Daim Ntawv Thov Kev Txhim Kho Ntawm Txhua Yam Khoom-Lub Zog Thin Film Lithium Roj teeb
Sep 15, 2020
Kev txhim kho ntawm cov khoom siv hluav taws xob muaj zog tau txav mus rau ntawm lub zog tshwj xeeb, lub neej ntev thiab kev nyab xeeb siab. All-solid-state thin-film lithium roj teeb tau dhau los ua hom roj teeb lithium uas nrov tshaj plaws. Inorganic txhua yam-tau-lub xeev nyias-zaj duab xis lithium roj teeb siv nyias-zaj duab xis zoo thiab tsis zoo electrodes thiab nyias-zaj duab xis khoom electrolytes. Qhov nyias ua yeeb yaj kiab zaj duab xis ntawm cov khoom hluav taws xob ua rau nws hloov tau cov kua roj electrolyte nrog cov khoom hluav taws xob nrog cov kua roj tsawg hluav taws xob. Cov yeeb yaj kiab nyias morphology ntawm qhov zoo thiab tsis zoo electrodes ua rau nws tuaj yeem thov ntau cov ntaub ntawv zoo thiab tsis zoo nrog kev hloov loj ntawm lub txim thiab tawm ntim, xws li hlau lithium thiab nyias zaj duab xis silicon Tos. Nyob rau tib lub sijhawm, vim muaj cov zaj duab xis morphology ntawm cov roj ntsha-lithium roj teeb, nws yooj yim rau cov khoom lag luam ua micron roj teeb, thiab txawm tias kev tshawb fawb ntxiv rau cov roj teeb ntawm nano. Yog li no, cov roj ntsha kua roj ntsha roj teeb roj tsis tau tsuas yog dhau los ua cov kev tshawb fawb hotspot ntawm cov khoom siv hluav taws xob hauv lub zog tom ntej, tab sis kuj tseem muaj kev tshawb nrhiav qhov cuam tshuam txog cov roj teeb me me. Kev taw qhia ntawm txoj kev loj hlob.
Cov kev tshawb fawb tam sim no rau cov inorganic txhua-solid-state thin-film lithium roj teeb tsuas yog muab faib ua: (1) Tshawb nrhiav thiab tsim cov roj teeb tshiab, txhim kho lub roj teeb muaj peev xwm ntawm ib cheeb tsam thiab tawm hluav taws xob, thiab daws cov teeb meem ntawm thaj chaw qis. muaj peev xwm thiab lub zog ntawm cov roj ntsha lithium roj teeb me me: (2) Kev tshawb fawb ntawm cov hom tshiab ntawm cov khoom siv roj ntsha nrog cov roj teeb ionic ntau dua los daws qhov teeb meem ntawm cov roj ntsha lithium ion conductivity rau inorganic solid electrolytes: (3) Kev tshawb fawb ntawm cov hom tshiab ntawm qhov zoo thiab tsis zoo electrodes. , yog li ntawd qhov zoo thiab tsis zoo electrodes tom qab tsim zaj duab xis muaj zoo dua
1. Kev soj ntsuam ntawm cov qauv ntawm cov roj teeb lithium nyias
Qhov nyias-zaj duab xis lithium roj teeb adopts classic laminated qauv, uas yog yooj yim hauv cov qauv thiab yooj yim txheej txheem. Txawm li cas los xij, txhawm rau txhawm rau txhim kho kev ua haujlwm ntawm lub roj teeb ntxiv, kev tshawb fawb ntawm cov qauv ntawm cov nyias nyias cov roj ntsha lithium roj teeb tau nce zuj zus, tshwj xeeb tshaj yog 3D qauv nyias zaj duab xis lithium roj teeb tau dhau los ua kev tshawb fawb hotspot vim nws qhov kev ua tau zoo. Hauv 3D qauv ntawm cov nyias zaj duab xis lithium roj teeb, nws zoo ib yam li cov qauv ntxeem tau ntawm 3D roj teeb. Cov roj teeb no ua tiav nrog ntau cov txheej txheem sib xyaw micropores ntawm silicon substrate, thiab Li Li diffusion barrier txheej TiN tso rau hauv cov micropores, thiab tom qab ntawd cov silicon siv los ua qhov tsis zoo electrode. LiPON yog Electrolyte, LiCoO2 yog qhov zoo electrode los ua lub roj teeb.
