Kev loj hlob ntawm Quasi-solid-state Na-ion roj teeb Raws li Dej-tsawg kawg Prussian Blue Cathode
WANG Kunpeng ,1, LIU Zhaolin 2, LIN Cunsheng 2, WANG Zhiyu ,1,2
1. State Key Lab ntawm Fine Chemicals, Tsev Kawm Ntawv ntawm Chemical Engineering, Dalian University of Technology, Dalian 116024, Tuam Tshoj
2. Ceg ntawm Cov Khoom Siv Tshiab Tsim, Valiant Co., Ltd., Yantai 265503, Tuam Tshoj
Abstract
Nyob rau hauv kev sib piv rau Li-ion roj teeb, Na-ion roj teeb muab cov txiaj ntsig ntawm tus nqi qis, kev ua haujlwm kub tsis zoo, thiab kev nyab xeeb, nyiam cov xim zoo nkauj hauv cov nqi- thiab kev ntseeg siab-sensitive daim ntaub ntawv. Nrog lub peev xwm siab thiab tus nqi qis, Prussian xiav-zoo li cov ntaub ntawv (PBAs) sawv ua cov ntaub ntawv cog lus cathode rau Na-ion roj teeb. Txawm li cas los xij, muaj cov dej crystalline nyob rau hauv lawv cov qauv ua rau kev ua haujlwm sai ntawm lub roj teeb, ua haujlwm tseem ceeb hauv kev txwv tsis pub lawv daim ntawv thov. Txoj haujlwm no qhia txog kev kho cua sov kom yooj yim kom tshem tawm cov dej crystalline los ntawm PBAs cathode cov ntaub ntawv, txhim kho lub peev xwm tuav tau los ntawm 73% mus rau 88% tom qab 340 cycles. Qhov kev ntsuam xyuas hauv-situ pom tau tias qhov pib poob ntawm Coulombic efficiency ntawm PBAs cathode yog los ntawm nws qhov kev hloov pauv tsis tau los ntawm daim ntawv trigonal mus rau cubic theem thaum lub sij hawm them thiab tawm. Qhov teeb meem no tuaj yeem daws tau los ntawm kev qhia txog Na2C2O4 kom them nyiaj rov qab tsis tau Na poob hauv cathode. Raws li lub hauv paus no, lub roj teeb ua tau zoo quasi-solid-state Na-ion yog tsim los ntawm kev sib txuas cov dej-cov ntsiab lus PBAs cathode nrog Na2C2O4 additive thiab hard carbon (HC) anode hauv poly (ethylene glycol) diacrylate (PEGDA). )-raws li quasi-solid-state electrolyte nrog siab ionic conductivity thiab electrochemical stability. Lub roj teeb no nthuav tawm cov peev txheej tshwj xeeb xws li 58 txog 105 mAh·g-1 ntawm qhov ceev tam sim no los ntawm 20 txog 500 mA·g-1, muaj peev xwm ua kom muaj kev ruaj khov rau ntau tshaj 200 cycles. Txoj kev tshawb no qhia txog kev txhim kho tseem ceeb hauv kev ruaj ntseg thiab muaj peev xwm ntawm PBAs cathode cov ntaub ntawv los ntawm kev tshem tawm cov dej crystalline hauv lawv.
Ntsiab lus: Na-ion roj teeb; quasi-solid-state roj teeb; Prussian xiav cathode; nyob rau hauv-situ tsom xam
Txoj kev loj hlob ntawm cov cuab yeej siv roj teeb ua tau zoo yog qhov kev xav tau tseem ceeb rau Tuam Tshoj los hloov pauv thiab txhim kho nws cov qauv siv hluav taws xob, txhawb kev lag luam qis-carbon huv si, thiab ua tiav lub hom phiaj ntawm "carbon neutrality thiab carbon ncov". Cov roj teeb lithium-ion yog ib qho ntawm cov roj teeb uas siv tau zoo tshaj plaws. Txawm li cas los xij, kev nplua nuj ntawm lithium hauv lub ntiaj teb pob zeb tsuas yog 0.0065%, Tuam Tshoj cov peev txheej lithium tsuas yog 7% ntawm lub ntiaj teb tag nrho, thiab ze li 70% ntawm lithium carbonate yog imported. Nws yuav nyuaj rau kev ua kom tau raws li qhov xav tau loj hauv thaj chaw ntawm lub zog cia thiab cov roj teeb hluav taws xob yav tom ntej. Qhov ntau ntawm sodium nyob rau hauv lub ntiaj teb crust yog ntau tshaj li 400 npaug tshaj lithium. Tuam Tshoj tus sodium reserves suav txog li 22% ntawm lub ntiaj teb tag nrho cov reserves. Los ntawm kev xav ntawm cov khoom siv raw, tus nqi ntawm cov roj teeb sodium-ion tuaj yeem txo los ntawm 30% mus rau 40% piv rau lithium-ion roj teeb. Tsis tas li ntawd, piv nrog cov roj teeb lithium-ion, cov roj teeb sodium-ion muaj qhov ua tau zoo ntawm qhov kub thiab txias, kev ua haujlwm kub ntau dua, thiab kev nyab xeeb dua. Cov txiaj ntsig tshwj xeeb no tau ua rau lawv ua kom pom tseeb ntawm cov nqi-rhiab thiab kev nyab xeeb-tseem ceeb rau kev siv zog cia [1].
