304 capillary chubhu Nanocomposites Kubva paTungsten Oxide/Fullerene seElectrocatalysts uye Inhibitors yeParasitic VO2+/VO2+ Reactions muMixed Acids.

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Stainless Simbi 304 Coil Tube Chemical Composition

304 Stainless Steel Coil Tube imhando yeaustenitic chromium-nickel alloy.Maererano neStainless Steel 304 Coil Tube Manufacturer, chikamu chikuru mairi Cr (17% -19%), uye Ni (8% -10.5%).Kuti ivandudze kurwisana kwayo nekuora, kune zvishoma zveMn (2%) uye Si (0.75%).

Stainless Simbi 304 Coil Tube Mechanical Properties

Iwo emakanika zvivakwa zve304 Stainless simbi coil chubhu ndeaya anotevera:

• Kusimba kwesimba: ≥515MPa
• Goho simba: ≥205MPa
• Elongation: ≥30%

Zvishandiso & Mashandisiro eStainless Simbi 304 Coil Tube

Mutengo wakakwira wevanadium redox kuyerera mabhatiri (VRFBs) unodzikamisa kushandiswa kwavo kwakapararira.Iyo kinetics ye electrochemical reactions inofanirwa kuvandudzwa kuitira kuwedzera kuwanda kwesimba uye kushanda nesimba kweVRFB, nekudaro kuderedza kWh mutengo weVRFB.Mubasa iri, hydrothermally synthesized hydrated tungsten oxide (HWO) nanoparticles, C76 uye C76/HWO, akaiswa pacarbon cloth electrodes uye akaedzwa semagetsi eVO2+/VO2+ redox reaction.Field emission scanning electron microscopy (FESEM), simba dispersive X-ray spectroscopy (EDX), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), infrared Fourier shandura Spectroscopy (FTIR) uye kuonana kona kuyerwa.Zvakaonekwa kuti kuwedzerwa kweC76 fullerene kuHWO kunogona kuwedzera kinetics ye electrode maererano neVO2 +/VO2 + redox reaction nekuwedzera kuitisa uye kupa okisijeni-ine mapoka anoshanda pamusoro payo.HWO/C76 composite (50 wt% C76) yakaratidza kuti ndiyo yakanyatsokodzera VO2+/VO2+ reaction neΔEp ye176 mV kana ichienzaniswa ne365 mV yekabhoni isina kubatwa jira (UCC).Mukuwedzera, iyo HWO / C76 inoumbwa yakaratidza kudziviswa kwakakura kweparasitic chlorine evolution reaction nekuda kweW-OH inoshanda mapoka.
Kuita kwakasimba kwevanhu uye kukurumidza kwekuchinja kwemaindasitiri kwakakonzera kudiwa kwakanyanya kwemagetsi, kuri kukura kunosvika 3% pagore.Kwemakumi emakore, kushandiswa kwakapararira kwefossil sechitubu chesimba kwakakonzera kuburitsa gasi regreenhouse, zvichikonzera kudziya kwepasi, kusvibiswa kwemvura nemhepo, zvichityisidzira zvisikwa zvese.Nekuda kweizvozvo, panosvika 2050 chikamu chesimba rinodzokororwa rakachena uye simba rezuva rinotarisirwa kusvika 75% yemagetsi ese1.Zvisinei, kana simba rekugadzirisa simba rinopfuura 20% yehuwandu hwemagetsi ekugadzirwa kwemagetsi, grid inova isina kugadzikana 1. Kuvandudzwa kwemaitiro ekuchengetedza simba kunokosha kune iyi shanduko, sezvo vachifanira kuchengetedza magetsi akawandisa uye kuenzanisa kugovera uye kudiwa.
Pakati pese masisitimu ekuchengetedza simba senge hybrid vanadium redox flow batteries2, ese vanadium redox flow mabhatiri (VRFBs) ndiwo akanyanya kufambira mberi nekuda kwekuwanda kwavo kwakanakira3 uye anoonekwa seyakanakisa mhinduro yekuchengetedza simba kwenguva refu (~ makore makumi matatu).Kushandiswa kwesimba rinowanikwazve4.Izvi zvinokonzerwa nekuparadzaniswa kwesimba uye simba remagetsi, kupindura nokukurumidza, hupenyu hurefu uye mari yakaderera yegore negore ye $ 65 / kWh ichienzaniswa ne $ 93-140 / kWh yeLi-ion uye mabhatiri e-lead-acid uye 279-420 USD / kWh./kWh mabhatiri zvichiteerana 4.
