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Igiciro kiri hejuru ya vanadium yose itembera muri bateri ya redox (VRFBs) igabanya imikoreshereze yabyo.Kunoza kinetics ya reaction ya electrochemic reaction birasabwa kongera ingufu nimbaraga zingirakamaro za VRFB, bityo bikagabanya igiciro cya kilowati ya VRFB.Muri uyu murimo, hydrothermally synthesized hydrated tungsten oxide (HWO) nanoparticles, C76 na C76 / HWO, yashyizwe kuri electrode yimyenda ya karubone hanyuma igeragezwa nka electrocatalysis ya VO2 + / VO2 + redox reaction.Ikwirakwizwa ry’imyuka ya elegitoronike microscopi (FESEM), ikwirakwiza ingufu za X-ray spectroscopi (EDX), imiyoboro ya elegitoronike ikwirakwiza mikorosikopi (HR-TEM), X-ray itandukanya (XRD), X-ray ifoto yerekana amashanyarazi (XPS), infrared Fourier ihindura Spectroscopy (FTIR) hamwe no gupima impande zose.Byagaragaye ko kongeramo C76 fullerène kuri HWO bishobora guteza imbere kinetike ya electrode mu kongera amashanyarazi no gutanga amatsinda akora ya okiside hejuru yayo, bityo bigatuma VO2 + / VO2 + redox reaction.HWO / C76 igizwe (50 wt% C76) byagaragaye ko aribwo buryo bwiza bwo guhitamo VO2 + / VO2 + hamwe na ΔEp ya mV 176, mugihe imyenda ya karubone itavuwe (UCC) yari mV 365.Byongeye kandi, HWO / C76 yibumbiye hamwe byagaragaje ingaruka zikomeye zo guhagarika ingaruka ziterwa na parasitike ya chlorine ya parasitike bitewe nitsinda rya W-OH.
Ibikorwa bikomeye byabantu hamwe n’impinduramatwara yihuse mu nganda byatumye amashanyarazi akenera bidasubirwaho amashanyarazi, yiyongera hafi 3% ku mwaka1.Mu myaka ibarirwa muri za mirongo, ikoreshwa ry’ibicanwa by’ibinyabuzima nk’isoko ry’ingufu byatumye imyuka ihumanya ikirere igira uruhare mu gushyuha kw’isi, amazi n’umwuka w’ikirere, bikangiza ibidukikije byose.Kubera iyo mpamvu, biteganijwe ko kwinjira mu muyaga usukuye kandi ushobora kuvugururwa n’ingufu n’izuba biteganijwe ko bizagera kuri 75% by’amashanyarazi yose mu 20501. Icyakora, iyo umugabane w’amashanyarazi uva ahantu hashobora kurenga 20% by’amashanyarazi yose, umuyoboro uhinduka udahungabana.
Muri sisitemu zose zo kubika ingufu nka batiri ya Hybrid vanadium redox flow bateri2, bateri ya redox ya redox yose (VRFB) yateye imbere byihuse kubera ibyiza byayo byinshi kandi ifatwa nkigisubizo cyiza cyo kubika ingufu z'igihe kirekire (hafi imyaka 30).) Amahitamo ahujwe ningufu zishobora kubaho4.Ibi biterwa no gutandukanya ingufu nubucucike bwingufu, igisubizo cyihuse, igihe kirekire cyumurimo, hamwe nigiciro gito cyumwaka kingana na $ 65 / kWt ugereranije na $ 93-140 / kWt kuri Li-ion na bateri ya aside-aside na 279-420 US $ kuri kilowati.bateri.
Nyamara, ubucuruzi bwabo bunini buracyafite imbogamizi kubiciro bya sisitemu yo hejuru cyane, bitewe ahanini na selile 4.5.Rero, kunoza imikorere ya stack mukongera kinetics yibice bibiri-bigize reaction irashobora kugabanya ingano ya stack bityo bikagabanya ibiciro.Kubwibyo, kwihuta kwa elegitoronike kwihuta hejuru ya electrode birakenewe, biterwa nigishushanyo, imiterere nuburyo imiterere ya electrode kandi bisaba gukora neza6.Nuburyo bwiza bwa chimique na electrochemicique hamwe nu mashanyarazi meza ya karubone electrode, kinetics zabo zitavuwe ziratinda kubera kubura amatsinda akora ya ogisijeni na hydrophilicity 7,8.Kubwibyo, amashanyarazi atandukanye ahujwe na electrode ishingiye kuri karubone, cyane cyane carbone nanostructures na oxyde de metal, kugirango itezimbere imikorere ya electrode zombi, bityo byongere imbaraga za electrode ya VRFB.