Tsav los ntawm "dual carbon" lub hom phiaj, Tuam Tshoj qhov kev thov rau lub zog cia thiab cov roj teeb hluav taws xob tau mus txog 158.5 GWh hauv 2020, thiab lub ntiaj teb xav tau roj teeb yuav tsum nkag mus rau TWh era hauv 2025. Nrog rau kev nce qib ntawm roj teeb technology, lub zog ceev ntawm Cov roj teeb tau nce sai heev, thiab cov kev cai rau kev nyab xeeb ntawm roj teeb tau dhau los ua qhov tseem ceeb. Cov roj teeb lithium/sodium ion tsoos siv cov kua dej organic electrolytes uas ua rau cov pa tawm, uas txo qhov kev ntseeg ntawm lub roj teeb [2-3]. Kev siv cov roj teeb hauv lub xeev uas muaj qhov ntsuas kub siab, muaj zog txhua yam, thiab tsis muaj qhov txaus ntshai yog qhov ua tau los daws qhov teeb meem kev ntseeg tau [4-5], tab sis nws muaj teeb meem xws li cov khoom siv electrolytes siab, tsawg ion conductivity, thiab kev sib cuag tsis zoo nrog "khoom-khoom" interface ntawm electrodes [6]. Quasi-solid electrolytes nruab nrab ntawm cov kua thiab cov khoom muaj kev ruaj ntseg zoo dua li cov kua electrolytes, thiab zoo dua rau cov khoom electrolytes nyob rau hauv cov nqe lus ntawm ion conductivity, yooj thiab interface compatibility [7⇓-9]. Cov txiaj ntsig zoo no ua rau cov roj teeb quasi-solid-state raws li lawv ib qho ntawm cov lus qhia ua tau zoo tshaj plaws hauv kev ua haujlwm ntawm cov roj teeb siab tshaj plaws.
Prussian xiav compounds (PBAs) yog tam sim no cov khoom siv cathode nrov tshaj plaws rau cov roj teeb sodium-ion. Lawv lub cev pob txha qhib thiab ntau qhov chaw cia khoom sodium muab rau lawv lub peev xwm theoretical siab (170 mAh g-1) thiab kev ua haujlwm zoo ion thauj mus los [10-11]. Hauv cov roj teeb uas muaj zog, PBAs tuaj yeem siv tsis yog cov khoom siv cathode nkaus xwb tab sis kuj yog cov khoom electrolytes [12-13]. Txawm li cas los xij, PBAs feem ntau yog npaj los ntawm kev daws los nag, uas yuav tsim Fe (CN) 64- qhov tsis xws luag thiab cov dej siv lead ua ntau ntau hauv lawv cov qauv, cuam tshuam cov embedding ntawm Na + rau hauv PBAs lattice thiab txwv lawv cov sodium cia muaj peev xwm. . Tsis tas li ntawd, cov dej siv lead ua hauv PBAs yuav maj mam tso rau hauv cov electrolyte thaum lub roj teeb cov tshuaj tiv thaiv, ua rau lub roj teeb ua haujlwm sai sai, kev cuam tshuam sab, flatulence thiab lwm yam teeb meem [11,14]. Cov teeb meem no txwv tsis pub siv PBAs hauv cov roj teeb uas muaj zog thiab ua rau nws nyuaj rau lawv nrog cov dej-sensitive inorganic khoom electrolytes. Kev tsim ntawm qhov tsis xws luag thiab dej crystalline hauv PBAs tuaj yeem cuam tshuam zoo los ntawm cov tswv yim xws li kev kho hydrothermal[15], qeeb coprecipitation[16], inhibition ntawm Fe2+ oxidation[17], tshuaj etching[18], thiab element doping[{17}}]. Txawm li cas los xij, cov txheej txheem kev cuam tshuam yog qhov nyuaj thiab nyuaj rau kev tswj hwm, thiab kev ua tau zoo ntawm PBAs cathodes kuj yuav tsum tau txhim kho. Raws li cov teeb meem saum toj no, txoj kev tshawb no nthuav tawm txoj kev kho cua sov yooj yim thiab ua tau zoo los txo cov ntsiab lus ntawm cov dej crystalline hauv PBAs thiab txhim kho lawv cov sodium cia ruaj khov. Los ntawm kev siv thev naus laus zis hauv-situ polymerization, polyethylene glycol diacrylate (PEGDA) benchmark khoom electrolyte nrog siab ionic conductivity thiab siab electrochemical stability tau tsim. Raws li lub hauv paus no, cov ntsiab lus dej qis PBAs cathode thiab cov roj carbon nyuaj (HC) anode tau sib tw hauv PEGDA cov khoom siv hluav taws xob electrolyte, thiab Na2C2O4 tau ntxiv rau cathode ua tus kheej-saib sodium compensator los tsim kom muaj kev ua tau zoo quasi- solid-state sodium ion roj teeb. Lub dynamic sodium cia mechanism ntawm PBAs cathode thiab HC anode tau qhia los ntawm in-site tsom xam tshuab.
1 Kev sim txoj kev
1.1 Kev npaj cov dej tsis tshua muaj PBAs cathode
116 mmol sodium citrate thiab 24 mmol FeSO4·7H2O tau yaj hauv 400 mL deoxygenated deionized dej. 116 mmol sodium citrate thiab 26 mmol Na4Fe (CN)6 tau yaj hauv 400 mL deoxygenated deionized dej. Cov tshuaj uas muaj FeSO4 tau maj mam ntxiv rau cov tshuaj uas muaj Na4Fe (CN) 6, thiab cov tshuaj tiv thaiv tau nplawm ntawm qhov kub thiab txias rau 6 teev. Cov khoom raug ntxuav peb zaug los ntawm centrifugation nrog ethanol thiab deoxygenated deionized dej, thiab qhuav hauv lub tshuab nqus tsev ntawm 120 degree rau 24 teev kom tau txais PBAs nrog cov dej crystalline siab (Hw-PBAs). Nws tau muab tso rau hauv qhov cub tiv thaiv argon thiab calcined ntawm 270 degree rau 2 h kom tau cov dej tsis tshua muaj PBAs (Lw-PBAs), nrog rau qhov cua sov ntawm 0.5 degree ·min-1.
1.2 Kev ua piv txwv
Cov qauv morphology thiab cov qauv tau txheeb xyuas siv lub teb emission scanning electron microscope. Cov qauv tshuaj muaj pes tsawg leeg tau txheeb xyuas siv lub X-ray photoelectron spectrometer thiab ib qho inductively txuas nrog ntshav emission spectrometer. Lub roj teeb tau soj ntsuam hauv qhov chaw siv cov hmoov X-ray diffractometer thiab laser Raman spectroscopy. Cov qauv siv lead ua dej cov ntsiab lus tau txheeb xyuas siv lub ntsuas ntsuas thermogravimetric hauv qhov chaw argon ntawm qhov cua sov ntawm 10 degree ·min-1.