Nekudaro, kushambadzira kwavo kwakapararira kuri kuramba kuchikanganiswa nemutengo wakakwira system capital, kunyanya nekuda kwebhatiri packs4,5.Nekudaro, kuvandudza mashandiro ebhatiri nekuwedzera kinetics maviri hafu-sero maitiro anogona kuderedza saizi yebhatiri nekudaro kuderedza mutengo.Nokudaro, kukurumidza kuendesa erekitironi kune electrode surface inodiwa, zvichienderana nekugadzirwa, kuumbwa uye chimiro che electrode, iyo inofanira kunyatsogadziriswa.Kunyange zvazvo carbon-based electrodes ine yakanaka yemakemikari uye electrochemical kugadzikana uye yakanaka yemagetsi conductivity, kana isina kusiyiwa, kinetics yavo ichanonoka nekuda kwekushayikwa kweakisijeni inoshanda mapoka uye hydrophilicity7,8.Naizvozvo, maelectrocatalyst akasiyana-siyana anosanganiswa nekabhoni electrode, kunyanya kabhoni nanostructures uye metal oxides, kuvandudza kinetics yeese maelectrodes, nekudaro kuwedzera kinetics yeVRFB electrodes.
Zvakawanda zvekabhoni zvakashandiswa, senge carbon paper9, carbon nanotubes10,11,12,13, graphene-based nanostructures14,15,16,17, carbon nanofibers18 and others19,20,21,22,23, kunze kwemhuri ye fullerene. .Muchidzidzo chedu chekare paC76, takashuma kekutanga basa rakanakisisa re electrocatalytic yeiyi fullerene yakananga kuVO2 +/VO2+, kana ichienzaniswa nekupisa-yakagadziriswa uye isina kuvharwa kabhoni jira, kupikisa kwekutengesa kutengesa kwakaderedzwa ne99.5% uye 97% 24.Iyo inokonzeresa kuita kwekabhoni zvinhu zveVO2+/VO2+ reaction kana ichienzaniswa neC76 inoratidzwa muTafura S1.Kune rimwe divi, akawanda masimbi oxides akadai seCeO225, ZrO226, MoO327, NiO28, SnO229, Cr2O330 uye WO331, 32, 33, 34, 35, 36, 37, 38 anoshandiswa nekuda kwekuwedzera kunyorova uye kukwira kweokisijeni.mapoka.Tafura S2 inoratidza kuita kwekuita kweaya simbi oxides muVO2+/VO2+ reaction.WO3 yakashandiswa muhuwandu hunokosha hwemabasa nekuda kwekudhura kwayo, kugadzikana kwepamusoro mu acidic media, uye high catalytic activity31,32,33,34,35,36,37,38.Nekudaro, WO3 yakaratidza kuvandudzwa kushoma mune cathode kinetics.Kuti uvandudze conductivity yeWO3, mhedzisiro yekushandisa yakaderedzwa tungsten oxide (W18O49) pane yakanaka electrode basa yakaedzwa38.Hydrated tungsten oxide (HWO) haina kumboedzwa muVRFB zvikumbiro, kunyange zvazvo yakaratidza basa repamusoro mumashandisirwo e-supercapacitor nekuda kwekukurumidza cation diffusion kana ichienzaniswa neanhydrous WOx39,40.Chizvarwa chechitatu chese-vanadium redox inoyerera bhatiri inoshandisa yakasanganiswa acid electrolyte inoumbwa neHCl neH2SO4 kuvandudza kushanda kwebhatiri nekuvandudza kunyungudika uye kugadzikana kwevanadium ions mu electrolyte.Nekudaro, iyo parasitic chlorine evolution reaction yave imwe yezvakashata zvechizvarwa chechitatu, saka kutsvaga nzira dzekudzvinyirira chlorine evaluation reaction rave basa remapoka akati wandei ekutsvagisa.
Pano, VO2+/VO2+ reaction tests yakaitwa paHWO/C76 macomposites akaiswa pamakabhoni machira emagetsi kuitira kuti awane chiyero pakati pemagetsi conductivity yemakompositi uye redox reaction kinetics panzvimbo ye electrode uku ichidzvanya parasitic chlorine deposition.kuita (KVR).Hydrated tungsten oxide (HWO) nanoparticles akagadzirwa nenzira iri nyore yehydrothermal.Maedzo akaitwa musanganiswa asidhi electrolyte (H2SO4/HCl) kutevedzera chizvarwa chechitatu VRFB (G3) kuitira kurerutsira uye kuongorora mhedzisiro yeHWO paparasitic chlorine evolution reaction42.
Vanadium (IV) sulfate oxide hydrate (VOSO4, 99.9%, Alfa-Aeser), sulfuric acid (H2SO4), hydrochloric acid (HCl), dimethylformamide (DMF, Sigma-Aldrich), polyvinylidene fluoride (PVDF, Sigma-Aldrich), sodium Tungsten oxide dihydrate (Na2WO4, 99%, Sigma-Aldrich) uye hydrophilic carbon cloth ELAT (Fuel Cell Store) yakashandiswa muchidzidzo ichi.
Hydrated tungsten oxide (HWO) yakagadzirwa ne hydrothermal reaction umo 2 g ye Na2WO4 munyu yakanyungudutswa mu 12 ml ye H O kusvikira mhinduro isina ruvara yawanikwa, uyezve 12 ml ye 2 M HCl yakawedzerwa inodonha kusvika yakareruka yero kumiswa. yakawanikwa.kumiswa.Iyo hydrothermal reaction yakaitwa muTeflon yakavharwa simbi isina simbi autoclave muovheni pa180 ºC kwemaawa matatu.Iyo yakasara yakaunganidzwa nefiltration, yakashambidzwa 3 nguva ne ethanol nemvura, yakaomeswa muchoto pa70 ° C kwe ~ 3 h, uye ipapo pasi kuti uwane bhuruu-grey HWO powder.