Usibye akazi kacu kambere kuri C76, twabanje kumenyesha ibikorwa byiza bya electrocatalytic yiyi fullerene ya VO2 + / VO2 +, kwishyuza amafaranga, ugereranije nubushyuhe bwa karubone butavuwe kandi butavuwe.Kurwanya byagabanutseho 99.5% na 97%.Imikorere ya catalitiki yibikoresho bya karubone kuri VO2 + / VO2 + ugereranije na C76 bigaragara mu mbonerahamwe S1.Ku rundi ruhande, okiside nyinshi z'icyuma nka CeO225, ZrO226, MoO327, NiO28, SnO229, Cr2O330 na WO331, 32, 33, 34, 35, 36, 37 zakoreshejwe kubera ubwinshi bw’amazi menshi ndetse n’imikorere myinshi ya ogisijeni., 38. itsinda.Igikorwa cya catalitiki yiyi oxyde yicyuma muri reaction ya VO2 + / VO2 + igaragara mumeza S2.WO3 yakoreshejwe mubikorwa byinshi bitewe nigiciro cyayo gito, ituze ryinshi mubitangazamakuru bya acide, hamwe nibikorwa bya catalitike 31,32,33,34,35,36,37,38.Ariko, iterambere rya cathodic kinetics kubera WO3 ntagaciro.Kugirango tunoze neza WO3, ingaruka zo gukoresha tide ya tungsten yagabanutse (W18O49) kubikorwa bya catodiki yageragejwe38.Hydrated tungsten oxyde (HWO) ntabwo yigeze igeragezwa mubikorwa bya VRFB, nubwo igaragaza ibikorwa byiyongera mubikorwa bya supercapacitor bitewe no gukwirakwiza cation byihuse ugereranije na WOx39,40.Igisekuru cya gatatu cya batiri ya redadium flux ikoresha acide electrolyte ivanze igizwe na HCl na H2SO4 kugirango itezimbere imikorere ya bateri kandi itezimbere kandi ihamye ya ion ya vanadium muri electrolyte.Nyamara, parasitike ya chlorine yihindagurika yabaye imwe mu mbogamizi zo mu gisekuru cya gatatu, bityo rero gushakisha uburyo bwo kubuza isuzuma rya chlorine byabaye intego yibanze mu matsinda menshi y’ubushakashatsi.
Hano, ibizamini bya VO2 + / VO2 + byakorewe kuri compte ya HWO / C76 yashyizwe kuri electrode yimyenda ya karubone kugirango haboneke uburinganire hagati yumuriro wamashanyarazi wibintu hamwe na redox kinetics yubuso bwa electrode mugihe uhagarika ubwihindurize bwa chlorine parasitike.igisubizo (CER).Hydrated tungsten oxyde (HWO) nanoparticles yashizwemo nuburyo bworoshye bwa hydrothermal.Ubushakashatsi bwakorewe muri electrolyte ivanze (H2SO4 / HCl) kugira ngo bigane igisekuru cya gatatu VRFB (G3) kugira ngo gikore kandi gikore iperereza ku ngaruka HWO yagize kuri parasitike ya chlorine ya parasitike.
Vanadium (IV) sulfate hydratate (VOSO4, 99,9%, Alfa-Aeser), aside sulfurike (H2SO4), aside hydrochloric (HCl), dimethylformamide (DMF, Sigma-Aldrich), polyvinylidene fluoride (PVDF, Sigma) -Aldrich), sodium Dung4 umwenda ELAT (Ububiko bwa Fuel Cell) wakoreshejwe muri ubu bushakashatsi.
Hydrated tungsten oxyde (HWO) yateguwe na hydrothermal reaction 43 aho g 2 yumunyu wa Na2WO4 yashonga muri ml 12 ya H2O kugirango itange igisubizo kitagira ibara, hanyuma ml 12 ya 2 M HCl yongewemo igitonyanga kugirango ihagarike umuhondo wijimye.Amashanyarazi yashyizwe muri Teflon yometseho ibyuma bitagira umuyonga hanyuma abikwa mu ziko kuri 180 ° C. amasaha 3 kugirango hydrothermal reaction.Ibisigarira byakusanyirijwe mu kuyungurura, gukaraba inshuro 3 hamwe na Ethanol n'amazi, byumishwa mu ziko kuri 70 ° C mu masaha ~ 3, hanyuma bikurikiranwa kugira ngo bitange ifu ya HWO y'ubururu.