1.3 Kev sib dhos roj teeb thiab kev kuaj xyuas electrochemical
1.3.1 Liquid sodium ion ib nrab roj teeb sib dhos
CR2016 lub pob khawm tau sib sau ua ke rau kev sim. Prussian xiav cathode khoom (Hw-PBAs los yog Lw-PBAs), Ketjen dub (KB) thiab polyvinylidene fluoride (PVDF) binder tau sib xyaw ua ke hauv qhov sib piv loj ntawm 8: 1: 1, N-methylpyrrolidone (NMP) tau ntxiv ua hnyav thiab dispersant, thiab lub resulting slurry yog uniformly coated ntawm carbon-coated txhuas ntawv ci raws li lub cathode, nrog ib tug active khoom loading ntawm 3 ~ 4 mg·cm{{10}}. Cov ntawv hlau sodium tau siv los ua cov txee electrodes thiab siv electrodes. Cov electrolyte yog DMC/EC tov (DMC: dimethyl carbonate, EC: ethylene carbonate, ntim ratio 1:1) ntawm 1.0 mol·L-1 NaClO4 thiab 5.0% fluoroethylene carbonate (FEC). Lub roj teeb tau sib sau ua ke hauv lub hnab looj tes uas muaj argon (cov ntsiab lus dej<10-7, oxygen content <10-7).
1.3.2 Cov kua sodium ion puv roj teeb sib dhos
Qhov zoo electrode tau npaj siv cov txheej txheem saum toj no, HC tau siv los ua qhov tsis zoo electrode, thiab N / P piv ntawm qhov zoo thiab tsis zoo electrodes raug tswj ntawm 1.1 ~ 1.2. Lub roj teeb tau sib sau ua ke hauv lub hnab looj tes uas muaj argon (cov ntsiab lus dej<10-7, oxygen content <10-7) using the above electrolyte.
1.3.3 Kev npaj ntawm quasi-solid electrolyte
PEGDA tau tov nrog cov kua electrolyte saum toj no ntawm qhov sib piv loj ntawm 7:93. 5.0% azobisisobutyronitrile (AIBN) tau ntxiv los ua cov txheej txheem polymerization los tsim cov tshuaj ua ntej ntawm quasi-solid electrolyte. Qhov kev daws teeb meem no tau ua kom sov ntawm 60 degree rau 10 h los tsim cov khoom siv hluav taws xob quasi-solid.
1.3.4 Sib dhos ntawm quasi-solid-state sodium-ion puv roj teeb
Cov khoom siv electrode zoo, Na2C2O4 sodium ntxiv, KB conductive tus neeg sawv cev thiab PVDF binder tau sib xyaw ua ke hauv qhov sib piv loj ntawm 6.4: 1.6: 1.0: 1.0, NMP tau ntxiv los ua cov kuab tshuaj thiab dispersant, thiab tau txais slurry yog uniformly coated ntawm ib tug carbon-coated txhuas ntawv ci raws li ib tug zoo electrode, nrog ib tug active khoom loading ntawm 3 ~ 4 mg·cm{14}}. HC tau siv los ua qhov tsis zoo electrode, thiab qhov zoo thiab tsis zoo electrode N / P piv tau tswj ntawm 1.1 ~ 1.2. Cov tshuaj precursor ntawm quasi-solid electrolyte tau ntxiv rau lub roj teeb, thiab tom qab lub roj teeb tau ntim, nws tau rhaub ntawm 60 degree rau 10 h kom tau txais lub roj teeb quasi-solid-state. Lub roj teeb tau sib sau ua ke hauv lub hnab looj tes uas muaj argon (cov ntsiab lus dej<10-7, oxygen content <10-7).
1.3.5 Kev ntsuas roj teeb ua haujlwm
Lub ionic conductivity ntawm quasi-solid electrolyte raug kuaj los ntawm electrochemical impedance spectroscopy (EIS) siv lub chaw ua haujlwm electrochemical. Qhov ntsuas zaus yog 1 Hz ~ 1000 kHz thiab qhov hluav taws xob perturbation amplitude yog 5.0 mV. Lub qhov rais electrochemical stability ntawm lub quasi-solid electrolyte raug kuaj los ntawm linear sweep voltammetry (LSV) nrog tus nqi cheb ntawm 5 mV·s-1. Cov khoom siv thiab roj teeb kev ua tau zoo tau kawm los ntawm kev them nqi tam sim no thiab tso tawm txoj kev siv Land CT2001A roj teeb tester. Lub qhov rais ib nrab ntawm qhov hluav taws xob yog 2.0 ~ 3.8 V (vs. Na / Na +), lub qhov rais puv ntawm tes yog 1.5 ~ 3.8 V, thiab qhov ceev tam sim no yog 10 ~ 500 mA·g-1. Thaum kuaj lub voj voog ruaj khov, lub roj teeb tau ua ntej 5 zaug ntawm qhov ceev tam sim no ntawm 50 mA·g-1, thiab tom qab ntawd lub voj voog kev ruaj ntseg tau ua ntawm qhov sib txawv tam sim no.
2 Cov txiaj ntsig thiab kev sib tham
2.1 Morphology thiab muaj pes tsawg leeg tsom xam
TGA nkhaus ntawm Hw-PBAs hauv daim duab 1(a) qhia ob thaj tsam ntawm kev poob phaus sai: 1) chav tsev kub txog 270 degree , 2) 440 txog 580 degree . Nyob rau hauv lub qub cheeb tsam, qhov hnyav poob ntawm chav tsev kub mus rau 120 degree (qhov loj ntawm 3.1%) yog tshwm sim los ntawm kev tshem tawm cov dej adsorbed; qhov hnyav poob los ntawm 120 mus rau 200 degree (loj feem 6.10%) yog tshwm sim los ntawm kev tshem tawm cov dej interstitial hauv PBAs cov qauv qauv; qhov hnyav poob ntawm 200 mus rau 270 degree (loj feem 6.89%) sib raug rau kev tshem tawm cov dej siv lead ua hauv PBAs. Yog li, 270 degree kev kho cua sov raug xaiv kom tshem tawm cov dej ntawm Hw-PBAs. Tom qab kev kho cua sov ntawm qhov ntsuas kub no, qhov tau txais Lw-PBAs tsuas yog poob li ntawm 1.18% ntawm lawv qhov hnyav ntawm chav tsev kub ~ 270 degree, uas yog 92.67% qis dua li ntawm Hw-PBAs; thiab poob txog 0.74% ntawm lawv qhov hnyav ntawm 200 ~ 270 degree, uas yog 89.26% qis dua li ntawm Hw-PBAs. Cov txiaj ntsig saum toj no qhia tau tias kev kho cua sov tuaj yeem tshem tawm ntau hom dej hauv PBAs, thiab tau txais cov ntsiab lus dej qis PBAs muaj qhov zoo thermal stability.