Iyo yakawanikwa (isina kubatwa) kabhoni jira electrodes (CCTs) yakashandiswa muchimiro iyo yakawanikwa kana kuiswa mukupisa kurapwa muchoto chechubhu pa450 ° C kwe10 h pakupisa kwe15 ° C / min mumhepo kusvika. kuwana kurapwa UCC (TCC), s Same sezvo yapfuura basa 24. UCC uye TCC akachekwa maelectrodes anenge 1.5 cm paupamhi uye 7 cm kureba.Kumiswa kweC76, HWO, HWO-10% C76, HWO-30% C76 uye HWO-50% C76 yakagadzirirwa nekuwedzera 20 mg yehupfu hwehupfu uye 10 wt% (~ 2.22 mg) yePVDF binder kusvika ~ 1 ml ye DMF yakagadzirirwa mukati uye sonicated kweawa imwe yekuvandudza kufanana.Zvadaro 2 mg yeC76, HWO uye HWO-C76 composites yakashandiswa kune inenge 1.5 cm2 yeUCC inoshanda electrode area.Zvose zvinogadzirisa zvakatakurwa paUCC electrodes uye TCC yakashandiswa pakuenzanisa zvinangwa chete, sezvo basa redu rekare rakaratidza kuti kupisa kupisa hakudiwi 24.Maonero ekugadzirisa akave akawanikwa nekutsvaira 100 µl yekumiswa (mutoro 2 mg) kuitira kufanana kukuru.Zvadaro magetsi ose akaomeswa muchoto usiku hwose pa60 ° C.Maelectrode anoyerwa pamberi uye mushure kuti ave nechokwadi chekutakura kwemasheya.Kuti tive nedzimwe nzvimbo yejometri (~ 1.5 cm2) uye kudzivirira kukwira kwevanadium electrolyte kune electrodes nekuda kwe capillary effect, yakaonda yeparafini yakashandiswa pamusoro pezvinhu zvinoshanda.
A field emission scanning electron microscope (FESEM, Zeiss SEM Ultra 60.5 kV) yakashandiswa kuona HWO pamusoro morphology.Energy dispersive X-ray spectroscopy yakashongedzerwa neFeii8SEM (EDX, Zeiss AG) yakashandiswa kumepu zvinhu zveHWO-50% C76 pamagetsi eUCC.A high resolution transmission electron maikorosikopu (HR-TEM, JOEL JEM-2100) ichishanda pamhepo inomhanya ye200 kV yakashandiswa kuwana mifananidzo yakakwirira uye zvindori zvediffraction zvezvikamu zveHWO.Shandisa Crystallographic Tool Box (CrysTBox) software kuongorora HWO diffraction mhete uchishandisa ringGUI basa uye enzanisa zvabuda neXRD modhi.Chimiro uye graphitization yeUCC neTCC yakagadziriswa ne-X-ray diffraction (XRD) pachiyero chekuongorora che 2.4 ° / min kubva ku5 ° kusvika ku70 ° neCu Kα (λ = 1.54060 Å) uchishandisa Panalytical X-ray diffractometer.(Muenzaniso 3600).XRD inoratidza chimiro chekristaro uye zvikamu zveHWO.Iyo PANalytical X'Pert HighScore software yakashandiswa kuenzanisa nhongonya dzeHWO kune tungsten oxide mepu inowanikwa mudura45.Enzanisa mhinduro dzeHWO nemhedzisiro yeTEM.Iko kuumbwa kwekemikari uye mamiriro emasampuli eHWO akatemerwa neX-ray photoelectron spectroscopy (XPS, ESCALAB 250Xi, ThermoScientific).Iyo CASA-XPS software (v 2.3.15) yakashandiswa peak deconvolution uye kuongorora data.Fourier shandura infrared spectroscopy (FTIR, uchishandisa Perkin Elmer kirasi KBr FTIR spectrometer) zviyero zvakaitwa kuti zvitarise mapoka epamusoro anoshanda eHWO neHWO-50% C76.Enzanisa zvawanikwa ne XPS zvawanikwa.Contact angle measurements (KRUSS DSA25) yakashandiswawo kuratidza kunyorova kwema electrode.