Imyenda ya karubone yabonetse (itavuwe) electrode (CCT) yakoreshejwe nkuko bisanzwe cyangwa ubushyuhe bwakorewe mu itanura rya tube kuri 450 ° C mu kirere hamwe n’ubushyuhe bwa 15 ºC / min mu masaha 10 kugirango ubone CC zavuwe (TCC).nkuko byasobanuwe mu ngingo ibanza24.UCC na TCC byaciwe muri electrode hafi cm 1.5 z'ubugari na cm 7 z'uburebure.Guhagarika C76, HWO, HWO-10% C76, HWO-30% C76 na HWO-50% C76 byateguwe hongerwaho mg 20%.Mg 2 za C76, HWO na HWO-C76 zashyizwe hamwe zikurikirana kuri UCC ikora electrode ikora hafi ya cm 1.5.Catalizator zose zashyizwe kuri electrode ya UCC kandi TCC yakoreshejwe mugereranya gusa, kuko akazi kacu kambere kerekanaga ko kuvura ubushyuhe bitari ngombwa24.Gukemura ibibazo byagezweho mugukaraba 100 µl yo guhagarikwa (umutwaro 2 mg) kugirango birusheho kuba byiza.Hanyuma electrode zose zumishijwe mu ziko kuri 60 ° C. ijoro ryose.Electrode ipimwa imbere n'inyuma kugirango harebwe neza ibicuruzwa.Kugirango habeho agace runaka ka geometrike (~ 1.5 cm2) no gukumira izamuka rya electrolyte ya vanadium kuri electrode kubera ingaruka ya capillary, hashyizweho urwego ruto rwa paraffine hejuru yibikoresho bikora.
Imyuka yoherezwa mu kirere isikana electron microscopi (FESEM, Zeiss SEM Ultra 60, 5 kV) yakoreshejwe mu kureba morfologiya ya HWO.Imashanyarazi ikwirakwiza X-ray yerekanwe ifite Feii8SEM (EDX, Zeiss Inc.) yakoreshejwe mugushushanya ibintu HWO-50% C76 kuri electrode ya UCC.Ikwirakwizwa ryinshi rya elegitoronike microscope (HR-TEM, JOEL JEM-2100) ikorera kuri voltage yihuta ya 200 kV yakoreshejwe mugushushanya hejuru ya HWO nuduce twinshi.Porogaramu ya Crystallography Toolbox (CrysTBox) ikoresha imikorere ya ringGUI mu gusesengura uburyo bwo gutandukanya impeta ya HWO no kugereranya ibisubizo nuburyo bwa XRD.Imiterere no gushushanya UCC na TCC byasesenguwe no gutandukanya X-ray (XRD) ku gipimo cya scan ya 2,4 ° / min kuva 5 ° kugeza 70 ° hamwe na Cu Kα (λ = 1.54060 Å) ukoresheje Panalytical X-ray diffractometer (Model 3600).XRD yerekanye kristu yuburyo nicyiciro cya KABIRI.Porogaramu ya PANalytical X'Pert HighScore yakoreshejwe mu guhuza impinga ya HWO ku ikarita ya tungsten oxyde iboneka muri data base45.Ibisubizo BIBIRI byagereranijwe nibisubizo bya TEM.Imiterere yimiti nuburyo byintangarugero ya HWO byagenwe na X-ray yifoto yerekana amashanyarazi (XPS, ESCALAB 250Xi, ThermoScientific).Porogaramu CASA-XPS (v 2.3.15) yakoreshejwe mu mpinga ya deconvolution no gusesengura amakuru.Kugirango umenye amatsinda yimikorere ya HWO na HWO-50% C76, ibipimo byakozwe hifashishijwe Fourier transform infrared spectroscopy (FTIR, Perkin Elmer spectrometer, ukoresheje KBr FTIR).Ibisubizo byagereranijwe nibisubizo bya XPS.Ibipimo byo guhuza impande (KRUSS DSA25) nabyo byakoreshejwe mukuranga wettable ya electrode.