Fig. 1 TGA, morphology thiab qauv kev txheeb xyuas ntawm PBAs cathode
(a) TGA curves and (b) XRD patterns of Hw-PBAs and Lw-PBAs; (cf) SEM images of (c, d) Hw-PBAs and (e, f) Lw-PBAs
Daim duab 1(b) qhia XRD spectra of Hw-PBAs thiab Lw-PBAs. Lub diffraction peaks ntawm Hw-PBAs ntawm 2θ=17.0 degree , 24.0 degree , thiab 34.4 degree sib haum mus rau (012), (220), thiab (024) siv lead ua dav hlau, feem. Tom qab kev kho cua sov, qhov sib txawv ntawm lub ncov sib haum mus rau (024) lub dav hlau siv lead ua ploj mus, qhia tias cov dej siv lead ua tau zoo tshem tawm, thiab qhov chaw diffraction ncov sib xws rau (012) thiab (220) siv lead ua dav hlau txav mus rau cov ces kaum siab dua, qhia tias chav tsev ntawm tes ntim txo qis tom qab cov dej siv lead ua raug tshem tawm. Tsis tas li ntawd, cov tshiab diffraction peaks tshwm sim ntawm 2θ=27.1 degree , 30.7 degree , thiab 36.9 degree , qhia tias cov qauv siv lead ua trigonal yog tsim tom qab kev kho cua sov. SEM tsom xam (Daim duab 1(c~e)) qhia tau hais tias Hw-PBAs thiab Lw-PBAs muaj xws li cubic morphologies nrog qhov nruab nrab loj ntawm 2 ~ 3 µm. Qhov saum npoo ntawm Lw-PBAs cov khoom tau txais tom qab kev kho cua sov yog me ntsis ntxhib (Daim duab 1(f)), tab sis vim yog qhov kub thiab txias, tsis muaj qhov pom tseeb melting thiab agglomeration tshwm sim. Qhov muaj pes tsawg leeg ntawm Lw-PBAs tau kwv yees yog Na1.91Fe- [Fe(CN)6]·3.2H2O los ntawm kev txheeb xyuas cov ntsiab lus hlau los ntawm ICP-OES thiab ntsuas cov dej ntsiab lus los ntawm TGA.
Txhawm rau tshawb nrhiav tshuaj lom neeg muaj pes tsawg leeg thiab cov qauv ntawm Hw-PBAs thiab Lw-PBAs, XPS tsom xam tau ua. Nyob rau hauv qhov kev daws teeb meem siab Fe2p XPS spectrum ntawm Hw-PBAs, ob lub cim ncov ntawm kev sib khi lub zog ntawm 708.6 thiab 721.4 eV sib haum rau Fe(II) thiab Fe(III), feem (Daim duab 2(a)) ). Fe(II) thiab Fe(III) kuj muaj nyob rau hauv Lw-PBAs, tab sis qhov kev faib ua feem ntawm Fe(III) nce ntau (Daim duab 2(b)). Qhov no yog vim [NaH2O] + raug tshem tawm los ntawm PBAs qauv thaum lub sij hawm kho cua sov, thiab Fe(II) hauv Lw-PBAs yog oxidized ib nrab los tswj valence equilibrium. Nyob rau hauv lub high-resolution O1s XPS spectrum ntawm Hw-PBAs, tus yam ntxwv peaks ntawm khi energies ntawm 536.0, 533.7, 531.9 thiab 529.7 eV sib haum mus rau interstitial dej, sib koom ua ke dej, nto hydroxyl pawg thiab oxygen hom. PBAs lattice, ntsig txog (Daim duab 2 (c)). Tom qab kev kho cua sov, tus yam ntxwv ncov sib xws rau cov dej sib koom ua ke ploj mus, qhia tias cov txheej txheem no tuaj yeem tshem tawm cov dej sib koom ua ke ntawm Lw-PBAs (Daim duab 2(d)). Thaum lub sij hawm tus txheej txheem no, Fe nyob rau saum npoo ntawm PBAs reacts nrog hydroxyl pawg los tsim hlau oxides, ua rau Fe-O tus yam ntxwv ncov ntawm lub binding zog ntawm 530.0 eV yuav zoo heev txhim khu kev qha.