2. Kev tshawb fawb ntawm cov khoom siv roj ntsha inorganic
Cov roj teeb uas siv cov inorganic solid electrolytes muaj ntau yam zoo dua li cov roj teeb hluav taws xob, xws li cov hluav taws xob zoo hluav taws xob, kev ruaj ntseg thermal, poob siab tsis kam, cuam tshuam tsis kam, tsis muaj teeb meem to thiab muaj kuab paug, thiab yooj yim miniaturization thiab nyias zaj duab xis. Cov khoom siv hluav taws xob zoo hauv cov khoom siv hluav taws xob yuav tsum muaj cov yam ntxwv hauv qab no: (1) High lithium ion conductivity thiab yuav luag tsis muaj qhov hluav taws xob muaj peev xwm tsis pub dhau lub lithium active lub xeev thiab thaj tsam kub; (2) Nws yuav tsum ruaj khov nyob rau hauv kev siv tshuaj hluav taws xob, tshwj xeeb tshaj yog Tus interface hauv kev sib cuag nrog cov tsis zoo ntawm cov roj ntsha lithium lossis lithium alloy; (3) Txhawm rau siv nws, cov khoom siv electrolyte yuav tsum yog ib puag ncig, tsis muaj tshuaj lom, tsis muaj nqi thiab npaj tau yooj yim, thiab nws yog qhov zoo tshaj plaws tias cov thermal expansion coefficient tuaj yeem ua tau raws li cov electrodes ntawm ob sab, tsawg kawg tsis txawv dhau.
(1) Crystalline inorganic electrolyte
Tam sim no, crystalline inorganic electrolytes tau pom tias muaj lub siab ionic conductivity nyob rau hauv ntau cov ntawv ceeb toom, thiab lawv tuaj yeem muab faib ua cov khoom hluav taws xob ntawm NASICON hom, LISICON hom, Thio-LISICON hom, perovskite hom thiab lwm cov qauv. Cov qauv ntawm NASICON cov khoom siv hluav taws xob zoo yog feem ntau M [A2B3O12]. Txawm hais tias NASICON electrolyte muaj kev ua haujlwm siab ionic, cov khoom lag luam T yog yooj yim txo los ntawm cov hlau lithium, uas ua rau muaj kev tiv thaiv tsis ruaj khov nrog cov hlau lithium.
LISICON tseem muaj lub siab ionic conductivity. Nws cov qauv tshwj xeeb yog Lisa.Zn1.GeO1sThio-LISl-CON hom electrolyte txhawm rau txhim kho lub ionic conductivity ntawm electrolyte. Hauv LISICON hom electrolyte, leej faj siv hluav taws xob siv, xws li Li2GeS3, Li4GeS4, Li2ZnGeS4 thiab lwm yam ntaub ntawv tshiab, nws cov ion conductivity tuaj yeem ncav cuag 6.5 × 10-5S / cm.
