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Batteries 2022, 8, 272 11 of 20 Based on a comprehensive understanding of the relationship between the properties Batteries 2022, 8, x FOR PEER REVIEW 11 of 19 of the sodium nucleation layer and the plating–striping CE, researchers tend to explore various nucleation layers such as the nanocarbon nucleation layer formed on Al current collectors [64], metal–organic frameworks (MOF)-derived copper-carbon (Cu@C) compos- (conductive carbon black, TIMCAL Super C45)−coated Al current collector could simplify the ite [65], or graphitic carbon–coated current collectors [23]. For instance, a nanocarbon sodium seeding process with a lower nucleation energy barrier (Figure 6a) [64]. Electrochem- nucleation layer (conductive carbon black, TIMCAL Super C45)–coated Al current col- ical analyses revealed that at a current density of 0.5 mA/cm−2 with loading up to 0.25 lector could simplify the sodium seeding process with a lower nucleation energy barrier mAh/cm−2, a sodium plating/stripping CE of 99.8% on average over 1000 cycles was a−c2- (Figure 6a) [64]. Electrochemical analyses revealed that at a current density of 0.5 mA/cm complished. Such a remarkable performance should be attributed to the high surface area with loading up to 0.25 mAh/cm−2, a sodium plating/stripping CE of 99.8% on average of the porous carbon black, the oxygen-containing functional groups with active sp3 car- over 1000 cycles was accomplished. Such a remarkable performance should be attributed to bon sites. In terms of the nucleation layer affecting the morphology of sodium depositions, the high surface area of the porous carbon black, the oxygen-containing functional groups Li et al. argued that the initial Na nucleation on the current collector dictates the subse- with active sp3 carbon sites. In terms of the nucleation layer affecting the morphology of quent deposition processes [23]. They selected two distinct current collectors, respectively sodium depositions, Li et al. argued that the initial Na nucleation on the current collec- mtoardeicotfataems othrpehsouubseaqnudengrtadpehpiotiscitciaornbopnro−ceosastesd[a2l3u].mTinhueymsefoleilct(eFdigtuwreo6dbi,sct)i.nWcthciulerrtehnet Ncoal‖leGctCorcse,llredsipspeclatiyvseblyotmhasldoepoinfgamanodrphlaotueasuanardeagsrawpihthitimcicnairmboalni–nciotiatlecdapaalucmityinlousms, fthoiel N(Faig‖uArCe6cbe,lcl)e.xWhihbiiltestaheslNopai∥nGgCchcaerlladctiesrpilsatiycswboitthaslsoupbinstganatnidalpinlaiteialucapreaacsitwyiltohssm.iMniomrea-l oinvietria,litccaapnacbietyshlosws,nthfreoNmat∥hAeCovcerl-ldeixschhibairtgseapsrlofpiliensgthchatarthaceteNrais‖tiGcCwcitehllaunsudbesrgtaonetsial sinmitailalel rcaspodaciuitmy lmosest.aMl nourceloevaetiro, nit ocvanerbpeotsehnotwialntfhraonmththaet ofvtehre-dNisac‖hGarCgeceplrl,owfilheischthcaot uthlde bNeaa∥dGvCanctealgleuonudsefrogrotehseaNsma dalelperosiotidoinumonmtheetaslonduiocplehaitliocnanodveorrpdoetreendticaalrtbhoanstuhraftaocef.thIne aNdad∥iGtioCncteoll,twhehiccahrbconu-lbdabsedadnvuacnletatgieoonulsafyoer,thteheNMa dOeFp-odseirtivoendonatnhoecsomdpioopshitielisc alnsod sohrdowered ecaffrebcotinvseunrefsascein. Ignuaididnigtiosnodtoiutmhedceaprboosnit-iboans.eVdenryucrlecaetinotnlyl,aLyiere,ttahle. rMepOoFr-tdeedritvheadt anannoovceolmpetoasli-toersgalnsiocsfhraomwewdoerfkfesc−tdivereinvesdsCinug@uCidcionmgpsosdiituemcandebpeoasirteiolinab. lVeesroydrieocpehnitlliyc, Li et al. reported that a novel metal-organic frameworks–derived Cu@C composite can layer for sodium metal deposition [65]. The findings showed that the carbon structure be a reliable sodiophilic layer for sodium metal deposition [65]. The findings showed that with a large surface area could accommodate the sodium’s overall volumetric expansion the carbon structure with a large surface area could accommodate the sodium’s overall during repeated plating/stripping procedures. Compared with the bare Cu or Al current volumetric expansion during repeated plating/stripping procedures. Compared with the collector, such a modified sodiophilic current collector effectively decreases the nucleation bare Cu or Al current collector, such a modified sodiophilic current collector effectively barrier, thus leading to excellent performances (Figure 6d). In the Na‖Cu−Cu@C asym- decreases the nucleation−2barrier, thus lead−i2ng to excellent performances (Figure 6d). In the metric cell at 0.5 mA cm and 1 mA h cm , nearly 1600 h (average CE of 99.9%) and 1200 Na∥Cu–Cu@C asymmetric cell at 0.5 mA cm−2 and 1 mA h cm−2, nearly 1600 h (average h (average CE of 99.8%) cycling life was achieved, significantly superior to that of the bare CE of 99.9%) and 1200 h (average CE of 99.8%) cycling life was achieved, significantly Na‖Cu cell. superior to that of the bare Na∥Cu cell. Figure 6. Schematic illustrations of the (a) anode–free cell compromising carbon-coated Al current Figure 6. Schematic illustrations of the (a) anode−free cell compromising carbon-coated Al current collector loadiing with in situ plated Na metal as the anode and Pyrite cathode [64];; copyright 2017 American Chemical Society. The Na deposition on (b) amorphous carbon (AC) and (c) graphitic carbon (GC): the grey strips stand for the deposited sodium on the carbon, where uneven and large cracks of Na layers formed on the AC, whereas uniform, small cracks of Na layer formed on the GC [23]; with permission from Springer Nature, copyright 2022. (d) Na deposition on bare Cu or Al foils and MOF−derived copper-carbon (Cu@C) composite [65]. Reproduced with the permission of ref. [66], copyright 2022 Wiley−VCH Verlag GmbH & Co. KGaA, Weinheim.PDF Image | Anode-Free Rechargeable Sodium-Metal Batteries
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