Kubipimo byose byamashanyarazi, hakoreshejwe Biologic SP 300 ikorerwamo.Voltammetry ya Cyclic (CV) hamwe na electrochemical impedance spectroscopy (EIS) yakoreshejwe mukwiga electrode kinetics ya VO2 + / VO2 + redox reaction n'ingaruka zo gukwirakwiza reagent (VOSO4 (VO2 +)) ku gipimo cya reaction.Ubwo buryo bwombi bwakoresheje selile ya electrode eshatu hamwe na electrolyte ya 0.1 M VOSO4 (V4 +) muri 1 M H2SO4 + 1 M HCl (imvange ya acide).Amakuru yose yamashanyarazi yatanzwe ni IR yakosowe.Electrode yuzuye ya Calomel (SCE) hamwe na colatine ya platine (Pt) yakoreshejwe nkibisobanuro hamwe na compte electrode.Kuri CV, igipimo cya scan (ν) cya 5, 20, na 50 mV / s cyakoreshejwe kuri VO2 + / VO2 + idirishya rishobora kuba (0–1) V na SCE, hanyuma rihindurwa kugirango SHE itegure (VSCE = 0.242 V na HSE).Kwiga kugumana ibikorwa bya electrode, CV zisubiramo zakozwe kuri ν 5 mV / s kuri UCC, TCC, UCC-C76, UCC-HWO, na UCC-HWO-50% C76.Kubipimo bya EIS, intera yumurongo wa VO2 + / VO2 + redox reaction yari 0.01-105 Hz, naho guhagarika ingufu za voltage kuri voltage yumuriro (OCV) byari mV 10.Buri igeragezwa ryasubiwemo inshuro 2-3 kugirango ibisubizo bihamye.Igipimo cya heterogeneous (k0) cyabonetse kuburyo bwa Nicholson46,47.
Hydrated tungsten oxyde (HVO) yashizwemo neza nuburyo bwa hydrothermal.SEM ishusho mugitabo.1a yerekana ko HWO yabitswe igizwe na cluster ya nanoparticles ifite ubunini buri hagati ya 25-50 nm.
Imiterere ya X-ray itandukanya HWO yerekana impinga (001) na (002) kuri ~ 23.5 ° na ~ 47.5 °, zikaba ziranga WO2.63 (W32O84) (PDF 077–0810, a = 21.4 Å, b = 17.8 Å, c = 3.8 Å, α = β = ∼).Izindi mpinga zigera kuri 20.5 °, 27.1 °, 28.1 °, 30.8 °, 35.7 °, 36.7 ° na 52.7 ° zahawe (140), (620), (350), (720), (740), (560 °).)) na (970) indege zitandukanya orthogonal kuri WO2.63, kimwe.Uburyo bumwe bwogukoresha bwakoreshejwe na Songara nabandi.43 kubona ibicuruzwa byera, byitirirwa kuba WO3 (H2O) 0.333.Nyamara, muri iki gikorwa, bitewe nuburyo butandukanye, habonetse ibicuruzwa byubururu-imvi, byerekana ko WO3 (H2O) 0.333 (PDF 087-1203, a = 7.3 Å, b = 12.5 Å, c = 7 .7 Å, α = β = γ = 90 °) nuburyo bwagabanutse bwa okiside ya tungsten.Isesengura rya Semiquantitative ukoresheje software ya X'Pert HighScore yerekanye 26% WO3 (H2O) 0.333: 74% W32O84.Kubera ko W32O84 igizwe na W6 + na W4 + (1.67: 1 W6 +: W4 +), ibigereranyo biri muri W6 + na W4 + ni 72% W6 + na 28% W4 +.Amashusho ya SEM, 1-isegonda XPS yerekanwe kurwego rwa nucleus, amashusho ya TEM, FTIR yerekanwe, na Raman yerekanwe ya C76 ibice byerekanwe mubiganiro byacu byabanjirije.Nk’uko Kawada n'abandi babivuga, 50,51 X-itandukanya X-ray ya C76 nyuma yo gukuraho toluene yerekanye imiterere ya monoclinic ya FCC.
SEM amashusho mugitabo.2a na b byerekana ko HWO na HWO-50% C76 zabitswe neza no hagati ya fibre ya karubone ya electrode ya UCC.Ikarita ya EDX ikarita ya tungsten, karubone, na ogisijeni ku mashusho ya SEM mu mutini.2c irerekanwa mugitabo.2d-f yerekana ko tungsten na karubone bivanze neza (byerekana isaranganya risa) hejuru ya electrode yose kandi ikomatanyirizo ntiribikwa kimwe kubera imiterere yuburyo bwo kubitsa.
SEM amashusho yabitswe HWO (a) na HWO-C76 ibice (b).Ikarita ya EDX kuri HWO-C76 yapakiye kuri UCC ukoresheje agace ku ishusho (c) yerekana ikwirakwizwa rya tungsten (d), karubone (e), na ogisijeni (f) muri sample.
