solid-state roj teeb ua tiav kev ua haujlwm zoo heev. Tsis tas li ntawd, alloying metallic lithium kuj yog ib txoj hauv kev tseem ceeb los daws cov teeb meem lithium anode interface ntawm tag nrho cov khoom-lub xeev lithium roj teeb. Nyob rau hauv cov ntaub ntawv tam sim no, lithium alloys tau qhia txog qee qhov zoo hauv kev daws teeb meem xws li kev cuam tshuam loj ntawm sab nraud thiab cov tiam ntawm lithium dendrites hauv lithium anodes, uas yuav qhia meej hauv qab no.
Fig.5 Kev tiv thaiv tsim ntawm graphite zaj duab xis rau Li/LGPS interface
Unfinished, mus txuas ntxiv.