Fig. 2 Tshuaj muaj pes tsawg leeg ntawm PBAs cathode
(a, b) Fe2p XPS spectra of (a) Hw-PBAs and (b) Lw-PBAs; (c, d) O1s XPS spectra of (c) Hw-PBAs and (d) Lw-PBAs
2.2 Electrochemical kev ua tau zoo
Daim duab 3(a) qhia txog qhov tsis tu ncua tam sim no-kho tawm lub voj voog nkhaus ntawm sodium ion ib nrab-hlwb nrog Hw-PBAs thiab Lw-PBAs zoo li electrodes ntawm qhov ceev tam sim no ntawm 100 mA·g -1, nrog lub qhov rais voltage ntawm 2.0 ~ 3.8 V (vs. Na/Na+). Tom qab 340 lub sij hawm them-tso tawm, Lw-PBAs zoo electrode tseem tuaj yeem tuav lub peev xwm tshwj xeeb ntawm 91 mAh·g-1, nrog lub peev xwm tuav tau ntawm 88%, thiab qhov nruab nrab ib qho kev them nqi poob qis. tsuas yog 0.035%, uas qhia txog kev ruaj ntseg zoo heev. Raws li tib qho kev them nqi-tso tawm, lub peev xwm tuav tau ntawm Hw-PBAs zoo electrode yam tsis tau tshem tawm cov dej siv lead ua tsuas yog 73%, uas qhia lub luag haujlwm tseem ceeb ntawm kev tshem cov dej siv lead ua hauv kev txhim kho lub voj voog ntawm PBAs zoo electrode. Daim duab 3(b) qhia qhov tsis tu ncua tam sim no tus nqi-kho tawm nkhaus ntawm Lw-PBAs cathode ntawm qhov ceev tam sim no ntawm 100 mA·g-1, uas qhia txog qhov zoo li qub dual-voltage platform feature: (1) Lub platform voltage ntawm txog 3.2 V sib raug rau cov txheej txheem redox ntawm qis-spin Fe2+/Fe3+ (coordinated nrog C); (2) Lub tshuab hluav taws xob ntawm li 2.9 V sib raug rau cov txheej txheem redox ntawm high-spin Fe2+/Fe3+ (coordinated nrog N). Qhov tshwm sim ntawm lub zog hluav taws xob ntawm li 3.2 V qhia tau hais tias kev tshem tawm cov dej siv lead ua muaj txiaj ntsig rau kev ntxiv dag zog rau cov tshuaj tiv thaiv redox ntawm qis-spin Fe2+/Fe3+ hauv PBAs, uas pab txhim kho nws cov sodium. muaj peev xwm cia. Nyob rau hauv cov txheej txheem tom ntej no, tus nqi-kho tawm nkhaus ntawm Lw-PBAs cathode tseem zoo ib yam, uas qhia txog kev ruaj ntseg zoo. Ntawm qhov ceev tam sim no ntawm 10, 50, 100, 200, thiab 500 mA·g-1, Lw-PBAs cathode tuaj yeem tuav cov peev txheej siab ntawm 126, 112, 110, 108, thiab 107 mAh·g{{ 60}} (Daim duab 3(c)). Tshwj xeeb, ntawm qhov ceev tam sim no ntawm 500 mA·g-1, Lw-PBAs cathode muaj peev xwm tuav tau zoo, thiab nws lub peev xwm tshwj xeeb yog kwv yees li 13.4% siab dua li ntawm Hw-PBAs. Thaum qhov ceev tam sim no poob rov qab mus rau 10 mA·g-1, lub peev xwm tshwj xeeb ntawm Lw-PBAs cathode tuaj yeem rov qab los rau 125 mAh·g-1, uas yog ze rau thawj lub peev xwm tshwj xeeb, qhia tias nws tuaj yeem tuav cov qauv kev ruaj ntseg zoo heev thaum lub sij hawm ceev sodium cia.
Daim duab 3 Electrochemical kev ua tau zoo ntawm PBAs cathode hauv Na-ion ib nrab ntawm tes
(a) Cycling kev ua tau zoo ntawm Lw-PBAs thiab Hw-PBAs cathodes ntawm qhov ceev tam sim no ntawm 100 mA·g-1; (b) Charge-discharge curves of Lw-PBAs cathode at 100 mA·g-1; (c) Rate peev xwm ntawm Lw-PBAs thiab Hw-PBAs cathodes ntawm ntau qhov ceev tam sim no los ntawm 10 mA·g-1 txog 500 mA·g-1; Lub qhov rais qhov hluav taws xob yog 2.0-3.8 V (vs. Na/Na+) rau txhua qhov kev xeem ib nrab ntawm tes; Cov duab muaj yeeb yuj muaj nyob rau ntawm lub vev xaib
2.3 In-site tsom xam ntawm sodium cia mechanism
Lub Lw-PBAs zoo electrode tau sib xyaw nrog HC qhov tsis zoo electrode, thiab DMC / EC tov uas muaj 1.0 mol·L-1 NaClO4 thiab 5.0% FEC los ntawm huab hwm coj yog siv los ua cov kua electrolyte (LE) los sib sau ua ke lub roj teeb puv (Lw-PBAs|LE|HC, Daim duab 4(a)). Cov qauv kev hloov pauv hloov pauv ntawm qhov zoo thiab qhov tsis zoo ntawm cov khoom siv hluav taws xob ntawm lub roj teeb tag nrho thaum lub sij hawm them nqi thiab cov kev cuam tshuam tawm tau raug kawm los ntawm kev siv thev naus laus zis hauv kev tsom xam. Kev soj ntsuam hauv-situ XRD ntawm Lw-PBAs zoo electrode tau pom tias tom qab qhov hluav taws xob them hluav taws xob tau nce mus rau 3.2 V, qhov sib txawv ntawm cov peaks sib xws rau (110) thiab (104) maj mam sib xyaw ua ke los ua qhov dav dav (Daim duab 4(b)). ). Qhov tshwm sim no sib raug rau cov txheej txheem ntawm Na + khiav tawm ntawm Lw-PBAs zoo electrode, ua rau nws cov qauv siv lead ua hloov los ntawm cov qauv trigonal mus rau cov qauv cubic [21]. Thaum lub sij hawm tus txheej txheem tso tawm, tsis muaj re-split ntawm no dav ncov mus rau hauv (110) thiab (104) diffraction peaks tau pom, qhia tias cov theem hloov txheej txheem yog irreversible, uas ua rau thawj coulombic efficiency poob. Tsis tas li ntawd, thaum lub sij hawm thawj tus nqi thiab tso tawm ntawm HC tsis zoo electrode, cov khoom electrolyte interphase (SEI) zaj duab xis tsim rau saum npoo ua rau irreversible lithium poob (18%), uas kuj yog ib qho ntawm cov laj thawj rau thawj coulombic efficiency. poob tag nrho cov roj teeb (Daim duab 4 (c, d)).
