Anode Rau Sulfide-raws li All-Solid-State Lithium Roj teeb - Ntu 2 Lwm yam Anodes

Kev nce qib tsis ntev los no ntawm anode rau sulfide-based all-solid-state lithium roj teeb

—— Ntu 2 Lwm cov anodes

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

Lithium alloy anode

Vim muaj kev cuam tshuam loj ntawm kev cuam tshuam sab nraud, cov lithium ntshiab yog qhov nyuaj rau siv ncaj qha rau hauv sulfide khoom electrolytes hauv lub sijhawm luv, yog li cov ntaub ntawv lithium alloy muab kev xaiv zoo dua. Piv nrog rau cov xim hlau lithium anodes, lithium alloy anodes tuaj yeem txhim kho kev sib txuas ntawm cov khoom sib txuas, inhibit qhov tshwm sim ntawm kev cuam tshuam sab nraud, txhim kho cov tshuaj lom neeg thiab kev ruaj ntseg ntawm cov khoom electrolyte interface, thiab zam kev luv luv los ntawm kev loj hlob ntawm lithium dendrites. Nyob rau tib lub sijhawm, piv nrog cov roj teeb lithium-ion ua kua, alloy anodes tuaj yeem pom muaj zog dua qhov ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom ntom. Txawm li cas los xij, cov hlau tsis zoo electrodes yuav dhau qhov ntim loj dua thiab cov qauv kev hloov pauv thaum lub sij hawm them nqi thiab tso tawm (xws li Li-Si alloy, Li-Sn alloy, thiab lwm yam), yog li kev tshawb fawb ntxiv yog xav tau ntawm kev txhim kho thiab siv cov ntaub ntawv alloy. Ntawm ntau yam lithium alloys, Li-In alloy yog nrov ntawm lub ntsuas ntsuas vim nws cov khoom siv zoo dua qub thiab cov peev xwm redox tas li (0.62 V vs Li + / Li) dhau ntawm qhov dav stoichiometric ntau yam. Li-In alloys feem ntau suav hais tias yog cov khoom siv thermodynamically thiab kinetically ruaj khov rau sulfide electrolytes. Nws yog dav siv nyob rau hauv lub chaw soj nstuam los ntsuam xyuas cov kev ua tau zoo ntawm electrolytes los yog cathode cov ntaub ntawv, thaum uas qhia zoo voj voog stability nyob rau hauv tsis tshua muaj tam sim no thiab tsawg load. Txawm li cas los xij, lub peev xwm redox thiab qhov hnyav molecular ntawm Li-In alloy yog siab, uas txo cov zog ceev kom zoo dua ntawm tag nrho cov khoom-lub xeev lithium-ion roj teeb. Feem ntau, kev tshawb fawb ntseeg tias tsis muaj kev loj hlob ntawm lithium dendrites hauv Li-In alloys. Txawm li cas los xij, Luo et al. ua cov nqi them thiab tso tawm ntawm Li-In|LPSCl|LNO@NCM622 all-solid-state roj teeb nyob rau hauv siab tam sim no ceev (3.8 mA·cm-2) thiab siab load (4 mA·h·cm{23} }). Lub roj teeb tau pom tias muaj luv luv tom qab kwv yees li 900 cycles. Lub roj teeb khaws cia lub voj voog ruaj khov thiab ze li ntawm 100% Coulombic efficiency thaum lub sij hawm them nqi mus txog 890 cycles, tab sis lub peev xwm pib poob sai sai tom qab 891 cycles, poob mus rau ze 0 ntawm 897th voj voog. Qhov cuam tshuam txog kev them nqi thiab qhov hluav taws xob tawm hluav taws xob ntawm lub roj teeb ntawm 891st mus rau 897th lub voj voog, uas lub peev xwm them tau maj mam nce, thaum lub peev xwm cuam tshuam tau txo qis. Nyob rau hauv lub voj voog 897th, lub roj teeb txuas ntxiv mus thiab lub peev xwm tseem nce ntxiv, nrog rau qhov qis dua qhov nce ntxiv, uas qhia txog qhov tshwm sim ntawm qhov tshwm sim ntawm ib qho luv luv thiab lub roj teeb tsis ua haujlwm. Txoj kev loj hlob ntawm Li-In dendrites tau tshwm sim los ntawm SEM, XPS thiab lwm yam cim thiab AIMD simulation. Qhia tau tias nyob rau hauv siab tam sim no thiab siab load tej yam kev mob. Cov hlau nyob hauv yog thermodynamically thiab kinetically tsis ruaj khov rau sulfide electrolytes. Kev hloov pauv thiab me ntsis cuam tshuam cuam tshuam cuam tshuam kev loj hlob ntawm Li-In dendrites, thaum kawg ua rau lub roj teeb tsis ua haujlwm thaum lub sijhawm ntev. Sib txawv ntawm txoj kev loj hlob ntsug ntawm lithium dendrites, txoj kev loj hlob ntawm Li-In dendrites yog kev loj hlob sab nraud raws lub pores thiab cov ciam teb. Qhov kev loj hlob qeeb thiab nws ua rau me ntsis kev puas tsuaj rau cov qauv sulfide electrolyte (Daim duab 6). Yog li ntawd, Li-In dendrite kev loj hlob tuaj yeem cuam tshuam los ntawm kev txhim kho electrochemical stability ntawm cov hlau electrode / khoom electrolyte thiab txo cov porosity ntawm electrolyte.