HR-TEM yakoreshejwe mugukuza cyane amashusho hamwe namakuru ya kristu (Ishusho 3).HWO yerekana morfologiya ya nanocube nkuko bigaragara ku gishushanyo cya 3a kandi bigaragara neza ku gishushanyo cya 3b.Mugukuza nanocube kugirango itandukane ahantu hatoranijwe, umuntu arashobora kwiyumvisha imiterere yo gusya hamwe nindege zitandukanya zujuje amategeko ya Bragg, nkuko bigaragara ku gishushanyo cya 3c, yemeza ko ibintu bitagaragara.Mu gushiramo ku gishushanyo cya 3c yerekana intera d 3.3 Å ihuye n’indege (022) na (620) itandukanya iboneka mu cyiciro cya WO3 (H2O) 0.333 na W32O84, uko bikurikirana 43,44,49.Ibi bihuye nisesengura rya XRD ryasobanuwe haruguru (Igishusho 1b) kuva intera yagaragaye indege ya d (Ishusho 3c) ihuye nimpinga ikomeye ya XRD murugero rwa HWO.Impeta z'icyitegererezo nazo zerekanwa mugitabo.3d, aho buri mpeta ihuye nindege itandukanye.Indege za WO3 (H2O) 0.333 na W32O84 zifite ibara ryera nubururu, kandi impinga za XRD zijyanye nazo zirerekanwa ku gishushanyo 1b.Impeta ya mbere yerekanwe ku gishushanyo cy’impeta ihuye nimpinga ya mbere yagaragaye mu ishusho ya x-ray yindege ya (022) cyangwa (620).Kuva kuri (022) kugeza kuri (402) impeta, agaciro ka d-intera ni 3.30, 3.17, 2.38, 1.93, na 1.69 Å, bihuye nagaciro ka XRD ka 3.30, 3.17, 2, 45, 1.93.na 1.66 Å, bingana na 44, 45.
(a) Ishusho ya HR-TEM ya HWO, (b) yerekana ishusho nini.Amashusho yindege ya grake yerekanwa muri (c), inset (c) yerekana ishusho nini yindege hamwe na d d ya 0.33 nm ihuye nindege (002) na (620).(d) Ishusho yimpeta ebyiri zerekana indege zijyanye na WO3 (H2O) 0.333 (cyera) na W32O84 (ubururu).
Isesengura rya XPS ryakozwe kugirango hamenyekane ubutaka bwa chimie na okiside ya tungsten (Ishusho S1 na 4).Ingano yagutse ya XPS scan ya synthesize HWO irerekanwa mumashusho S1, byerekana ko tungsten ihari.XPS ifunganye-scan yerekana urwego rwa W 4f na O 1s rwerekanwe mubishushanyo.4a na b.Ikirangantego cya W 4f kigabanyijemo kabiri kuzenguruka-kuzenguruka gukwiranye ningufu zihuza za W okiside ya leta.na W 4f7 / 2 kuri 36.6 na 34.9 eV biranga leta ya W4 + ya 40, uko bikurikirana.) 0.333.Amakuru yashyizwe ahagaragara yerekana ko ijanisha rya atome rya W6 + na W4 + ari 85% na 15%, ibyo bikaba byegeranye nagaciro kagereranijwe kuva muri XRD urebye itandukaniro riri hagati yuburyo bubiri.Ubwo buryo bwombi butanga amakuru yuzuye hamwe nukuri, cyane cyane XRD.Na none, ubu buryo bubiri busesengura ibice bitandukanye byibikoresho kuko XRD nuburyo bwinshi mugihe XPS nuburyo bwubuso bwegera nanometero nkeya.Ikirangantego cya O 1s kigabanijwemo impinga ebyiri kuri 533 (22.2%) na 530.4 eV (77.8%).Iya mbere ihuye na OH, naho iya kabiri ihuza ogisijeni muri latike muri WO.Kubaho kwa OH amatsinda akora birahuye na hydration ya HWO.
Hakozwe kandi isesengura rya FTIR kuri izi ngero zombi kugira ngo harebwe niba hari amatsinda akora no guhuza molekile z’amazi mu miterere ya HWO.Ibisubizo byerekana ko icyitegererezo cya HWO-50% C76 hamwe na FT-IR HWO ibisubizo bisa nkaho HWO ihari, ariko ubukana bwimpinga buratandukanye bitewe nubunini butandukanye bw'icyitegererezo bwakoreshejwe mugutegura isesengura (Ishusho 5a).) HWO-50% C76 yerekana ko impinga zose, usibye impinga ya tungsten oxyde, zifitanye isano na fullerene 24. Birambuye mumitini.5a yerekana ko ingero zombi zigaragaza umurongo mugari cyane kuri ~ 710 / cm bitewe na OWO irambuye ihindagurika mu miterere ya HWO, hamwe nigitugu gikomeye kuri ~ 840 / cm bitirirwa WO.Kurambura kunyeganyega, umurongo utyaye kuri 1610 / cm biterwa no kunama kunyeganyega kwa OH, mugihe umugozi mugari wa 3400 / cm biterwa no kurambura ibinyeganyega bya OH mumatsinda ya hydroxyl43.Ibisubizo birahuye na XPS yerekanwe mubishushanyo.4b, aho amatsinda ya WO ashobora gutanga imbuga zikora kuri VO2 + / VO2 + reaction.