Daim duab 4 In-situ tsom xam ntawm Na cia mechanism rau Lw-PBAs cathode thiab HC anode
(a) Charge-discharge curves of Lw-PBAs|LE|HC full cell; (b) Hauv-situ XRD qauv ntawm Lw-PBAs cathode thaum lub sijhawm ua haujlwm ntawm tes puv; (c) Charge-discharge curves rau thawj lub voj voog thiab (d) cycling stability ntawm HC anode ntawm qhov ceev tam sim no ntawm 300 mA·g-1; (e) In-situ XRD qauv thiab (f) in-situ Raman spectra ntawm HC anode thaum lub sijhawm ua haujlwm ntawm tag nrho ntawm tes; Cov duab muaj yeeb yuj muaj nyob rau ntawm lub vev xaib
Nyob rau hauv-situ XRD spectrum ntawm HC anode, tsis pom tseeb (002) ncov hloov pauv tau pom thaum lub sij hawm them nqi thiab tso tawm, qhia tias Na + tsis tau muab tso rau hauv cov txheej txheem graphitized, thiab tsis muaj qhov sib txawv ntawm cov hlau sodium tau pom ( Daim duab 4(e)). Yog li ntawd, sodium cia muaj peev xwm ntawm HC anode tej zaum yuav yog vim adsorption thiab sau ntawm Na + nyob rau hauv cov nplua nuj defect qhov chaw thiab pores ntawm HC, es tsis yog Na + intercalation los yog metallic sodium nag lossis daus [22]. Txhawm rau kawm ntxiv txog sodium cia cov tshuaj tiv thaiv hauv HC, in-situ Raman tsom xam tau ua tiav ntawm HC tsis zoo electrode thaum lub sij hawm them nqi thiab tso tawm (Daim duab 4(f)). Lub HC tsis zoo electrode muaj qhov pom tseeb Raman tus yam ntxwv ncov ntawm 1350 thiab 1594 cm{11}}. Cov yam ntxwv ncov nrog yoj tus naj npawb ntawm 1350 cm-1 sib raug rau cov pa roj carbon monoxide configuration stretching vibration (G hom), thiab cov yam ntxwv ncov nrog yoj tus naj npawb ntawm 1594 cm-1 sib raug rau cov pa roj carbon monoxide tsis zoo. qauv (D hom). Qhov sib piv ntawm D hom thiab G hom (ID / IG) tuaj yeem siv los ntsuas qhov ntsuas ntawm qhov tsis xws luag thiab tsis zoo ntawm cov khoom siv carbon. Thaum lub sijhawm tso tawm, ID / IG ntawm HC anode poob qis nrog kev sib txuas txuas ntxiv ntawm Na +, qhia tias tus cwj pwm tseem ceeb ntawm Na + ntawm nws qhov chaw tsis xws luag yog lub hauv paus tseem ceeb ntawm sodium cia muaj peev xwm ntawm HC anode.
2.4 Kev tsim kho thiab kev ua haujlwm ntawm quasi-solid-state full-cell
Thawj coulombic efficiency ntawm sodium-ion puv-cell tsim siv Lw-PBAs zoo electrode thiab HC tsis zoo electrode tsuas yog 67.3% (Daim duab 4(a)). Txhawm rau daws qhov teeb meem no, ib puag ncig tus phooj ywg, tsis muaj tshuaj lom, thiab huab cua ruaj khov Na2C2O4 yog siv los ua tus kheej-saib sodium compensator hauv Lw-PBAs zoo electrode los txhim kho thawj coulombic efficiency ntawm tag nrho-cell [23]. Qhov loj me me ntawm kev lag luam Na2C2O4 yog ntau tshaj li pua pua microns thiab muaj cov khoom siv hluav taws xob tsis zoo. Yog li ntawd, nws yog recrystallized kom tau Na2C2O4 nrog ib tug particle loj ntawm ob peb microns (Daim duab 5(a)). Micron-loj Na2C2O4 tuaj yeem tso tawm qhov muaj peev xwm tshwj xeeb ntawm 407 mAh·g−1 thaum thawj cov txheej txheem them nyiaj hauv lub qhov rais voltage ntawm 2.0 ~ 4.2 V, zoo them rau thawj qhov tsis muaj peev xwm poob ntawm qhov zoo electrode (Daim duab 5(b)). Thawj qhov tso tawm tshwj xeeb ntawm lub peev xwm ntawm Lw-PBAs|LE|HC tag nrho ntawm tes nrog kev sib ntxiv ntawm Na2C2O4 (ntau seem 20%) tuaj yeem ncav cuag 158 mAh·g-1, uas yog 92.7% siab dua li ntawm tag nrho cov xov tooj ntawm tes. tsis muaj qhov sib ntxiv ntawm Na2C2O4 (Daim duab 5(c)). Lw-PBAs|LE|HC tag nrho ntawm tes nrog kev sib ntxiv ntawm Na2C2O4 tuaj yeem tuav lub peev xwm thim rov qab ntawm 110, 101, 92, 87 thiab 80 mAh·g-1 ntawm qhov ceev tam sim no ntawm 10, 50, 100, 200 thiab 500 mA·g-1 (Daim duab 5(d)). Ntawm qhov ceev tam sim no ntawm 500 mA·g-1, tom qab 1400 lub voj voog ruaj khov, Lw-PBAs|LE|HC tag nrho ntawm tes nrog kev sib ntxiv ntawm Na2C2O4 tuaj yeem tuav lub peev xwm ntawm 64 mAh·g{{71} }, uas yog 25.4% siab dua li ntawm tag nrho cov xov tooj ntawm tes tsis muaj qhov sib ntxiv ntawm Na2C2O4 (Daim duab 5(e)).