Kune ese electrochemical zviyero, Biologic SP 300 workstation yakashandiswa.Cyclic voltammetry (CV) uye electrochemical impedance spectroscopy (EIS) yakashandiswa kudzidza electrode kinetics yeVO2+/VO2+ redox reaction uye mhedzisiro ye reagent diffusion (VOSO4 (VO2+)) padanho rekuita.Matekinoroji ese ari maviri anoshandisa sero re-electrode ine electrolyte concentration ye0.1 M VOSO4 (V4+) yakanyungudika mu1 M H2SO4 + 1 M HCl (yakasanganiswa asidhi).Yese data ye electrochemical inoratidzwa ndeye IR yakagadziriswa.A saturated calomel electrode (SCE) uye platinum (Pt) coil yakashandiswa sereferensi uye counter electrode, zvichiteerana.Kune CV, ma scan rates (ν) e5, 20, uye 50 mV/s akaiswa kune angangoita hwindo (0–1) V zvichienzaniswa neSCE yeVO2+/VO2+, yobva yagadziriswa pachiyero cheSHE kuronga (VSCE = 0.242 V maererano neHSE) .Kuongorora kuchengetwa kwechiitiko che electrode, CV recycle yakaitwa paUCC, TCC, UCC-C76, UCC-HWO uye UCC-HWO-50% C76 pa ν yakaenzana ne5 mV/s.Kuyero yeEIS yeVO2 +/VO2+ redox reaction, frequency range ye 0.01-105 Hz uye yakavhurika yedunhu voltage (OCV) kukanganisa kwe10 mV yakashandiswa.Kuedza kwega kwega kwakadzokororwa 2-3 nguva kuti ive nechokwadi chekuenderana kwemhedzisiro.The heterogeneous rate constants (k0) yakawanikwa neNicholson method46,47.
Hydrated tungsten oxide (HVO) yakabudirira kugadzirwa nenzira yehydrothermal.SEM mufananidzo mufig.1a inoratidza kuti iyo HWO yakaiswa ine masumbu e nanoparticles ane particle sizes muhuwandu hwe25-50 nm.
Iyo X-ray diffraction pateni yeHWO inoratidza mapeaks (001) uye (002) pa ~ 23.5 ° uye ~ 47.5 °, zvichiteerana, ayo ari maitiro enonstoichiometric WO2.63 (W32O84) (PDF 077-0810, a = 21.4 Å, b = 17.8 Å, c = 3.8 Å, α = β = γ = 90 °), iyo inoenderana neyakajeka ruvara rwebhuruu (Fig. 1b)48,49.Mimwe mikwidza inosvika 20.5°, 27.1°, 28.1°, 30.8°, 35.7°, 36.7° ne52.7° iri pa(140), (620), (350), (720), (740), (560).uye (970) diffraction ndege, maererano, 49 orthorhombic WO2.63.Songara et al.43 yakashandisa nzira imwechete yekugadzira kuti iwane chigadzirwa chichena, icho chainzi kuvepo kweWO3 (H2O) 0.333.Zvisinei, mubasa iri, nekuda kwemamiriro akasiyana-siyana, chigadzirwa chebhuruu-grey chakawanikwa, chichiratidza kugarisana kweWO3 (H2O) 0.333 (PDF 087-1203, a = 7.3 Å, b = 12.5 Å, c = 7.7) muÅ , α = β = γ = 90 °) uye yakaderedzwa fomu ye tungsten oxide.Semiquantitative ongororo neX'Pert HighScore software yakaratidza 26% WO3(H2O)0.333: 74% W32O84.Sezvo W32O84 iine W6+ neW4+ (1.67:1 W6+:W4+), iyo inofungidzirwa yemukati yeW6+ neW4+ ingangoita 72% W6+ uye 28% W4+, zvichiteerana.SEM mifananidzo, 1-second XPS spectra padanho renucleus, TEM mifananidzo, FTIR spectra uye Raman spectra yeC76 zvimedu zvakaunzwa mune yedu yapfuura bepa24.Maererano naKawada et al.50,51, X-ray diffraction pattern yeC76 inoratidza monoclinic structure yeFCC mushure mekubviswa kwe toluene.
SEM mifananidzo mune fig.2a uye b inoratidza kubudirira kweHWO neHWO-50% C76 pa uye pakati pe carbon fibers yeUCC electrodes.Elemental mepu ye tungsten, kabhoni uye oksijeni mumufananidzo weSEM muFig. 2c inoratidzwa mufig.2d–f inoratidza kuti tungsten nekabhoni zvakasanganiswa zvakafanana (ichiratidza kugoverwa kwakafanana) pamusoro penzvimbo ye electrode uye iyo composite haina kuiswa zvakafanana.nekuda kwechimiro chenzira yekunaya kwemvura.
SEM mifananidzo yeakaiswa HWO zvidimbu (a) uye HWO-C76 zvidimbu (b).Mamepu eEDX akaiswa kuHWO-C76 kuUCC achishandisa nzvimbo iri mumufananidzo (c) inoratidza kugoverwa kwetungsten (d), kabhoni (e), uye oxygen (f) mumuenzaniso.