Isesengura rya FTIR rya HWO na HWO-50% C76 (a), ryerekanye amatsinda akora hamwe no gupima inguni (b, c).
Itsinda rya OH rishobora kandi guhagarika reaction ya VO2 + / VO2 +, mugihe byongera hydrophilique ya electrode, bityo bikazamura umuvuduko wo gukwirakwizwa no kohereza electron.Nkuko byerekanwe, icyitegererezo cya HWO-50% C76 cyerekana impinga yinyongera kuri C76.Impinga kuri ~ 2905, 2375, 1705, 1607, na 1445 cm3 zirashobora guhabwa CH, O = C = O, C = O, C = C, na CO irambuye.Birazwi neza ko amatsinda akora ya ogisijeni C = O na CO ashobora kuba ibigo bikora kuri redox reaction ya vanadium.Kugerageza no kugereranya ubushuhe bwa electrode ebyiri, ibipimo byo guhuza impande zafashwe nkuko bigaragara ku gishushanyo cya 5b, c.HWO electrode yahise ikuramo ibitonyanga byamazi, byerekana superhydrophilicite kubera amatsinda ya OH aboneka.HWO-50% C76 ni hydrophobique, hamwe nu mpande zingana na 135 ° nyuma yamasegonda 10.Nyamara, mubipimo by'amashanyarazi, electrode ya HWO-50% C76 yahindutse rwose muminota itarenze umunota.Ibipimo bya wettability bihuye nibisubizo bya XPS na FTIR, byerekana ko amatsinda menshi ya OH hejuru ya HWO atuma hydrophilique iba myinshi.
VO2 + / VO2 + reaction ya HWO na HWO-C76 nanocomposite yageragejwe kandi byari byitezwe ko HWO izahagarika ihindagurika rya chlorine muri reaction ya VO2 + / VO2 + muri aside ivanze, naho C76 ikarushaho guhagarika icyifuzo cya VO2 + / VO2 + redox.%, 30%, na 50% C76 muguhagarika HWO na CCC yashyizwe kuri electrode yuzuye yuzuye hafi mg / cm2.
Nkuko bigaragara ku gishushanyo.6, kinetics ya VO2 + / VO2 + reaction kuri ecran ya electrode yasuzumwe na CV muri electrolyte ivanze.Inzira zerekanwa nka I / Ipa kugirango ugereranye byoroshye ΔEp na Ipa / Ipc kuri catalizator zitandukanye ku gishushanyo.Agace kamwe kamwe mubice byerekanwe mubishusho 2S.Ku mutini.Igicapo 6a cerekana ko HWO yongerera gato igipimo cyo kohereza electron ya VO2 + / VO2 + redox reaction kuri electrode hejuru kandi igahagarika reaction yubwihindurize bwa parasitike ya chlorine.Nyamara, C76 yongerera cyane igipimo cyo kohereza electron kandi igahindura reaction ya chlorine.Kubwibyo, ibice byateguwe neza bya HWO na C76 byitezwe ko bifite ibikorwa byiza nubushobozi bukomeye bwo kubuza ihindagurika rya chlorine.Byagaragaye ko nyuma yo kongera ibiri muri C76, ibikorwa byamashanyarazi ya electrode byateye imbere, nkuko bigaragazwa no kugabanuka kwa ΔEp no kwiyongera kwa Ipa / Ipc (Imbonerahamwe S3).Ibi kandi byashimangiwe n’agaciro ka RCT yakuwe mu kibanza cya Nyquist ku gishushanyo cya 6d (Imbonerahamwe S3), wasangaga igabanuka hamwe no kwiyongera kwa C76.Ibisubizo kandi bihuye nubushakashatsi bwa Li, aho kongeramo karubone ya mesoporous kuri mesoporous WO3 yerekanaga uburyo bwiza bwo kohereza amafaranga kuri VO2 + / VO2 + 35.Ibi byerekana ko reaction itaziguye ishobora guterwa cyane nubushakashatsi bwa electrode (C = C inkwano) 18, 24, 35, 36, 37. Ibi birashobora kandi guterwa nimpinduka ya geometrie ihuza hagati ya [VO (H2O) 5] 2+ na [VO2 (H2O) 4] +, C76 igabanya umuvuduko ukabije mukugabanya ingufu za tissue.Ariko, ibi ntibishoboka hamwe na HWO electrode.