Fig. 5 Cov nyhuv ntawm Na2C2O4 ntawm kev ua haujlwm electrochemical ntawm Lw-PBAs cathode
(a) SEM duab thiab (b) them-tso curves ntawm Na2C2O4 nrog micrometer loj ntawm qhov ceev tam sim no ntawm 180 mA·g-1; (c) Charge-discharge curves of Lw-PBAs|LE|HC tag nrho cov hlwb nrog lossis tsis siv Na2C2O4 ntawm qhov ceev tam sim no ntawm 100 mA·g-1; (d) Rate kev ua tau zoo ntawm Lw-PBAs|LE|HC tag nrho ntawm tes nrog Na2C2O4 ntawm ntau qhov ceev tam sim no ntawm 10 txog 500 mA·g-1; (e) Cycling stability ntawm Lw-PBAs|LE|HC tag nrho ntawm tes nrog lossis tsis siv Na2C2O4 ntawm qhov ceev tam sim no loj ntawm 500 mA·g-1; Lub qhov rais qhov hluav taws xob yog 1.5-3.8 V rau tag nrho cov kev ntsuas ntawm tes; Cov duab muaj yeeb yuj muaj nyob rau ntawm lub vev xaib
Raws li qhov no, PEGDA tau tov nrog 1.0 mol·L-1 NaClO4 thiab DMC/EC electrolyte nrog ib feem ntawm 5.0% FEC, thiab AIBN tau siv los ua ib qho thermal polymerization pib los tsim kom muaj kev ua tau zoo quasi-solid electrolyte (GPE). Piv nrog rau LE, GPE muaj qhov zoo ntawm qhov tsis tshua muaj qhov to thiab tsis tshua muaj hluav taws xob. Nws tuaj yeem nyob ruaj khov ntawm qhov hluav taws xob siab ntawm 4.9 V (vs. Na / Na +) thiab muaj qhov dav dav electrochemical stability qhov rais (Daim duab 6(a)). Piv nrog cov khoom siv electrolytes, GPE muaj ionic conductivity ntau dua thiab kev sib txuas sib txuas, thiab chav tsev kub ionic conductivity yog 3.51 mS·cm-1 (Daim duab 6(b)). Nws tau txuas ntxiv nrog cov dej-cov ntsiab lus qis Lw-PBAs zoo electrode thiab HC tsis zoo electrode los tsim lub quasi-solid-state sodium-ion puv roj teeb (Lw-PBAs|GPE|HC). Ntawm qhov ceev tam sim no ntawm 100 mA·g-1, thawj qhov tso tawm tshwj xeeb ntawm Lw-PBAs|GPE|HC quasi-solid-state roj teeb mus txog 147.8 mAh·g-1 (Daim duab 6(c )). Ntawm qhov ceev tam sim no ntawm 20, 50, 100, 200 thiab 500 mA·g-1, cov peev txheej tshwj xeeb tuaj yeem khaws cia ntawm 105, 94, 82, 70 thiab 58 mAh·g-1 (Daim duab 6( d)). Ntawm qhov ceev tam sim no ntawm 100 mA·g-1, nws tuaj yeem ruaj khov rau ntau tshaj 200 zaug, thiab Coulombic efficiency yog ze rau 100% (Daim duab 6(e)).
Daim duab 6 Electrochemical kev ua tau zoo ntawm quasi-solid-state tag nrho cell raws li Lw-PBAs cathode thiab PEGDA-raws li GPE
(a) LSV nkhaus ntawm tus nqi scan ntawm 5 mV·s-1; (b) EIS spectrum; (c) Charge-discharge curves ntawm qhov ceev tam sim no ntawm 100 mA·g-1; (d) Ntsuas kev ua tau zoo ntawm qhov ceev tam sim no ntawm 20-500 mA·g-1; (e) Cycling kev ua tau zoo ntawm 100 mA·g-1; Lub qhov rais qhov hluav taws xob yog 1.5-3.8 V rau tag nrho cov kev ntsuas ntawm tes
3 Kev xaus
Hauv txoj kev tshawb no, cov dej tsis tshua muaj PBAs cathode cov ntaub ntawv tau npaj los ntawm txoj kev kho cua sov yooj yim thiab ua tau zoo. Nws tau pom tias kev tshem tawm cov dej siv lead ua tsis yog tsuas yog ua kom muaj peev xwm tuav tau ntawm PBAs cathode los ntawm 73% mus rau 88% tom qab 340 cycles, tab sis kuj tau pab ntxiv dag zog rau cov tshuaj tiv thaiv redox ntawm qis-spin Fe2+/Fe 3+ nyob rau hauv PBAs, yog li txhim kho nws cov sodium cia muaj peev xwm. Lub dynamic sodium cia mechanism ntawm PBAs cathode thiab HC anode tau tshwm sim los ntawm situ Raman thiab hauv situ XRD cov tswv yim. Kev tsom xam pom tau tias cov txheej txheem ntawm Na + khiav tawm ntawm PBAs cathode ua rau nws cov qauv siv lead ua rau irreversibly hloov los ntawm peb-dimensional cubic, uas ua rau poob ntawm thawj coulombic efficiency, thiab cov adsorption ntawm Na + ntawm nws qhov chaw tsis xws luag yog lub hauv paus ntsiab lus. Sodium cia peev xwm ntawm HC anode. Tom qab ntxiv Na2C2O4 sodium compensator (feem ntau 20%) rau lub cathode, thawj lub peev xwm tawm ntawm PBAs cathode nce 92.7%. Raws li cov thermal polymerization ntawm PEGDA pib los ntawm AIBN, ib qho kev ua tau zoo quasi-solid electrolyte nrog chav kub ionic conductivity ntawm 3.51 mS·cm-1 thiab electrochemical stability qhov rais widened mus rau 4.9 V (vs. Na / Na +) yog tsim tawm. Rau lub hauv paus no, cov dej tsis tshua muaj PBAs cathode nrog ntxiv Na2C2O4 sodium compensator, HC anode thiab PEGDA benchmark khoom electrolyte tau muab tso ua ke los tsim lub quasi-solid-state sodium-ion roj teeb uas tuaj yeem ruaj khov rau ntau tshaj 200 zaug ntawm tam sim no ceev ntawm 100 mA·g-1. Cov kev tshawb fawb tau pom tias kev tshem tawm cov dej siv lead ua tau zoo yog qhov tsim nyog los txhim kho lub voj voog kev ruaj ntseg ntawm PBAs cathode thiab paub txog kev tsim cov roj teeb uas ua tau zoo quasi-solid-state sodium-ion roj teeb.
