Nyob rau hauv xyoo tas los no, muaj kev loj hlob sai ntawm sulfide khoom electrolytes xws li Li2S-SiS2, Li2S-B2S3, Li2S-P2S5, Li(10±1)MP2S12(M=Ge, Si, Sn, Al, P) , Li6PS5X(X=Cl, Br, I). Tshwj xeeb, thio-LISICON qauv sulfide, sawv cev los ntawm Li10GeP2S12 (LGPS), nthuav tawm chav tsev kub lithium ion conductivity ntawm 12mS / cm siab tshaj li cov kua electrolytes, uas tau ib feem daws qhov tsis txaus ntawm intrinsic conductivity ntawm cov khoom electrolytes.
Daim duab 1(a) qhia txog tag nrho cov khoom siv-lub xeev lithium roj teeb uas siv 2.2 cm × 2.2 cm Li1.5Al0.5Ge1.5(PO4)3. Nws yog sib sau los ntawm cov iav-ceramic khoom electrolyte daim ntawv, LiFePO4 zoo electrode khoom, PEO-raws li polymer hloov txheej txheej thiab nws yog xim hlau lithium tsis zoo electrode. Nws tuaj yeem tso tawm ib txwm nyob ntawm chav tsev kub thiab teeb ci LED teeb. Daim duab schematic ntawm nws cov khoom tseem ceeb yog qhia hauv daim duab 1(b). Nws tuaj yeem pom los ntawm nws tias cov txheej txheem electrode zoo, cov khoom siv tsis zoo electrolyte txheej, cov txheej txheem tsis zoo electrode interface hloov kho, thiab lithium ntawv ci tau zoo sib xws, thiab lawv cov ntaub ntawv thiab cov khoom muaj feem cuam tshuam rau kev ua haujlwm roj teeb. Qhov kev npaj ntawm txhua yam yog piav qhia hauv qab no.
Daim duab 1 All-solid-state lithium roj teeb raws li oxide khoom electrolyte
1. Kev npaj ntawm cathode
Cov Young's modulus ntawm sulfide electrolyte hmoov yog hais txog 20 GPa, nws muaj siab adhesion thiab compressibility, nws yog nws cov yas deformation, thiab muaj cov qoob loo tsawg ciam teb tom qab txias nias. Yog li ntawd, thaum lub sij hawm kev npaj ntawm lub zoo electrode txheej, nws yog tsim nyog yuav tsum tau ncaj qha qhuav-sib tov nrog zoo electrode hmoov [Daim duab 2(a)]. Thaum sib tov qhuav, tus neeg sawv cev, sulfide electrolyte, thiab cov khoom siv cathode tau ntxiv rau hauv mortar tib lub sijhawm, thiab tom qab ntawd grinded manually lossis mechanically tov rau hauv ib lub tov khoom. Nws yuav tsum raug sau tseg tias kev sib txuam ntawm cov khoom sib txawv cathode thiab electrolytes, lub sijhawm siv ntawm cov neeg ua haujlwm sib txawv, thiab cov txheej txheem cathode sib txawv yuav tsum tau txiav txim siab raws li qhov tseeb. Piv txwv li, Tan et al. [30] tshawb xyuas qhov sib txawv ntawm VGCF thiab carbon dub tsim nyob rau hauv cov roj theem ntawm decomposition ntawm LPSC. Nws tau pom tias Li-In / LPSC / LPSC-carbon roj teeb uas siv 30% pawg ntawm cov pa roj carbon dub thiab vapor deposition zus carbon fibers tau them. Cov roj teeb uas siv cov pa roj carbon dub qhia tau tias muaj peev xwm decomposition ntau dua thiab sai dua decomposition kinetics piv rau carbon fibers nrog cov cheeb tsam me me. Nyob rau tib lub sijhawm, nws muab piv rau cov nqi thiab tawm qhov nkhaus ntawm Li-In / LPSC / NCM811 ib nrab ntawm cov hlwb nrog ob cov khoom siv ntxiv. Cov txiaj ntsig tau pom tias cov roj teeb uas qhia tias txo cov electrolyte decomposition thaum siv vapor deposition zus carbon fibers li additives. Piv nrog carbon dub additives, coulombic efficiency ntawm thawj lub voj voog yog siab dua thiab lub roj teeb polarization qis dua.