HR-TEM yakashandiswa pakakwirira magnification imaging uye crystallographic ruzivo (Mufananidzo 3).HWO inoratidza nanocube morphology sezvakaratidzwa muMufananidzo 3a uye zvakajeka muMufananidzo 3b.Nekukudza nanocube ye diffraction yenzvimbo yakasarudzwa, iyo grating dhizaini uye diffraction ndege inogutsa mutemo weBragg inogona kuratidzwa sezvakaratidzwa muFigure 3c, ichisimbisa crystallinity yezvinhu.Muchikamu cheMufananidzo 3c inoratidza chinhambwe d 3.3 Å inoenderana ne (022) uye (620) ndege dzekuparadzanisa muWO3 (H2O) 0.333 uye W32O84, 43, 44, 49 nhanho, zvichiteerana.Izvi zvinopindirana nepamusoro XRD kuongororwa (Fig. 1b) sezvo yakacherechedza grating ndege kureba d (Fig. 3c) inopindirana nepamusoro pe XRD yakasimba mumuenzaniso weHWO.Zvindori zvemuenzaniso zvinoratidzwawo mufig.3d, apo mhete imwe neimwe inoenderana nendege yakasiyana.Iyo WO3 (H2O) 0.333 uye W32O84 ndege dzine mavara machena uye bhuruu, zvichiteerana, uye iwo anowirirana XRD peaks anoratidzwawo muFig. 1b.Mhete yekutanga inoratidzwa patani yemhete inoenderana neyekutanga yakanyorwa peak mu x-ray pateni ye (022) kana (620) plane diffraction.Kubva (022) kusvika (402) zvindori, d-madistance e3.30, 3.17, 2.38, 1.93, uye 1.69 Å akawanikwa, ayo anofambirana neXRD tsika dze3.30, 3.17, 2 .45, 1.63 uye 1.63.Å, 44, 45, zvichiteerana.
(a) HR-TEM mufananidzo weHWO, (b) inoratidza mufananidzo wakakurisa.Mifananidzo ye grating ndege inoratidzwa mu (c), uye inset (c) inoratidza mufananidzo wakakura wendege uye nguva d 0.33 nm inoenderana ne (002) uye (620) ndege.(d) HWO ring pattern inoratidza ndege dzakabatanidzwa neWO3 (H2O) 0.333 (white) uye W32O84 (blue) zvikamu.
XPS ongororo yakaitwa kuona iyo yepamusoro chemistry uye oxidation mamiriro e tungsten (Figure S1 uye 4).Mutsara wehupamhi hwe XPS scan yeHWO yakagadzirwa inoratidzwa muFig.S1, inoratidza kuvapo kwe tungsten.Iyo XPS yakamanikana-scan spectra yehukuru hweW 4f uye O 1s mazinga anoratidzwa muFig.4a uye b, zvichiteerana.Iyo W 4f spectrum yakakamurwa kuita maviri spin-orbit kaviri anoenderana nesimba rinosunga reiyo oxidation state W. Nzvimbo dzepamusoro W 4f5/2 uye W 4f7/2 pakusunga masimba e37.8 uye 35.6 eV ndeeW6+, nepamusoro-soro W. 4f5/2 uye W 4f7/2 pa 36.6 uye 34.9 eV hunhu hweW4+ state, zvichiteerana.Kuvapo kweiyo oxidation state (W4 +) inowedzera kusimbisa kuumbwa kweiyo isiri-stoichiometric WO2.63, nepo kuvapo kweW6 + kunoratidza stoichiometric WO3 nekuda kweWO3 (H2O) 0.333.Iyo data yakaiswa yakaratidza kuti maatomu muzana eW6+ neW4+ aive 85% uye 15%, zvichiteerana, ayo anga ari padyo nehunhu hwaifungidzirwa kubva kudata reXRD, zvichipihwa musiyano pakati pehunyanzvi huviri.Nzira mbiri idzi dzinopa ruzivo rwehuwandu nekudzika kwakadzika, kunyanya XRD.Pamusoro pezvo, nzira mbiri idzi dzinoongorora zvikamu zvakasiyana zvechinyorwa nekuti XRD inzira yakawanda nepo XPS iri nzira yepasi inongosvika mashoma nanometers.Iyo O 1s spectrum inokamukana kuita mbiri yepamusoro pa533 (22.2%) uye 530.4 eV (77.8%).Yekutanga inoenderana neOH, uye yechipiri kune oxygen zvisungo mulatisi muWO.Kuvapo kweOH mashandiro emapoka anowirirana neiyo hydration properties yeHWO.
Ongororo yeFTIR yakaitwawo pane aya masampuli maviri kuti aongorore kuvepo kwemapoka anoshanda uye akabatanidza mamorekuru emvura mune hydrated HWO chimiro.Mhedzisiro inoratidza kuti HWO-50% C76 sampuli uye FT-IR HWO zvabuda zvinotaridzika zvakafanana nekuda kwekuvapo kweHWO, asi kusimba kwepamusoro-soro kwakasiyana nekuda kwehuwandu hwakasiyana hwemuenzaniso unoshandiswa panguva yekugadzirira kuongororwa (Fig. 5a )HWO-50% C76 Yese fullerene 24 peaks inoratidzwa kunze kweiyo tungsten oxide peak.Detailed in fig.5a inoratidza kuti sampuli dzese dziri mbiri dzinoratidza bhendi rakasimba kwazvo pa ~ 710/cm, inonzi iOWO inotambanudza kudengenyeka muHWO lattice chimiro, uye pfudzi rakasimba pa ~ 840/cm, inonzi WO.bhendi rinopinza pa ~ 1610/cm rine hukama nekukotama kweOH, uye bhendi rakafara rekunyudza pa ~ 3400/cm rine hukama nekutambanudza kweOH muboka rehydroxyl43.Migumisiro iyi inopindirana ne XPS spectrum muFig. 4b, apo boka rinoshanda reWO rinogona kupa nzvimbo dzinoshanda dzeVO2 +/VO2 + reaction.