Fig.6 Ua ntej thiab tom qab cycling interface evolution rau Li-In|LPSCl|LNO@NCM622 cell

Al muaj qhov zoo ntawm ductility siab, siab reserves, thiab siab hluav taws xob conductivity. Nws muaj lub peev xwm theoretical siab (990 mA·g-1) thiab qhov ntim me me nthuav dav (96%) ntawm cov ntaub ntawv lithium alloy. Nws yog ib qho kev cog lus ntau dua tag nrho cov khoom-lub xeev lithium roj teeb anode cov ntaub ntawv. Raws li pom hauv daim duab 7(a), Pan et al. npaj lub Li-Al alloy tsis zoo electrode yam tsis muaj binder thiab conductive tus neeg sawv cev (Li{11}}.8Al, tshwj xeeb muaj peev xwm 793 mA·h·g-1, 0.35 V vs Li+/Li). Nws muaj kev sib raug zoo nrog LGPS electrolyte. Qhov no yog vim qhov tseeb tias lub peev xwm ua haujlwm ntawm kev npaj Li-Al alloy anode yog nyob rau hauv qhov tseeb electrochemical stability qhov rais ntawm LGPS [Daim duab. 7(b)] ib. Tiv thaiv cov electrolyte los ntawm kev txo qis thiab decomposed, tag nrho cov khoom-lub xeev cov roj teeb sib sau ua ke tau pom zoo rov qab, nrog lub peev xwm tuav tau siab txog 93.29% hauv 200 cycles. Raws li qhov xwm txheej ntawm N / P piv ntawm 1.25, lub roj teeb lub zog ceev tau mus txog 541 W·h·kg-1, ua pov thawj tias Li-Al alloy muaj qhov zoo tshaj plaws rau kev thov.

Fig.7 Schematics ntawm Li-Al alloy anode hauv ASSLBs

Sakuma et al. tau kawm txog kev sib piv ntawm Li-Sn alloy, Li-Si alloy thiab Li4-x Ge1-x P x S4 electrolyte, thiab pom me me interface kuj thiab muaj peev xwm redox ntau dua. Hashimoto et al. siv lub pob hluav taws xob loj milling los npaj cov koob ntawm Li4.4Ge x Si1-x (x=0~1.0). Ntawm lawv, Li4.4Ge0.67Si0.33 qhia tau hais tias muaj peev xwm loj tshaj plaws (190 mA·h·g-1) thiab muaj kev them nqi zoo thiab tso tawm rov qab. Park et al. siv cov khoom siv pob zeb los sib tov thiab sib tsoo lithium hmoov thiab silicon hmoov los npaj cov Li4.4Si alloy, Li4Ti5O12 zoo electrode, thiab Li2S-P2S5 electrolyte los sib sau ua ke tag nrho cov khoom-lub xeev lithium roj teeb. Txoj kev tshawb nrhiav pom tias qhov kev ua tau zoo ntawm lub roj teeb tau txhim kho zoo tom qab lub pob thib ob ntawm Li-Si alloy, uas yog, qhov txo qis hauv qhov loj me ntawm lithium-Si alloy yog qhov tsim nyog rau kev tso nyiaj tsis zoo thiab tshem tawm ntawm lithium thaum lub sijhawm ua haujlwm. kev them nqi thiab tso tawm.