Fig. 2 Kev npaj ntawm cathode rau tag nrho cov-solid-state lithium roj teeb cathode raws li sulfide khoom electrolyte
Thaum npaj cov roj teeb sulfide nyob rau hauv high-volume yob-rau-yob ntau lawm, txheej txheej ntub dej [Daim duab 2(b)] tej zaum yuav haum rau scale-up. Qhov no yog vim qhov yuav tsum tau siv cov polymer binders thiab cov kuab tshuaj los ua cov txheej txheem nyias nyias electrolyte txheej thiab cov txheej txheem electrode kom muab cov khoom siv hluav taws xob xav tau rau cov txheej txheem yob-rau-yob. Tsis tas li ntawd, qhov muaj cov polymers hloov tau yooj yim hauv cov electrolyte / electrode tuaj yeem cuam tshuam qhov kev ntxhov siab thiab cov kab mob uas tsim los ntawm kev rov ua kom rov ua dua thiab txo cov teeb meem xws li tawg tsim thiab particle shedding. Txawm li cas los xij, cov teeb meem hauv qab no yuav tsum tau sau tseg thaum lub sijhawm npaj. ① Cov nplaum nplaum polymer yuav tsum tau yaj nyob rau hauv qhov tsis muaj polar lossis tsawg dua polar solvent (xws li xylene) nrog qhov tsis zoo ntawm cov tshuaj sulfides. ②Polymer adhesives uas muaj zog adhesion muaj peev xwm yuav tsum tau siv, txwv tsis pub tshaj polymer yuav adversely cuam tshuam lub conductivity thiab thermal stability ntawm electrolyte / electrode. ③ Polymer adhesives yuav tsum tau hloov tau yooj yim. Txawm hais tias cov polymers xws li polystyrene (PS) thiab polymethylmethacrylate (PMMA) tuaj yeem yaj hauv xylene, lawv nyuaj heev tom qab cov kuab tshuaj dries. Nws yuav ua rau cov electrolyte / electrode raug crushed, yog li nitrile roj hmab (NBR) thiab styrene-butadiene roj hmab raug xaiv rau feem ntau ua hauj lwm. Qhov teeb meem nrog roj hmab, txawm li cas los xij, yog tias nws tsis tuaj yeem tsim cov ionic conductivity sab hauv, uas ua rau txo qis electrochemical kev ua tau zoo ntawm lub roj teeb txawm tias siv me me ntawm nitrile roj hmab. Vim li no, kev siv cov polymers uas muaj ionic conductivity, siab thermal stability, soluble nyob rau hauv non-polar los yog tsawg dua polar solvents, thiab insoluble polysulfides yog yav tom ntej txoj kev loj hlob ntawm sulfide electrolyte ntub txheej. Aw et al. [31] npaj 70 μm tuab hloov tau yooj yim sulfide electrolyte membrane thiab zoo electrode los ntawm kev sib xyaw thiab txheej triethylene glycol dimethyl ether, lithium bistrifluoromethanesulfonimide (LiTFSI), LPSC, thiab NBR. Tom qab sib piv cov hlau lithium, LiNi{16}}.6Co0.2Mn0.2O2//Li roj teeb muaj peev xwm ntawm 174 mA·h / g, thiab lub peev xwm thauj khoom ntawm cov khoom cathode tuaj yeem ncav cuag 45 mg/cm2.
Txawm li cas los xij, ntub dej pulping hauv cov txheej txheem saum toj no yuav siv cov kuab tshuaj ntau, uas yuav ua rau muaj qee qhov me me ntawm cov kuab tshuaj uas tseem tshuav hauv qhov sib tov [32], thiab tom qab ntawd cov kev cuam tshuam yuav tshwm sim, ua rau txo qis hauv electrolyte conductivity thiab hnyav attenuation ntawm roj teeb lub neej. Qhov loj ntawm cov polymer binder nyob rau hauv cov kev daws teeb meem wrapping cov khoom nquag yog qhov nyuaj rau kev tswj, uas tuaj yeem yooj yim ua rau kev thauj mus los tsis ua haujlwm. Lub volatilization ntawm cov kuab tshuaj ua rau ib tug tsawg ntom ntawm cov electrode daim ntawv, uas yog tsis conducive rau lub kinetic txheej txheem ntawm lub roj teeb. Tsis tas li ntawd, emissions thiab recycling ntawm cov kuab tshuaj tom qab scale-up kuj yog ib qho teeb meem uas yuav zam tsis tau. Yog li ntawd, cov txheej txheem qhuav txheej siv PTFE [Daim duab 2(c)] tau dhau los ua lwm txoj kev xaiv. Nws feem ntau suav nrog peb kauj ruam: ① qhuav-sib xyaw cov electrolyte, electrode, thiab PTFE pob zeb; ② yob cov hmoov rau hauv zaj duab xis; ③ yob cov zaj duab xis thiab cov khoom siv tam sim no rau