FTIR kuongororwa kweHWO neHWO-50% C76 (a) kuratidza mapoka ekushanda uye zviyero zvekusangana nemakona (b, c).
Boka reOH rinogonawo kukonzeresa maitiro eVO2+/VO2+, zvichibva zvawedzera hydrophilicity ye electrode, zvichisimudzira kupararira uye mareti ekufambisa erekitironi.Iyo HWO-50% C76 sampuli inoratidza yakawedzera C76 peak sezvakaratidzwa mumufananidzo.Nzvimbo dzepamusoro pa ~ 2905, 2375, 1705, 1607, uye 1445 cm3 dzinogona kupihwa kune CH, O=C=O, C=O, C=C, uye CO inotambanudzira vibrations, zvichiteerana.Zvinonyatsozivikanwa kuti mapoka eokisijeni anoshanda C=O uye CO anogona kushanda senzvimbo dzinoshanda dzekuita redox kwevanadium.Kuti uedze uye uenzanise kunyorova kwema electrode maviri, zviyero zvemakona zvakashandiswa sezvakaratidzwa mumufananidzo 5b, c.Iyo HWO electrode pakarepo inotora madonhwe emvura, zvichiratidza superhydrophilicity nekuda kweiyo iripo OH inoshanda mapoka.HWO-50% C76 inowedzera hydrophobic, ine kona yekubata inosvika 135 ° mushure memasekondi gumi.Nekudaro, mukuyera kwe electrochemical, iyo HWO-50% C76 electrode yakanyoroveswa zvachose mukati isingasviki miniti.Izvo zviyero zvekunyorova zvinowirirana neXPS neFTIR zvawanikwa, zvichiratidza kuti mamwe mapoka eOH ari pamusoro peHWO anoita kuti ive yakawanda hydrophilic.
Iyo VO2+/VO2+ maitiro eHWO neHWO-C76 nanocomposites akaedzwa uye zvaitarisirwa kuti HWO yaizodzvanya shanduko yegesi yechlorine inoitika panguva yeVO2+/VO2+ maitikiro emusanganiswa asidhi, ukuwo C76 ichizowedzera kukonzeresa yaidiwa VO2+/ VO2+.HWO suspensions ine 10%, 30% uye 50% C76 yakashandiswa kuUCC electrodes ine mutoro wose we2 mg/cm2.
Sezvinoratidzwa mufig.6, iyo kinetics yeVO2 +/VO2+ reaction pa electrode surface yakaongororwa uchishandisa CV mune yakasanganiswa acidic electrolytes.Currents inoratidzwa seI/Ipa kufambisa kuenzanisa kweΔEp uye Ipa/Ipc.Various catalysts inowanikwa zvakananga kubva pamufananidzo.Iyo yazvino nzvimbo unit data inoratidzwa muMufananidzo 2S.Pamusoro pemuonde.Mufananidzo 6a unoratidza kuti HWO inowedzera zvishoma muyero wekuchinjisa maerekitironi eVO2+/VO2+ redox reaction panzvimbo ye electrode uye inodzvanyirira kuita kweparasitic chlorine evolution.Nekudaro, C76 inowedzera zvakanyanya mwero wekufambisa erekitironi uye inokonzeresa kushanduka kweklorini.Naizvozvo, yakaoma ine kurongeka kwakaringana kweHWO neC76 kunofanirwa kuve neakanakisa basa uye kugona kwepamusoro kuvharidzira kuita kweklorini.Yakawanikwa kuti mushure mekuwedzera zvinyorwa zveC76, basa re electrochemical re electrode rakavandudzwa, sezvinoratidzwa nekuderera kwe ΔEp uye kuwedzera kweIpa / Ipc ratio (Table S3).Izvi zvakasimbiswawo neRCT tsika dzakatorwa kubva kuNyquist plot muFig. 6d (tafura S3), kwakawanikwa kuti RCT values ​​yakadzikira nekuwedzera zvirimo zveC76.Mhedzisiro iyi zvakare inopindirana nekudzidza kwaLee uko kuwedzera kwemesoporous kabhoni kune mesoporous WO3 kwakavandudza kubhadharisa kinetics paVO2+/VO2+35.Izvi zvinoratidza kuti kuita kwakanaka kunogona kuvimba zvakanyanya pane conductivity ye electrode (C = C bond) 18,24,35,36,37.Pamusana pekuchinja kwekugadzirisa geometry pakati pe [VO (H2O) 5] 2+ uye [VO2 (H2O) 4]+, C76 inogonawo kuderedza mhinduro inopfurikidza nekuderedza simba remaviri.Zvisinei, izvi zvingave zvisingagoneki neHWO electrodes.