Lithium alloy films kuj tseem siv tau los ua ib txoj hauv kev kom stabilize qhov tsis zoo electrode interface. Choi et al. siv txoj kev yooj yim dov los ua ke Ag nrog lub thickness ntawm 10 μm thiab Li nrog lub thickness ntawm 150 μm thiab tom qab ntawd sab nraud siv lub siab kom tau txais Li-Ag alloy zaj duab xis. Cov ntsiab lus siab ntawm Ag yooj yim tsim ib qho chaw ruaj khov nrog cov sulfide electrolyte thiab inhibits kev loj hlob ntawm lithium dendrites. Tsis tas li ntawd, qhov seem me me ntawm Ag uas tsis tsim cov Li-Ag alloy koom nrog cov tshuaj tiv thaiv zoo nrog Li, uas txo qis kev loj hlob tsis sib xws ntawm lithium. Cov roj teeb uas sib sau ua ke tau pom tias muaj peev xwm tuav tau ntawm 94.3% dhau 140 lub voj voog, thiab tseem tuaj yeem mus ncig ruaj khov ntawm tus nqi siab ntawm 12 C. Kev tshawb fawb los ntawm Kato li al. pom tias kev ntxig rau Au zaj duab xis ntawm Li / Li3PS4 electrolyte interface tuaj yeem tiv thaiv kev tsim cov voids tom qab pib lithium dissolution thiab nce Li deposition qhov chaw, uas yuav pab txhim kho lub reversibility ntawm roj teeb. Tsis tas li ntawd, kev tawg ntawm Au zaj duab xis rau hauv cov hlau lithium tuaj yeem yog qhov laj thawj rau kev txhim kho cov khoom siv hluav taws xob ntawm qhov tsis zoo electrode interface. Li-symmetric cells nrog Au zaj duab xis tso rau ntawm Li/Li3PS4 interface tuaj yeem ua haujlwm ruaj khov ntawm qhov ceev tam sim no (1.3 mA·cm-2) thiab thaj tsam loj (6.5 mA·h·cm-2 ) tsis muaj luv luv Circuit Court. Lub sib dhos Li/Au/Li3PS4/LiNi1/3Mn1/3Co1/3O2 all-solid-state battery muaj lub neej voj voog ntau tshaj 200 zaug ntawm qhov ceev tam sim no ntawm 2.4 mA·cm-2.

Silicon anode

Si raug suav hais tias yog ib qho ntawm cov khoom siv zoo tshaj plaws anode vim nws qhov muaj peev xwm theoretical siab (4200 mA·h·g-1), siab reserves, tsis tshua muaj nqi, ib puag ncig tus phooj ywg, non-toxicity, thiab tsis tshua muaj peev xwm ua haujlwm ntawm 0.4 V. Kev tshawb fawb ntawm kev siv Si anodes hauv cov roj lithium-ion kua tau tsim rau ntau tshaj peb caug xyoo thiab tseem nrov heev. Tsis ntev los no, raws li tag nrho cov-zog-lub xeev lithium roj teeb tau nkag mus rau hauv kev tshawb fawb ntawm lub zog, kev ua haujlwm tau pib hloov cov tshuab silicon zoo los ntawm cov kua lithium-ion roj teeb tshuab rau tag nrho cov roj teeb hauv lub xeev. Txawm li cas los xij, piv nrog cov kev tshawb fawb txog kev tsim cov khoom muaj peev xwm silicon anodes rau cov kua lithium-ion roj teeb, txawm hais tias muaj ob peb tsab ntawv ceeb toom ntawm kev siv silicon anodes raws li sulfide all-solid-state batteries, cov txiaj ntsig tau pom tseem ceeb heev. Txawm li cas los xij, Si anode tsis tshua muaj hluav taws xob conductivity (1.56 × 10-3 S·m-1), tsawg lithium ion diffusion coefficient (10-14-10-13 cm2·S{23}}), thiab loj ntim expansion (Li4. 4Si yog hais txog 360%) thiab lwm yam kev tsis zoo, uas txwv nws daim ntawv thov. Yog vim li cas vim li cas Si tsis zoo electrode tsis nyob rau hauv lub roj teeb feem ntau yog vim lub ntim loj ntawm Si thaum lub sij hawm lithiation / delithiation txheej txheem, uas ua rau hmoov, tawg thiab kev ntxhov siab loj, thiab ua rau muaj kev puas tsuaj loj heev. Piv txwv li: (1) Deterioration ntawm cov qauv kev ncaj ncees ntawm cov electrode vim rov crushing thaum lub sij hawm tso tawm / nqi. (2) Disconnection ntawm electrode thiab tam sim no collector tshwm sim los ntawm interfacial kev nyuaj siab. (3) Lithium ions tau noj tsis tu ncua thaum lub sij hawm tsim kho-kev puas tsuaj-kev hloov pauv ntawm SEI txheej.