hauv cov duab. Vim tias lub zog sib xyaw ua ke ntawm cov fluorine-carbon chains hauv PTFE yog qhov tsawg heev, cov saw hlau molecular muaj qhov hloov tau zoo. Loj molecular hnyav PTFE nplua hmoov hais yuav tsim fibrillation nyob rau hauv qhov kev txiav txim ntawm kev taw qhia quab yuam, uas yog, cov hais nyob rau hauv cov hais yog tsis tu ncua teem nyob rau hauv ib tug tej yam kev taw qhia nyob rau hauv qhov kev txiav txim ntawm shear quab yuam los tsim fibrous thiab network lug [33]. Yog li ntawd, ib tug loj tus naj npawb ntawm cov khoom siv, electrolytes, thiab cov pa roj carbon conductive tuaj yeem txuas nrog nruj tab sis tsis npog tag nrho. Hippauf et al. [34] pom tias 93 μm tuab tus kheej txhawb nqa cathode daim nyias nyias tuaj yeem npaj tau los ntawm txheej txheej tshuab siv NCM cathode, sulfide electrolyte, thiab VGCF siv tsuas yog 0.3% pawg ntawm PTFE. Nyob rau tib lub sijhawm, nws qhia tau hais tias muaj peev xwm saum npoo ntawm 6.5 mA·h / cm2. Duong et al. [35] siv ntau yam khoom siv anode (xws li cov khoom siv silicon thiab lithium titanate) thiab cov ntaub ntawv cathode (xws li NMC, NCA, LFP, sulfur) los npaj yob-rau-yob qhuav electrodes thiab ua tiav kev lag luam rau lawv. Lee et al. [36] kuj siv cov txheej txheem qhuav txheej los npaj cov roj teeb uas muaj peev xwm sulfide cathode uas tuaj yeem ruaj khov rau 1000 zaug hauv chav kuaj. Qhov kev ua haujlwm saum toj no ua pov thawj qhov ruaj khov thiab universality ntawm cov txheej txheem qhuav txheej electrode hauv sulfide all-solid-state lithium roj teeb.
2. Txoj kev npaj ntawm anode
Thio-LISICON tus qauv ternary sulfide electrolyte muaj kev ua haujlwm siab. Txawm li cas los xij, raws li kev sim thiab suav cov ntaub ntawv qhia txog kev ua haujlwm [37], nws yog xim hlau lithium reacts spontaneously thiab maj mam nrog txuas txuas nrog LGPS, Li10Sn2PS12, thiab lwm yam. Qee qhov cuam tshuam nrog qis ion conductivity xws li Li2S, Li3P, thiab lwm yam. Li15Ge4 yuav raug tsim tawm. Qhov no ua rau muaj kev nce ntxiv hauv kev cuam tshuam ntawm Li / LGPS thiab luv luv Circuit Court nyob rau hauv tag nrho cov khoom-lub xeev lithium roj teeb, uas cuam tshuam txoj kev loj hlob ntawm nws cov high-zog-density all-solid-state lithium roj teeb. Txhawm rau txhim kho cov tshuaj lom neeg / hluav taws xob ruaj ntseg ntawm sulfide electrolytes, tshwj xeeb tshaj yog cov ternary sulfides uas muaj germanium, tin, zinc, thiab lwm yam, rau cov hlau lithium, tam sim no muaj peb lub ntsiab kev daws teeb meem.
(1) Qhov saum npoo ntawm cov hlau lithium raug kho los tsim cov txheej txheem kev hloov pauv ion conductivity hauv qhov chaw los tiv thaiv sulfide electrolyte. Raws li pom hauv daim duab 3(a), Zhang et al. [25] tswj lub LiH2PO4 tiv thaiv txheej tsim los ntawm cov tshuaj tiv thaiv ntawm Li thiab ntshiab H3PO4 kom muaj kev sib cuag ntawm cov txheej txheem hloov thiab nws yog xim hlau lithium thiab zam kev sib cuag ncaj qha ntawm cov hlau lithium thiab LGPS. Nws tiv thaiv kev sib xyaw ion hluav taws xob hluav taws xob nruab nrab theem los ntawm kev nkag mus rau sab hauv ntawm LGPS thiab txhim kho qhov teeb meem ntawm kev cuam tshuam ntawm lithium ion dynamics. Cov txiaj ntsig tau pom tias dhau los ntawm kev hloov kho ntawm LiH2PO4, lithium kev ruaj ntseg ntawm LGPS tau txhim kho tau zoo, thiab LCO/LGPS/LiH2PO{{10}}Li all-solid-state lithium roj teeb tuaj yeem muab lub voj voog ntev. lub neej thiab muaj peev xwm. Ntawd yog, ntawm 25 degree thiab 0.1 C tus nqi, lub peev xwm thim rov qab ntawm 500th voj voog tseem nyob ntawm 113.7 mA·h / g, nrog tus nqi tuav ntawm 86.7%. Li / Li symmetrical roj teeb tuaj yeem ua haujlwm ruaj khov rau ntau tshaj 950 teev ntawm qhov ceev tam sim no ntawm 0.1 mA / cm2.