[1] WANG WL, GANG Y, PENG J, et al. Cov nyhuv ntawm kev tshem tawm cov dej hauv Prussian xiav cathode rau cov roj teeb sodium-ion. Adv. Ua haujlwm. Mater., 2022, 32(25): 2111727.
[2] MENG XY, LIU YZ, WANG ZY, et al. Lub quasi-solid-state rechargeable cell nrog lub zog siab thiab kev nyab xeeb zoo dua tau qhib los ntawm kev ruaj khov redox chemistry ntawm Li2S hauv gel electrolyte. Zog Zog. Sci., 2021, 14(4): 2278.
[3] CHE HY, Chen SL, XIE YY, et al. Electrolyte tsim cov tswv yim thiab kev tshawb fawb kev nce qib rau chav-kub sodium-ion roj teeb. Zog Zog. Sci., 2017, 10(5): 1075.
[4] Li WK, ZHAO N, BI ZJ, et al. Na3Zr2Si2PO12 ceramic electrolytes rau Na-ion roj teeb: kev npaj siv cov tshuaj tsuag kom qhuav thiab nws cov cuab yeej. J. Inorg. Mater., 2022, 37(2): 189.
[5] LI D, LEI C, LAI H, et al. Kev nce qib tsis ntev los no hauv kev sib tshuam ntawm cathode thiab garnet khoom electrolyte rau tag nrho cov khoom hauv lub xeev Li-ion roj teeb. J. Inorg. Xyoo 2019, 34(7): 694.
[6] KIM KJ, BALAISH M, WADAGUCHI M, et al. Cov roj teeb ntawm lub xeev Li-hlau: cov kev sib tw thiab lub qab ntug ntawm oxide thiab sulfide khoom electrolytes thiab lawv cov kev sib tshuam. Adv. Zog Mater., 2021, 11(1): 2002689.
[7] GAO H, GUO B, SONG J, et al. Ib qho kev sib xyaw gel-polymer / iav fiber ntau electrolyte rau cov roj teeb sodium-ion. Adv. Zog Mater., 2015, 5(9): 1402235.
[8] LIU YZ, MENG XY, Shi Y, et al. Lub neej ntev quasi-solid-state anode-dawb roj teeb tau qhib los ntawm Li them nyiaj txuas nrog kev sib txuas engineering. Adv. Mater., 2023, 35(42): e2305386.
[9] DU GY, TAO ML, Li J, et al. Tsawg-ua haujlwm kub, highrate thiab ruaj khov-state sodium-ion roj teeb raws li polymer electrolyte thiab Prussian xiav cathode. Adv. Zog Mater., 2020, 10(5): 1903351.
[10] PENG J, ZHANG W, LIU QN, et al. Prussian xiav analogues rau sodium-ion roj teeb: yav dhau los, tam sim no, thiab yav tom ntej. Adv. Mater., 2022, 34(15): 2108384.
[11] Lu YH, WANG L, CHENG JG, et al. Prussian xiav: lub moj khaum tshiab ntawm cov khoom siv hluav taws xob rau cov roj teeb sodium. Chem. Commun., 2012, 48(52): 6544.
[12] SÅNGELAND C, MOGENSEN R, BRANDELL D, et al. Lub voj voog ruaj khov ntawm sodium hlau tag nrho cov khoom-lub xeev cov roj teeb nrog polycarbonate raws li polymer electrolytes. ACS Appl. Poly. Xyoo 2019, 1(4): 825.
[13] KIM T, AHN SH, Song YY, et al. Prussian xiav-hom sodium-ion ua cov khoom electrolytes rau tag nrho cov roj teeb hauv lub xeev. Angew. Chem. Int. Ed., 2023, 62(42): e202309852.
[14] SONG J, WANG L, LU YH, et al. Tshem tawm ntawm interstitial H2O nyob rau hauv hexacyanometallates rau ib tug superior cathode ntawm sodium-ion roj teeb. J. Am. Chem. Soc., 2015, 137(7): 2658.
[15] LIU Y, FAN S, GAO Y, et al. Isostructural synthesis ntawm hlau-raws li Prussian xiav analogs rau sodium-ion roj teeb. Me, 2023, 19(43): e2302687.
[16] WANG W, GANG Y, HU Z, et al. Reversible structural evolution ntawm sodium-nplua nuj rhombohedral Prussian xiav rau sodium-ion roj teeb. Nat. Peb Hlis 2020, 11:980.
[17] YU XQ, YIN YX, et al. Sodium hlau hexacyanoferrate nrog cov ntsiab lus Na-nplua nuj cathode rau Na-ion roj teeb. Nano Res., 2014, 8(1): 117.
[18] REN WH, QIN MS, ZHU ZX, et al. Ua kom muaj sodium chaw cia hauv Prussian xiav analogues ntawm qhov chaw etching. Nano Lett., 2017, 17(8): 4713.
[19] Zhang H, GAO Y, PENG J, et al. Prussian xiav analogues nrog optimized siv lead ua dav hlau orientation thiab siv lead ua tsis xws luag rau 450 Wh·kg-1 alkali-ion roj teeb. Angew. Chem. Int. Ed., 2023, 62(27): e202303953.
[20] Zhang ZH, AVDEEV M, CHEN HC, et al. Lithiated Prussian xiav analogues zoo li cov khoom siv hluav taws xob zoo rau cov roj teeb lithium-ion ruaj khov. Nat. Peb., 2022, 13:7790.
[21] JIANG M, HOU Z, MA H, et al. Kev daws qhov deactivation ntawm qhov chaw qis-spin Fe los ntawm kev faib cov hluav taws xob ceev mus rau kev ua kom muaj zog sodium cia. Nano Lett., 2023, 23(22): 10423.
[22] TANG Z, Zhang R, WANG HY, et al. Tshaj tawm qhov kaw qhov pore tsim ntawm cov khib nyiab ntoo-derived hard carbon rau qib siab sodium-ion roj teeb. Nat. Peb., 2023, 14:6024.
[23] NIU YB, GUO YJ, YIN YX, et al. High-efficiency cathode sodium them rau sodium-ion roj teeb. Adv. Mater., 2020, 32(33): e2001419.