Tam sim no, feem ntau siv txoj hauv kev los txhim kho silicon anodes rau tag nrho cov khoom-lub xeev lithium roj teeb suav nrog kev tswj qhov loj me (nano-silicon), cov qauv tsim, nyias zaj duab xis anodes, alloying, siab thov, sib xyaw anodes nrog cov ntaub ntawv qib siab / cov khoom siv hluav taws xob (xws li Si -C anodes), thiab lwm yam. Sakabe et al. siv magnetron sputtering los npaj cov tsis ntxeem tau thiab ntxeem tau amorphous silicon anodes, thiab ua ke nrog 80Li2S · 20P2S5 electrolyte los ua lub voj voog muaj peev xwm kuaj. Tom qab 100 cycles, 3.00 µm-thick nonporous amorphous silicon zaj duab xis tsuas pom txog 47% muaj peev xwm txheeb ze rau 10 lub voj voog. Lub 4.73 µm ntxeem tau amorphous silicon zaj duab xis qhia tau hais tias muaj peev xwm lithiation siab li 3000 mA·h·g-1. Tom qab 100 lub voj voog, lub peev xwm tuav tau piv rau 10 lub voj voog ntau dua 93%. Nws qhia tau hais tias cov qauv ntxeem tau tuaj yeem txhim kho lub voj voog ruaj khov ntawm lub roj teeb. Okuno et al. siv cov ntxeem tau silicon composite anode rau tag nrho cov khoom-lub xeev roj teeb nrog Li3PS4 electrolyte thiab pom tias muaj peev xwm tuav tau ntau dua 90% hauv 100 cycles. Qhov no yog vim qhov pores hauv silicon hais daws qhov hloov pauv loj thaum lub sij hawm lithiation thiab delithiation, txhim kho lub voj voog stability. Nyob rau hauv sib piv, lub voj voog stability ntawm kev lag luam uas tsis yog-porous silicon anodes yog pluag, thiab lub peev xwm tuav tus nqi nyob rau hauv 100 cycles tsuas yog 20% ​​los yog txawm qis dua. Poetke et al. tau tshaj tawm tias silicon-carbon composite void nanomaterials tau siv los ua cov electrodes tsis zoo rau tag nrho cov khoom-lub xeev lithium-ion roj teeb thiab tau ua tiav rau Si-C|Li6PS5Cl|NCM roj teeb tag nrho. Cov nanostructured Si-C composite siv nyob rau hauv txoj kev tshawb no muab ib tug sib txawv ntawm silicon nanoparticles (SiNPs) thiab ib tug txheej carbon plhaub. Cov pa roj carbon plhaub tuaj yeem ua rau muaj txiaj ntsig zoo rau kev hloov pauv ntawm silicon, txhim kho electrochemical kev ua tau zoo piv nrog SiNPs liab qab.