Daim duab 3 Kev hloov kho ntawm cov anode rau tag nrho cov khoom-lub xeev lithium roj teeb raws li sulfide khoom electrolyte
(2) Siv cov txheej txheem hloov pauv txheej sulfide electrolyte uas ruaj khov rau cov hlau lithium los tiv thaiv lwm txheej. Raws li pom hauv daim duab 3(b), Yao et al. [38] tau npaj ib LPS / LPOS ob-txheej electrolyte qauv los txhim kho ion conduction thiab stability ntawm LGPS / Li interface. Thiab ua tiav cov txiaj ntsig zoo hauv ntau lub tshuab roj teeb [39], tab sis cov txheej tuab ntawm ob txheej electrolyte tuaj yeem txo tag nrho lub zog loj ntawm lub roj teeb. Txoj kev sib dhos yog thawj zaug txias-nias ib txheej ntawm electrolyte, tom qab ntawd txias-nias ib txheej ntawm electrolyte rau ntawm nws qhov chaw, thiab tom qab ntawd muab cov electrodes zoo thiab tsis zoo thiab siv siab ua ke.
(3) Tsim cov txheej txheem hloov kho nyob rau hauv qhov chaw ntawm electrolyte nto (electrolyte / electrode interface). Raws li pom hauv daim duab 3(c). Gao et al. [40] siv 1 mol/L LiTFSI DOL-DME electrolyte dropwise rau LGPS/Li interface los tsim cov organic-inorganic mix lithium ntsev xws li LiO-(CH2O)n-Li, LiF, -NSO{{ 10}}Li, and Li 2O. Li / LGPS / Li symmetric roj teeb tau ruaj khov ntawm 0.1 mA / cm2 rau 3000 h. Chien et al. [41] siv cov khoom siv hauv xeev nuclear sib nqus duab los kawm thiab pom tias qhov cuam tshuam Li tau poob qis tom qab kev caij tsheb kauj vab ntawm Li / LGPS / Li symmetrical roj teeb, thiab qhov tsis muaj qhov cuam tshuam Li thiab nws qhov tsis sib xws tuaj yeem txhim kho los ntawm txheej PEO-LiTFSI. . Wang et al. [42] hloov cov polymer Alucone rau saum npoo ntawm Li10SnP2S12 los ntawm molecular txheej deposition. Cov txiaj ntsig tau pom tias qhov txo qis ntawm Sn 4+ tau cuam tshuam loj heev. Cov txheej txheem saum toj no txhim kho kev sib raug zoo ntawm sulfide electrolyte thiab lithium hlau anode rau qee qhov, tab sis kuj tseem muaj teeb meem xws li lub hauv paus ntsiab lus ntawm cov dej ntws electrolyte tsis tau qhia meej, thiab qhov sib ntxiv ntawm cov polymers ua rau txo qis hauv thermal. stability ntawm electrolyte.
3. Kev sib dhos txoj kev ntawm sulfide khoom electrolyte-based all-solid-state lithium roj teeb
Kev sib dhos ntawm sulfide khoom electrolyte-based all-solid-state lithium roj teeb feem ntau muab faib ua cov kauj ruam hauv qab no, raws li pom hauv daim duab 4. ① Electrolyte yog pressurized thiab molded. Lub siab dav dav yog 120 ~ 150 MPa. ② Cov electrode zoo yog nias-tsim thiab ib daim ntawv hlau txuas raws li cov khoom siv tam sim no. Lub siab dav dav yog 120 txog 150 MPa. ③ Cov electrode tsis zoo yog nias tsim. Rau lithium hlau, lub siab dav dav yog 120-150 MPa, thiab rau graphite, lub siab dav yog 250-350 MPa, thiab ib daim ntawv hlau yog txuas raws li cov khoom siv tam sim no. ④ Tighten lub roj teeb bolts. Nws yuav tsum tau muab sau tseg tias qhov taw qhia ntawm hydraulic xovxwm meter yuav tsum tau hloov raws li lub roj teeb pwm zoo, thiab tib lub sij hawm, lub roj teeb yuav tsum tau tiv thaiv los ntawm luv luv Circuit Court thaum lub sij hawm sib dhos.
Daim duab 4 los ua ke txoj kev ntawm tag nrho cov-solid-state lithium roj teeb raws li sulfide khoom electrolyte.
CUI Yanming. Prototype all-solid-state battery electrodes npaj thiab sib dhos tshuab [J].Energy Storage Science thiab Technology, 2021, 10(3): 836-847