Cov kev tshawb fawb tam sim no rau cov inorganic txhua-solid-state thin-film lithium roj teeb tsuas yog muab faib ua: (1) Tshawb nrhiav thiab tsim cov roj teeb tshiab, txhim kho lub roj teeb muaj peev xwm ntawm ib cheeb tsam thiab tawm hluav taws xob, thiab daws cov teeb meem ntawm thaj chaw qis. muaj peev xwm thiab lub zog ntawm cov roj ntsha lithium roj teeb me me: (2) Kev tshawb fawb ntawm cov hom tshiab ntawm cov khoom siv roj ntsha nrog cov roj teeb ionic ntau dua los daws qhov teeb meem ntawm cov roj ntsha lithium ion conductivity rau inorganic solid electrolytes: (3) Kev tshawb fawb ntawm cov hom tshiab ntawm qhov zoo thiab tsis zoo electrodes. , yog li ntawd qhov zoo thiab tsis zoo electrodes tom qab tsim zaj duab xis muaj zoo dua
1. Kev soj ntsuam ntawm cov qauv ntawm cov roj teeb lithium nyias
Qhov nyias-zaj duab xis lithium roj teeb adopts classic laminated qauv, uas yog yooj yim hauv cov qauv thiab yooj yim txheej txheem. Txawm li cas los xij, txhawm rau txhawm rau txhim kho kev ua haujlwm ntawm lub roj teeb ntxiv, kev tshawb fawb ntawm cov qauv ntawm cov nyias nyias cov roj ntsha lithium roj teeb tau nce zuj zus, tshwj xeeb tshaj yog 3D qauv nyias zaj duab xis lithium roj teeb tau dhau los ua kev tshawb fawb hotspot vim nws qhov kev ua tau zoo. Hauv 3D qauv ntawm cov nyias zaj duab xis lithium roj teeb, nws zoo ib yam li cov qauv ntxeem tau ntawm 3D roj teeb. Cov roj teeb no ua tiav nrog ntau cov txheej txheem sib xyaw micropores ntawm silicon substrate, thiab Li Li diffusion barrier txheej TiN tso rau hauv cov micropores, thiab tom qab ntawd cov silicon siv los ua qhov tsis zoo electrode. LiPON yog Electrolyte, LiCoO2 yog qhov zoo electrode los ua lub roj teeb.
2. Kev tshawb fawb ntawm cov khoom siv roj ntsha inorganic
Cov roj teeb uas siv cov inorganic solid electrolytes muaj ntau yam zoo dua li cov roj teeb hluav taws xob, xws li cov hluav taws xob zoo hluav taws xob, kev ruaj ntseg thermal, poob siab tsis kam, cuam tshuam tsis kam, tsis muaj teeb meem to thiab muaj kuab paug, thiab yooj yim miniaturization thiab nyias zaj duab xis. Cov khoom siv hluav taws xob zoo hauv cov khoom siv hluav taws xob yuav tsum muaj cov yam ntxwv hauv qab no: (1) High lithium ion conductivity thiab yuav luag tsis muaj qhov hluav taws xob muaj peev xwm tsis pub dhau lub lithium active lub xeev thiab thaj tsam kub; (2) Nws yuav tsum ruaj khov nyob rau hauv kev siv tshuaj hluav taws xob, tshwj xeeb tshaj yog Tus interface hauv kev sib cuag nrog cov tsis zoo ntawm cov roj ntsha lithium lossis lithium alloy; (3) Txhawm rau siv nws, cov khoom siv electrolyte yuav tsum yog ib puag ncig, tsis muaj tshuaj lom, tsis muaj nqi thiab npaj tau yooj yim, thiab nws yog qhov zoo tshaj plaws tias cov thermal expansion coefficient tuaj yeem ua tau raws li cov electrodes ntawm ob sab, tsawg kawg tsis txawv dhau.
(1) Crystalline inorganic electrolyte
Tam sim no, crystalline inorganic electrolytes tau pom tias muaj lub siab ionic conductivity nyob rau hauv ntau cov ntawv ceeb toom, thiab lawv tuaj yeem muab faib ua cov khoom hluav taws xob ntawm NASICON hom, LISICON hom, Thio-LISICON hom, perovskite hom thiab lwm cov qauv. Cov qauv ntawm NASICON cov khoom siv hluav taws xob zoo yog feem ntau M [A2B3O12]. Txawm hais tias NASICON electrolyte muaj kev ua haujlwm siab ionic, cov khoom lag luam T yog yooj yim txo los ntawm cov hlau lithium, uas ua rau muaj kev tiv thaiv tsis ruaj khov nrog cov hlau lithium.
LISICON tseem muaj lub siab ionic conductivity. Nws cov qauv tshwj xeeb yog Lisa.Zn1.GeO1sThio-LISl-CON hom electrolyte txhawm rau txhim kho lub ionic conductivity ntawm electrolyte. Hauv LISICON hom electrolyte, leej faj siv hluav taws xob siv, xws li Li2GeS3, Li4GeS4, Li2ZnGeS4 thiab lwm yam ntaub ntawv tshiab, nws cov ion conductivity tuaj yeem ncav cuag 6.5 × 10-5S / cm.