Nyob rau hauv xyoo tas los no, lub zej zog kev kawm tau rov ua tiav qhov kev tshawb fawb ntawm cov ntshiab silicon anodes. Hauv 2020, Cangaz et al. qhia txog columnar silicon anode npaj los ntawm PVD txheej txheem, thiab ua ke nrog Li6PS5Cl electrolyte thiab LiNi0.9Co{{90}}}05Mn0.05O2 cathode los npaj ib qho all-solid-state roj teeb nrog lub peev xwm tshwj xeeb (210 mA·h·g-1). Lub columnar silicon anode tau ruaj khov rau ntau tshaj 100 zaug nyob rau hauv siab load ntawm 3.5 mA·h·cm{17}}, nrog rau Coulombic efficiency siab li 99.7% ~ 99.9%. Thaum lub sij hawm lub voj voog, cov qauv columnar silicon nthuav tawm ib qho kev ua pa ntawm ib sab zoo ib yam li lithium anode nyob rau hauv txoj kab ntsug. Qhov kev ua pa ib sab no tuaj yeem raug them los ntawm qhov porosity intrinsic ntawm columnar silicon qauv thiab sab nraud pawg siab, ua kom ruaj khov SEI ob sab. Nyob rau tib lub sijhawm, pawg siab (20 MPa) kuj tseem cuam tshuam cov delamination ntawm columnar silicon thiab cov khoom siv tam sim no. Piv nrog cov hlau lithium anodes, qhov columnar silicon anode tshem tawm qhov kev pheej hmoo ntawm lithium dendrites, luv circuits thiab tuag lithium poob. Xyoo 2021, Tan et al. qhia txog 99.9.9% (mass) coj mus muag micron-qib ntshiab silicon Si (μ-Si) anode. Qhov chaw sib cuam tshuam ntawm qhov tsis zoo electrode thiab Li6PS5Cl electrolyte yog lub dav hlau ob sab, txawm tias qhov ntim nthuav dav tshwm sim thaum them nqi thiab tawm. Txawm li cas los xij, lub dav hlau ob-dimensional tseem khaws cia, thiab tsis muaj qhov cuam tshuam tshiab tsim. Lub Li-Si alloy tsim los ntawm lithiated μ-Si tsis zoo electrode muaj cov tshuaj lom neeg thiab cov khoom siv, uas ua rau muaj kev sib cuag ntawm cov electrode tsis zoo thiab cov electrolyte [Daim duab 8(a)]. Lub roj teeb tag nrho-lub xeev lithium sib sau ua ke los ntawm μ-Si, Li6PS5Cl electrolyte thiab NCM811 tuaj yeem ua haujlwm ruaj khov nyob rau hauv qhov siab tam sim no ntom ntom (5 mA·cm-2) thiab qhov kub ntawm qhov dav (-20~ 80 degree). Nws muaj peev xwm tuav tau ntawm 80% tom qab 500 lub voj voog ruaj khov thiab qhov nruab nrab Coulombic efficiency ntawm 99.95% [Daim duab 8(b)], uas yog qhov ua tau zoo tshaj plaws ntawm micro-silicon all-solid-state roj teeb qhia txog tam sim no. Nws yog ib qho tsim nyog hais tias μ-Si anode tau dhau los ua qhov ceev ceev tam sim no yam tsis muaj cov ntaub ntawv carbon conductive, ua rau muaj txiaj ntsig zoo rau kev puas tsuaj ntawm sulfide electrolyte. Nws muab cov tswv yim tshiab rau qhov tsis zoo ntawm cov pa roj carbon hauv Si-C cov khoom siv hluav taws xob hauv kev xav. Xyoo 2022, Cao et al. npaj cov khoom tsis zoo electrode muaj xws li nano-silicon (nm-Si) hais, conductive carbon, thiab Li6PS5Cl los ntawm pob milling. Cov tshuaj sib xyaw tsis zoo electrode muaj zoo hluav taws xob thiab ons zoo nyob rau hauv, uas tuaj yeem txo cov nyiaj hauv nroog tam sim no thiab inhibit ntau tiam neeg ntawm cov chaw tsis zoo electrode. Nws yog ua ke nrog ib leeg siv lead ua NMC811 cathode khoom coated los ntawm txoj kev sol-gel. Siv ib zaj duab xis Li6PS5Cl nrog lub thickness ntawm 47 μm raws li cov electrolyte, tag nrho cov-solid-state lithium roj teeb nrog lub zog ceev txog li 285 W·h·kg-1 tau. Lub roj teeb tag nrho ua tiav lub peev xwm siab ntawm 145 mA·h·g-1 ntawm C/3 rau 1000 lub voj voog ruaj khov. Qhov sib xyaw silicon anode qhia tau hais tias qhov kev cia siab ntawm kev tsim khoom loj, txo cov nqi, thiab muab kev taw qhia rau kev lag luam ntawm tag nrho cov khoom-lub xeev lithium roj teeb. Qhov sib txawv ntawm Tan's negative electrode tsim lub tswv yim, qhov sib xyaw tsis zoo electrode tsis tsuas yog ntxiv electrolyte tab sis kuj ntxiv cov pa roj carbon conductive. Yog vim li cas yog tias piv nrog μ-Si, nm-Si muaj thaj tsam ntau dua, muaj ntau thaj tsam ntawm silicon anode, thiab feem ntau muaj txheej ntawm SiO nyob rau saum npoo ntawm nm-Si. Yog li, cov hluav taws xob conductivity feem ntau yog 3 qhov kev txiav txim siab qis dua li ntawm μ-Si, uas cuam tshuam cov electron conduction thaum them nqi thiab tawm. Cov kev sim qhia tau hais tias thaum lub sij hawm txheej txheem ntawm tshem lithium ntawm no nm-Si anode, cov electrolyte tsuas yog decomposes me ntsis, thiab tsis muaj lithium dendrites raug tsim. Raws li cov txheej txheem saum toj no, Cao et al. npaj ib lub roj teeb architecture nrog ib tug bipolar pawg tsim. Cov tib lub hlwb txuas nrog hauv cov koob los ntawm cov khoom siv tam sim no kom txo tau kev siv cov khoom siv tsis muaj zog, yog li ua kom muaj zog ntau dua. Tshwj xeeb tshaj yog, ob-txheej txheej stacked tag nrho cov-solid-state lithium roj teeb ua los ntawm kev sib txuas-ruaj khov ib leeg muaju LiNi0.8Mn0.1Co0.1O2, Li6PS5Cl, thiab nm-Si ua haujlwm zoo li electrode, electrolyte, thiab tsis zoo electrode feem, muab lub siab voltage ntawm 8.2 V. Lub roj teeb-theem zog ceev yog 204 W·h·kg{104}}, uas yog siab tshaj 189 W·h·kg-1 ntawm ib lub roj teeb. Qhov no bipolar stacked tsim muaj qhov zoo siv tseem ceeb rau tag nrho cov roj teeb-lub xeev tag nrho.