(a) Cyclic voltammetric maitiro eUCC neHWO-C76 macomposites ane akasiyana HWO:C76 ratios muVO2+/VO2+ reactions mu0.1 M VOSO4/1 M H2SO4 + 1 M HCl electrolyte (pa ν = 5 mV/s).(b) Randles-Sevchik uye (c) Nicholson's VO2+/VO2+ nzira yekufungidzira kufambiswa kwakanaka uye kuwana k0 kukosha ​​(d).
Haisi chete HWO-50% C76 yairatidza inenge yakafanana ne electrocatalytic chiitiko seC76 yeVO2+/VO2+ reaction, asi, chinonyanya kufadza, yakawedzera kudzvanya kushanduka kwe chlorine gasi kana ichienzaniswa neC76, sezvakaratidzwa mumufananidzo.6a, kuwedzera pakuratidza diki semicircle mufig.6g (yakaderera RCT).C76 yakaratidza yakakwirira inooneka Ipa / Ipc kupfuura HWO-50% C76 (Tafura S3), kwete nekuda kwekuvandudzwa kwekuita reversibility, asi nekuda kwekupindirana nepamusoro pekuderedza chlorine pa 1.2 V kana ichienzaniswa neSHE.Kuita kwakanakisisa kweHWO-50% C76 kunonzi kunokonzerwa nekubatana pakati peC76 inopomerwa zvakashata zvikuru uye yakanyanya kunyorova uye inogadzirisa kushanda kweW-OH paHWO.Nepo kushomeka kweklorini kuchizovandudza kuchaja kwesero rakazara, kinetics yakagadziridzwa inowedzera kushanda kweiyo yakazara cell voltage.
Maererano ne equation S1, kune quasi-reversible (inononoka electron transfer) maitiro anodzorwa nekupararira, peak current (IP) inoenderana nehuwandu hwemagetsi (n), electrode area (A), diffusion coefficient (D), nhamba. zvemaerekitironi kutamisa coefficient (α) uye kumhanya kwekutarisa (ν).Kuti udzidze kupararira kunodzorwa maitiro ezvakaedzwa zvinhu, hukama pakati pe IP ne ν1/2 hwakarongwa uye hwakaratidzwa muFig. 6b.Sezvo zvese zvishandiso zvichiratidza hukama hwemutsara, maitiro anodzorwa nekupararira.Sezvo iyo VO2 +/VO2+ reaction iri quasi-reversible, kutsetseka kwemutsara kunoenderana neiyo diffusion coefficient uye kukosha kwe α (equation S1).Nekuda kwekusagadzikana kweiyo coefficient (≈ 4 × 10-6 cm2 / s) 52, mutsauko mumutsara wemutsetse unoratidza zvakananga kukosha kwakasiyana kwea uye nekudaro mwero wakasiyana wekuchinjisa maerekitironi kunzvimbo ye electrode, ine C76 neHWO -50. % C76, ichiratidza materu akanyanya (yakakwirira maerekitironi kutamisa mwero).
Iyo yakaverengerwa yakaderera-frequency Warburg materu (W) anoratidzwa muTable S3 (Fig. 6d) ane kukosha padyo ne1 kune ese zvigadzirwa, zvichiratidza kupararira kwakakwana kwezvikamu zveredox uye kusimbisa mutsara maitiro eIP maringe ne1/2 yeCV.zviyero .Nokuda kweHWO-50% C76, mutsetse weWarburg unotsauka kubva pakubatana kuenda ku1.32, zvichiratidza mupiro kwete chete kubva kune semi-infinite diffusion ye reactants (VO2+), asiwo ingangove yakatetepa-layer maitiro mukupararira kwemaitiro nekuda kwe electrode porosity.
Kuenderera mberi nekuongorora kudzoreredzwa (electron transfer rate) yeVO2+/VO2+ redox reaction, Nicholson quasi-reversible reaction method yakashandiswawo kuona mwero wakajairwa unogara k041.42.Izvi zvinoitwa nekuronga iyo dimensionless kinetic parameter Ψ sebasa reΔEp sebasa re ν−1/2 uchishandisa S2 equation.Tafura S4 inoratidza inoguma Ψ kukosha kune yega yega electrode zvinhu.Ronga zvabuda (Mufananidzo 6c) kuti uwane k0 × 104 cm/s (yakanyorwa padivi pemutsara wega wega uye inoratidzwa muTable S4) uchishandisa equation S3 pamateru echikamu chimwe nechimwe.HWO-50% C76 yakawanikwa iine slope yakakwirira (Fig. 6c) uye saka iyo yepamusoro k0 inokosha ye2.47 × 10-4 cm / s.Izvi zvinoreva kuti electrode iyi inopa inokurumidza kinetics inoenderana neCV uye EIS mhedzisiro muFigure 6a uye d uye Tafura S3.Uye zvakare, iyo k0 tsika dzakawanikwawo kubva kuNyquist plots (Fig. 6d) yeEquation S4 uchishandisa iyo RCT kukosha (Tafura S3).Iyi k0 mhedzisiro kubva kuEIS inopfupikiswa muTebhura S4 uye zvakare inoratidza kuti HWO-50% C76 inoratidza yakakwira maerekitironi kutamisa mwero nekuda kweiyo synergistic mhedzisiro.Kunyangwe kukosha kwek0 kwakasiyana nekuda kwekusiyana kwakasiyana kwenzira yega yega, ichiri kuratidza kurongeka kwakafanana kwehukuru uye inoratidza kuenderana.