.(b) Randles-Sevchik na (c) Nicholson VO2 + / VO2 + uburyo bwo gusuzuma imikorere ikwirakwizwa no kubona indangagaciro za k0 (d).
Ntabwo HWO-50% C76 yerekanaga ibikorwa bya electrocatalytic hafi ya C76 kubikorwa bya VO2 + / VO2 +, ariko, igishimishije, byongeye kandi ko byahinduye ubwihindurize bwa chlorine ugereranije na C76, nkuko bigaragara ku gishushanyo cya 6a, kandi ikanagaragaza Semicircle Ntoya mu mutini.6d (RCT yo hepfo).C.Imyuka ya chlorine nkeya izamura imikorere yumuriro wa selile yuzuye, mugihe kinetics yatezimbere izamura imikorere ya voltage yuzuye.
Ukurikije ikigereranyo cya S1, kubijyanye na quasi-reversible (ugereranije na buhoro buhoro ihererekanyabubasha rya elegitoronike) igenzurwa no gukwirakwizwa, impinga ya mpinga (IP) iterwa numubare wa electron (n), agace ka electrode (A), coefficient de diffuzione (D), umubare wa coefficient de electron (α) n'umuvuduko wo gusikana (ν).Kugirango twige imyitwarire igenzurwa no gukwirakwiza ibikoresho byageragejwe, umubano hagati ya IP na ν1 / 2 wateguwe kandi utangwa ku gishushanyo cya 6b.Kubera ko ibikoresho byose byerekana umurongo umwe, reaction igenzurwa no gukwirakwizwa.Kubera ko VO2 + / VO2 + reaction ari quasi-reversible, umurongo wumurongo uterwa na coefficient de diffuzione nagaciro ka α (kugereranya S1).Kubera ko coefficient de diffuzione ihoraho (≈ 4 × 10-6 cm2 / s) 52, itandukaniro mumurongo wumurongo ryerekana indangagaciro zitandukanye za α, bityo rero igipimo cyo kohereza electron hejuru ya electrode, cyerekanwe kuri C76 na HWO -50% C76 Ahantu hahanamye (igipimo kinini cyo kohereza electron).
Imisozi ya Warburg (W) ibarwa kuri radiyo ntoya yerekanwe ku mbonerahamwe ya S3 (Igishusho 6d) ifite agaciro kegereye 1 ku bikoresho byose, byerekana ikwirakwizwa ry’ubwoko bwa redox kandi byemeza imyitwarire y'umurongo wa IP ugereranije na ν1 / 2. CV irapimwa.Kuri HWO-50% C76, umusozi wa Warburg uva kuri 1 ugera kuri 1.32, byerekana ko bitagabanijwe gusa na kimwe cya kabiri kitagira umupaka wa reagent (VO2 +), ariko kandi byerekana uruhare rushoboka rwimyitwarire yoroheje mu myitwarire ikwirakwizwa na electrode.
Kugirango turusheho gusesengura ihinduka (igipimo cyo kohereza electron) ya VO2 + / VO2 + redox reaction, uburyo bwa Nicholson quasi-reversible reaction nabwo bwakoreshejwe kugirango hamenyekane igipimo gisanzwe gihoraho k041.42.Ibi bikorwa hifashishijwe ikigereranyo cya S2 kugirango wubake ibipimo bitagira urugero bya kinetic Ψ, bikaba imikorere ya ΔEp, nkibikorwa bya ν-1/2.Imbonerahamwe S4 yerekana Ψ agaciro kabonetse kuri buri kintu cya electrode.Ibisubizo (Igishusho 6c) byateguwe kugirango ubone k0 × 104 cm / s uhereye kumurongo wa buri kibanza ukoresheje Ikigereranyo S3 (cyanditswe kuruhande rwa buri murongo kandi gitangwa mumeza S4).HWO-50% C76 wasangaga ifite ahantu hahanamye (Igishusho 6c), bityo agaciro ntarengwa k0 ni 2,47 × 10-4 cm / s.Ibi bivuze ko iyi electrode igera kuri kinetics yihuta, ijyanye nibisubizo bya CV na EIS mubishusho 6a na d no mumeza S3.Mubyongeyeho, agaciro ka k0 nako kabonetse mubibanza bya Nyquist (Igishusho 6d) cyo kugereranya S4 ukoresheje agaciro ka RCT (Imbonerahamwe S3).Ibisubizo k0 biva muri EIS byegeranijwe mu mbonerahamwe ya S4 kandi byerekana ko HWO-50% C76 yerekana igipimo kinini cyo kohereza electron kubera ingaruka zifatika.Nubwo k0 indangagaciro zitandukanye bitewe ninkomoko itandukanye ya buri buryo, baracyerekana gahunda imwe yubunini kandi berekana guhuza.