Fig.8 Interfacial characterization thiab cycling kev ua tau zoo ntawm µ-Si anode thiab Li6PS5Cl hauv ASSLBs

Table 1 piav qhia txog cov kev daws teeb meem rau sulfide khoom electrolyte / anode interface thiab cov txiaj ntsig zoo thiab qhov tsis zoo.

Table 1 Hais txog cov tswv yim ntawm cov teeb meem interfacial ntawm anodes thiab sulfide-based solid-state electrolytes

Lwm yam anodes

Silver carbon tsis zoo electrode

Lee et al. qhia txog tag nrho cov khoom-lub xeev cov roj teeb tsim siv nyiaj-carbon (Ag/C) interlayer [Daim duab 9(a)]. Qhov no interlayer tsim tau zoo tswj cov txheej txheem lithium deposition, thiab reversible lithium deposition thiab stripping phenomena raug soj ntsuam ntawm Ag / C txheej thiab cov khoom tam sim no. Ntawm lawv, C yog siv los cais cov Li6PS5Cl electrolyte los ntawm deposited metallic lithium, uas tsis tsuas yog zam qhov txo ntawm electrolyte tab sis kuj tiv thaiv cov tiam ntawm lithium dendrites. Ag tuaj yeem txo lub zog nucleation ntawm cov hlau lithium los tsim Ag-Li alloy. Ib feem ntawm Ag txav mus rau saum npoo ntawm cov khoom siv tam sim no los tsim cov khoom siv nrog cov hlau lithium, txhawb nqa cov lithium deposition zoo ib yam. Tom qab tso tawm, cov hlau lithium txheej yog yaj tag, thaum Ag tseem nyob nruab nrab ntawm cov khoom siv tam sim no thiab Ag-C txheej. Qhov kev tsim no tuaj yeem ua kom haum lub ntim hloov pauv ntawm cov hlau lithium thaum caij tsheb kauj vab, txo qhov ceev hauv zos tam sim no ntawm lithium anode, thiab txhim kho lub voj voog stability. Raws li pom nyob rau hauv daim duab 9(b), lub hnab ntim cov roj teeb sib sau ua ke (0.6 A·h) nthuav tawm lub zog siab ceev (ntau dua 900 W·h·L-1) ntawm 60 degree . Stable Coulombic efficiency tshaj 99.8%. Lub neej voj voog ntev (1000 cycles). Nws muab cov tswv yim tshiab rau kev lag luam daim ntawv thov ntawm tag nrho cov khoom-lub xeev lithium roj teeb.

Fig.9 Cov qauv thiab kev ua haujlwm cycling rau sulfide-based ASSLBs siv Ag-C anode

Graphite

Ntawm ntau cov ntaub ntawv sib txuas sib txuas rau cov roj teeb lithium-ion, graphite yog cov khoom lag luam zoo tshaj plaws vim nws cov nqi qis, cov khoom loj, thiab lub neej ntev. Txawm li cas los xij, nyob rau hauv lub tshav pob ntawm tag nrho cov-solid-state roj teeb, graphite tsis tau ua lub hom phiaj ntawm tsis zoo electrode cov khoom xaiv vim nws txwv theoretical muaj peev xwm. Hauv cov ntawv ceeb toom thaum ntxov, graphite feem ntau siv los ua cov khoom siv anode rau cov khoom siv hluav taws xob tshiab sulfide. Tom qab kev tshawb fawb tau tig los tsom rau cov txheej txheem ua haujlwm yooj yim ntawm graphite hauv sulfide ASSLBs txhawm rau txhim kho kev tsim thiab tsim cov electrodes. Graphite feem ntau yog siv los ua lub hauv paus rau cov khoom siv hluav taws xob anode hauv kev tshawb fawb tsis ntev los no, muab cov qauv kev ntseeg siab thiab hluav taws xob conductivity. Txawm li cas los xij, lwm yam tsis zoo electrodes tam sim no xws li lithium thiab silicon tseem muaj teeb meem xws li tus nqi siab, qhov ntim loj loj, thiab lub voj voog tsis ruaj khov. Yog li ntawd, graphite, raws li cov khoom siv uas tsis tshua muaj nqi, muaj peev xwm loj, qib siab ntawm kev lag luam thiab kev ruaj ntseg siab, tuaj yeem ua lub luag haujlwm tseem ceeb hauv cov txheej txheem kev txhim kho ntawm tag nrho cov khoom-lub xeev cov roj teeb nyob rau theem pib. Nws yog ib qho tsim nyog yuav tsum tau ua kom zoo dua qhov muaj peev xwm ntawm graphite.