Kuti unzwisise zvizere kinetics yakanakisa inogona kuwanikwa, zvakakosha kuenzanisa iyo yakakwana electrode zvinhu neuninsulated UCC uye TCC electrodes.Kune iyo VO2 +/VO2+ reaction, HWO-C76 haina kungoratidza yakaderera ΔEp uye nani kudzoreredza, asi zvakare yakadzvanya zvakanyanya parasitic chlorine evolution reaction kana ichienzaniswa neTCC, sezvakaratidzwa nekudonha kwakakosha ikozvino pa1.45 V kana ichienzaniswa nekuona OHA (Fig. 7a).Mukutaura kwekugadzikana, takafunga kuti HWO-50% C76 yakagadzikana mumuviri nokuti iyo catalyst yakasanganiswa nePVDF binder ndokubva yashandiswa kune carbon cloth electrodes.Kuenzaniswa ne50 mV yeUCC, HWO-50% C76 yakaratidza kuchinja kwepamusoro kwe44 mV mushure me150 cycles (degradation rate 0.29 mV / cycle) (Mufananidzo 7b).Inogona kunge isiri mutsauko mukuru, asi kinetics yeUCC electrode inononoka uye inosvibisa nekuchovha bhasikoro, kunyanya kumusana.Kunyangwe kudzoreredzwa kweTCC kuri nani kupfuura kweUCC, TCC yakawanikwa iine shanduko huru ye 73 mV mushure memazana zana nemakumi mashanu, izvo zvingave zvichikonzerwa nehuwandu hweklorini yakaburitswa kubva pamusoro payo.Kuve nechokwadi chekuti catalyst inonamatira zvakanaka kune electrode pamusoro.Sezvinoonekwa pamagetsi ese akaedzwa, kunyangwe ayo asina anotsigirwa anokonzeresa anoratidza dhigirii dzakasiyana dzekusagadzikana kwebhasikoro, zvichiratidza kuti shanduko mukuparadzana kwepamusoro panguva yebhasikoro imhaka yekudzima zvinhu nekuda kwekuchinja kwemakemikari pane kuparadzanisa kupatsanurwa.Zvakare, kana huwandu hukuru hwezvimedu zvinokonzeresa zvaifanira kuparadzaniswa kubva kune electrode pamusoro, izvi zvaizoita kuti kuwedzere kukuru kwekuparadzaniswa kwepamusoro (kwete chete ne44 mV), sezvo substrate (UCC) isingashande yeVO2 +/VO2 + redox reaction.
Kuenzanisa kweCV (a) uye kugadzikana kweiyo redox reaction VO2 +/VO2+ (b) yeakanakisa electrode zvinhu zvine chekuita neCCC.Mu electrolyte 0.1 M VOSO4/1 M H2SO4 + 1 M HCl, maCV ose akaenzana ne ν = 5 mV/s.
Kuwedzera kukwezva kwehupfumi kweVRFB tekinoroji, kuvandudza uye kunzwisisa kinetics yevanadium redox reaction kwakakosha kuti uwane yakakwira simba.Composites HWO-C76 yakagadzirirwa uye yavo electrocatalytic mhedzisiro paVO2+/VO2+ reaction yakadzidzwa.HWO yakaratidza kuwedzeredza kinetic asi yakanyanya kudzvanya chlorine shanduko mune yakasanganiswa acidic electrolytes.Mareshiyo akasiyana eHWO: C76 akashandiswa kuenderera mberi nekunatsiridza kinetics yeHWO-based electrodes.Kuwedzera zvirimo zveC76 kusvika kuHWO zvinogona kuvandudza maelectron transfer kinetics eVO2+/VO2+ reaction pane yakagadziridzwa electrode, pakati payo HWO-50% C76 ndiyo yakanakisa zvinhu nekuti inodzikisa kubhadharisa kutamisa kuramba uye kunowedzera kudzvanya kushanduka kwegesi yeklorini kana ichienzaniswa ne. C76.uye TCC inoburitswa.Izvi zvakakonzerwa nekubatana pakati peC=C sp2 hybridization, OH neW-OH inoshanda mapoka.Kuderera kwehuwandu hweHWO-50% C76 yakawanikwa iine 0.29mV / cycle pasi pemabhasikoro akawanda apo UCC neTCC dziri 0.33mV / cycle uye 0.49mV / cycle zvakateerana, zvichiita kuti igadzikane zvikuru mumasanganiswa e-acid electrolytes.Mhedzisiro yakaratidzwa inobudirira kuona yakakwirira performance electrode zvinhu zveVO2+/VO2+ reaction ine fast kinetics uye yakanyanya kugadzikana.Izvi zvichawedzera magetsi ekubuda, nekudaro zvichivandudza kugona kwemagetsi kweVRFB, nekudaro kuderedza mutengo wekutengesa kwayo kweramangwana.
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