Kugirango usobanukirwe neza kinetics nziza zabonetse, ni ngombwa kugereranya ibikoresho bya electrode nziza hamwe na electrode ya UCC na TCC idafunze.Kubisubizo VO2 + / VO2 +, HWO-C76 ntiyerekanye gusa ΔEp yo hasi kandi ihindagurika neza, ariko kandi yahagaritse cyane reaction ya parasitike ya chlorine ihindagurika ugereranije na TCC, nkuko byapimwe nubu kuri 1.45 V ugereranije na SHE (Ishusho 7a).Mu rwego rwo gutuza, twatekereje ko HWO-50% C76 yari ihagaze neza mumubiri kuko catalizator yavanze na pVDF hanyuma igashyirwa kuri electrode yimyenda ya karubone.HWO-50% C76 yerekanye ihinduka ryinshi rya mV 44 (igipimo cyo guta agaciro 0.29 mV / cycle) nyuma yizunguruka 150 ugereranije na mV 50 kuri UCC (Ishusho 7b).Ibi ntibishobora kuba itandukaniro rinini, ariko kinetics ya UCC electrode iratinda cyane kandi itesha agaciro gusiganwa ku magare, cyane cyane kubisubizo byinyuma.Nubwo guhinduka kwa TCC ari byiza cyane kurenza UCC, wasangaga TCC ifite impinduka nini ya mV 73 nyuma yizunguruka 150, zishobora guterwa na chlorine nyinshi zakozwe hejuru yacyo.kugirango catalizator ifatanye neza hejuru ya electrode.Nkuko bigaragara kuri electrode zose zapimwe, ndetse na electrode idafite catalizator zishyigikiwe zerekanye urwego rutandukanye rw’imidugararo y’amagare, byerekana ko ihinduka ry’itandukanyirizo ry’imisozi mu gihe cyo gusiganwa ku magare riterwa no gukuraho ibikoresho biterwa n’imihindagurikire y’imiti aho gutandukana na catalizator.Byongeye kandi, niba umubare munini wibikoresho bya catalizator byari gutandukana nubuso bwa electrode, ibi byavamo kwiyongera gukomeye gutandukana kwa mpinga (ntabwo ari mV 44 gusa), kubera ko substrate (UCC) idakora cyane kuri reaction ya VO2 + / VO2 + redox.
Kugereranya CV yibikoresho byiza bya electrode ugereranije na UCC (a) hamwe no guhagarara kwa VO2 + / VO2 + redox reaction (b).ν = 5 mV / s kuri CV zose muri 0.1 M VOSO4 / 1 M H2SO4 + 1 M HCl electrolyte.
Kongera ubukungu bushimishije bwa tekinoroji ya VRFB, kwagura no gusobanukirwa kinetics ya vanadium redox reaction ningirakamaro kugirango tugere ku mbaraga nyinshi.Hateguwe HWO-C76 kandi ubushakashatsi bwakozwe ningaruka za electrocatalytic kuri reaction ya VO2 + / VO2 +.HWO yerekanye imbaraga nke za kinetic muri electrolytike ivanze ariko ihagarika cyane ubwihindurize bwa chlorine.Ibipimo bitandukanye bya HWO: C76 byakoreshejwe kugirango turusheho kunoza imikorere ya electrode ya HWO.Kongera C76 kuri HWO bitezimbere uburyo bwo kohereza electronique ya VO2 + / VO2 + reaction kuri electrode yahinduwe, muri yo HWO-50% C76 nibikoresho byiza kuko bigabanya kurwanya ihererekanyabubasha kandi bikarwanya chlorine ugereranije no kubitsa C76 na TCC..Ibi biterwa ningaruka zo guhuza hagati ya C = C sp2 kuvanga, OH na W-OH amatsinda akora.Igipimo cyo kwangirika nyuma yo gusiganwa ku magare inshuro ebyiri HWO-50% C76 byagaragaye ko ari 0.29 mV / cycle, mu gihe igipimo cyo kwangirika kwa UCC na TCC ari 0.33 mV / cycle na 0.49 mV / cycle, bigatuma gihagarara neza.muri aside ivanze ya electrolytike.Ibisubizo byatanzwe byerekana neza ibikoresho bya electrode ikora cyane kuri VO2 + / VO2 + reaction hamwe na kinetics byihuse kandi bihamye.Ibi bizongera ingufu za voltage zisohoka, bityo byongere ingufu za VRFB, bityo bigabanye igiciro cyibicuruzwa bizaza.
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