Tam sim no collector pretreatment

Anodeless lithium-ion roj teeb sib sau ua ke cov khoom tam sim no ncaj qha nrog lub roj teeb yam tsis ntxiv lithium ntau dhau, qhov twg nws yog xim hlau lithium tsim los ntawm kev txo cov lithium ions ntawm cov khoom siv tam sim no los ntawm tag nrho lithiated cathode plating thaum thawj lub voj voog. Lub tswv yim no tau kawm ntau yam hauv thaj tsam ntawm lithium-ion roj teeb, thiab qee pawg tau txuas ntxiv qhov kev tsim no rau tag nrho cov khoom siv-lub xeev lithium roj teeb. Gu et al. etched nto ntawm stainless hlau tam sim no collector (SSCC) mus rau txawv degrees, matched nws nrog Li5.5PS4.5Cl1.5 khoom electrolyte, thiab ua electrostatic cycling siv lub asymmetric roj teeb configuration (lithium ntawv nyiaj|stainless hlau ntawv ci). Cov txiaj ntsig kev sim qhia tau hais tias qhov sib txawv ntawm SSCC roughnesses muaj kev cuam tshuam ntau dua rau kev ua haujlwm ntawm roj teeb. Tag nrho cov khoom-lub xeev cov roj teeb sib sau ua ke nrog SSCCs nrog roughness ntawm 180 nm muaj kev ua tau zoo ntawm electrochemical voj voog zoo dua li cov roj teeb uas muaj qhov ntxhib ntawm tsuas yog 20 nm. Qhov no yog vim qhov ntxhib saum npoo ua rau cov ntsiab lus sib txuas ntawm cov electrolyte thiab cov khoom siv tam sim no, muab ntau cov ntsiab lus tshuaj tiv thaiv thiab tso cai rau kev tso tawm ntawm lithium rau ntawm qhov sib txuas. Txawm li cas los xij, thaum qhov roughness saum npoo ntau tshaj 500 nm, qhov roughened nto heev ua rau cov lithium ions NW nyuam qhuav ncav cuag cov ntsiab lus txwv nyob rau hauv qab ntawm cov khoom siv tam sim no. Qhov no txo ​​cov nag lossis daus ntawm lithium thiab qhia kev ua haujlwm tsis zoo. Qhov tshwm sim no tsis tshwm sim hauv cov roj teeb ua kua. Qhov no qhia tau hais tias kev sib cuam tshuam ntawm cov khoom electrolyte thiab cov khoom siv tam sim no sib txawv ntawm cov kua electrolyte. Nws yog ib qho tsim nyog yuav tsum tshawb nrhiav cov txheej txheem ua haujlwm yooj yim thiab cov yam ntxwv ua ntej cov khoom siv tam sim no tsim ntawm cov roj teeb tsis zoo electrode-dawb tag nrho lub xeev tuaj yeem nqa tawm.

Summary thiab Outlook

Nrog rau qhov tshwm sim ntawm LGPS nrog siab ionic conductivity, kev tshawb fawb ntawm sulfide all-solid-state lithium-ion roj teeb tau nce zoo heev. Ntawm lawv, kev xaiv cov khoom siv anode thiab kev daws teeb meem ntawm kev sib tshuam tau dhau los ua ib qho ntawm cov kev tshawb fawb tsom. Ntau tus kws tshawb fawb tau ua tiav cov ntsiab lus kev tshawb fawb ntawm lithium anode / sulfide electrolyte interface. Tsab ntawv xov xwm no muab cov ntsiab lus tseem ceeb ntawm cov ntaub ntawv tseem ceeb anode rau tag nrho cov khoom-lub xeev lithium roj teeb raws li sulfide electrolytes, xws li hlau lithium, lithium alloys, thiab silicon anodes. Qhov teeb meem cuam tshuam ntawm lithium anode thiab sulfide electrolyte tau npaj tseg, thiab cov tswv yim zoo los txhim kho cov khoom sib txuas tau muab sau tseg. Tam sim no, tag nrho cov khoom-lub xeev lithium-ion roj teeb tseem nyob deb ntawm daim ntawv thov kev lag luam thiab tsis muaj kev tshawb fawb theoretical thiab kev txhawb nqa. Yog li ntawd, cov teeb meem hauv qab no tseem yuav tsum tau them nyiaj rau hauv kev tshawb fawb yav tom ntej.

(1) Lithium alloy anodes muaj peev xwm cia lithium zoo heev thiab kev ua haujlwm ruaj khov, thiab tau pom tias muaj peev xwm daws tau lithium anode dendrite kev loj hlob thiab luv luv Circuit Court, ua kom muaj zog ceev thiab lub sij hawm ntev ruaj khov tag nrho-lub xeev lithium roj teeb. Nyob rau hauv lub tshav pob ntawm tag nrho cov-solid-state roj teeb, vim hais tias ntawm cov kev sib cuag yam ntxwv ntawm cov khoom-khoom interface, qhov teeb meem ntawm rov SEI tiam tshwm sim los ntawm cov tshuaj tiv thaiv ntawm alloy cov ntaub ntawv thiab kua electrolytes yuav daws tau. Txhawm rau kom siv tau zoo dua cov hlau anodes, kev ua haujlwm yooj yim thiab siv tau yuav tsum tau ua kom nkag siab txog chemistry, electrochemistry, mechanical zog thiab ua hauj lwm mechanism ntawm alloy anodes nyob rau hauv solid-state roj teeb, thiaj li ua tau raws li qhov kev thov rau high-zoo. muaj peev xwm, lub sij hawm ntev ruaj khov-state roj teeb. .

(2) Silicon anodes tuaj yeem ua kom lub zog ceev ntawm tag nrho cov khoom-lub xeev lithium-ion roj teeb. Txawm li cas los xij, vim tias silicon muaj cov khoom siv hluav taws xob tsawg, feem ntau siv cov pa roj carbon conductive cov neeg ua haujlwm yuav ua rau kom cov khoom tawg ntawm sulfide electrolytes. Yuav ua li cas tswj cov txheej txheem tsis sib xws ntawm silicon anode kom nws tsis cuam tshuam rau txoj hauv kev ntawm cov electrode los yog ua rau lub decomposition ntawm sulfide electrolyte yog ib qho kev sib tw tseem ceeb ntawm silicon anode npaj txheej txheem. Nws kuj yog ib qho kev cuam tshuam rau kev lag luam loj ntawm silicon anodes hauv sulfide solid-state roj teeb.

(3) Cov teeb meem ntawm cov khoom me me thiab cov nqi siab ntawm cov hlau lithium kuj yuav tsum tau them nyiaj rau hauv cov ntawv thov kev lag luam. Txawm hais tias nws yog xim hlau lithium anode muaj txiaj ntsig zoo rau cov txheej txheem lithium plating, nws tsis yog qhov tsim nyog los ua kom tiav cov tshuaj tiv thaiv electrochemical lithium plating. Kev siv cov xwm txheej ntawm lithium hlau yog qhov hnyav heev, thiab kev tsim cov roj teeb lithium loj yuav ua rau muaj kev nyab xeeb loj heev. Yog li ntawd, txhawm rau txo cov nqi, txhim kho kev nyab xeeb thiab ua tiav kev lag luam zoo tshaj plaws, kev txhim kho tag nrho cov khoom siv-lub xeev lithium roj teeb uas tsis muaj lithium anodes yog kev tshawb fawb. Piv txwv li, kev tshawb fawb ntawm Ag-C composite electrode muab lub tswv yim zoo rau kev ua haujlwm tom ntej. Tsis tas li ntawd, cov txheej txheem kev ua haujlwm yooj yim thiab cov yam ntxwv ntawm cov khoom siv tam sim no tseem xav tau kev tshawb fawb ntxiv los ua ntej cov khoom siv tam sim no nyob rau hauv lub hom phiaj kom tau txais kev ua tau zoo ntawm cov roj teeb uas tsis muaj hluav taws xob tsis zoo.

Txoj kev loj hlob ntawm cov khoom tsis zoo electrode nyob rau hauv lub tshav pob ntawm tag nrho cov-solid-state roj teeb tseem muaj ib tug ntev txoj kev mus. Nrog rau kev tshawb fawb tob zuj zus, tag nrho cov khoom siv-lub xeev cov roj teeb raws li cov hluav taws xob tsis zoo electrodes yuav twv yuav raug hu lawv cov txiaj ntsig tshwj xeeb hauv cov roj teeb theem nrab.