304 capillary tube Nanocomposite ishingiye kuri Oxide ya Tungsten / Fullerene nka Electrocatalysis na Inhibitor za Parasitike VO2 + / VO2 + Imyitwarire muri Acide ivanze

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Ibyuma bitagira umwanda 304 Coil Tube Ibigize imiti

304 Ibyuma bitagira umuyonga Coil Tube ni ubwoko bwa chromium-nikel alloy.Ukurikije ibyuma bitagira umuyonga 304 Coil Tube Manufacturer, ibyingenzi muri byo ni Cr (17% -19%), na Ni (8% -10.5%).Mu rwego rwo kunoza kurwanya ruswa, hari bike bya Mn (2%) na Si (0,75%).

Ibyuma bitagira umwanda 304 Coil Tube Ibikoresho bya mashini

Ibikoresho bya mashini ya 304 ibyuma bitagira umuyonga ni ibi bikurikira:

• Imbaraga zingana: 15515MPa
• Imbaraga zitanga umusaruro: ≥205MPa
• Kurambura: ≥30%

Porogaramu & Gukoresha Ibyuma bitagira umwanda 304 Coil Tube

Igiciro kiri hejuru ya bateri ya redadium itemba (VRFBs) igabanya imikoreshereze yabyo.Ibikorwa bya electrochemic reaction bigomba kunozwa kugirango hongerwe ubwinshi bwingufu ningufu za VRFB, bityo bigabanye kWh 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 spectroscopy (EDX), imiyoboro ya elegitoronike ikwirakwiza mikorosikopi (HR-TEM), itandukaniro rya X-ray (XRD), X-ray ifoto yerekana amashanyarazi (XPS), infrared Fourier hindura Spectroscopy (FTIR) hamwe no gupima inguni.Byagaragaye ko kwiyongera kwa C76 fullerene kuri HWO bishobora kuzamura kinetics ya electrode kubijyanye na reaction ya VO2 + / VO2 + redox mukongera imbaraga no gutanga amatsinda akora ya ogisijeni hejuru yayo.HWO / C76 ikomatanya (50 wt% C76) byagaragaye ko ari byiza cyane kuri VO2 + / VO2 + hamwe na ΔEp ya mV 176 ugereranije na mV 365 ku mwenda wa karubone utavuwe (UCC).Byongeye kandi, HWO / C76 yibumbiye hamwe yerekanye ko yabujije cyane ubwihindurize bwa parasitike ya chlorine bitewe na matsinda ya W-OH.
Ibikorwa bikomeye byabantu hamwe n’impinduramatwara yihuse mu nganda byatumye amashanyarazi akenera bidasubirwaho amashanyarazi, yiyongera kuri 3% ku mwaka1.Mu myaka ibarirwa muri za mirongo, ikoreshwa ry’ibicanwa by’ibinyabuzima nk’isoko ry’ingufu byatumye imyuka ihumanya ikirere, bituma ubushyuhe bw’isi, amazi n’umwanda bihumanya ikirere, byangiza ibidukikije byose.Kubera iyo mpamvu, mu 2050 umugabane w’ingufu zishobora kongera ingufu n’izuba biteganijwe ko uzagera kuri 75% y’amashanyarazi yose1.Nyamara, iyo ingufu zishobora kongera ingufu zirenga 20% yumusaruro w’amashanyarazi yose, umuyoboro uhinduka udahungabana 1. Iterambere rya sisitemu yo kubika ingufu neza ni ingenzi kuri iyi nzibacyuho, kuko igomba kubika amashanyarazi arenze kandi ikaringaniza itangwa n’ibisabwa.
Muri sisitemu zose zo kubika ingufu nka batiri ya Hybrid vanadium redox itemba2, bateri zose za redox redox (VRFBs) nizo zateye imbere cyane kubera ibyiza byinshi3 kandi bifatwa nkigisubizo cyiza cyo kubika ingufu z'igihe kirekire (~ 30 ans).Gukoresha ingufu zishobora kongera ingufu4.Ibi biterwa no gutandukanya ingufu nubucucike bwingufu, igisubizo cyihuse, kuramba hamwe nigiciro gito cyumwaka kingana na $ 65 / kWt ugereranije na $ 93-140 / kWh kuri Li-ion na bateri ya aside-aside na 279-420 USD / kWt.Batteri ya kilowat.
Nyamara, ubucuruzi bwabo bwamamaye bukomeje kubangamirwa nigiciro kinini cya sisitemu yo hejuru, bitewe ahanini nudupapuro twa batiri4,5.Rero, kunoza imikorere ya bateri mukongera kinetics ya kabiri-selile reaction irashobora kugabanya ingano ya bateri bityo bikagabanya ibiciro.Kubwibyo, kwihuta kwa elegitoronike kwerekanwa hejuru ya electrode birasabwa, bitewe nigishushanyo, imiterere nuburyo imiterere ya electrode, igomba kuba nziza.Nubwo electrode ishingiye kuri karubone ifite imiti ihamye ya chimique na electrochemicique hamwe nu mashanyarazi meza, iyo itavuwe, kinetics yabo izatinda bitewe no kubura amatsinda akora ya ogisijeni na hydrophilicity 7,8.Kubwibyo rero, amashanyarazi atandukanye ahujwe na electrode ya karubone, cyane cyane imyuka ya karubone na oxyde yicyuma, kugirango itezimbere imikorere ya electrode zombi, bityo byongere imbaraga za electrode ya VRFB.
Ibikoresho byinshi bya karubone byakoreshejwe, nk'impapuro za karubone9, carbone nanotubes10,11,12,13, nanostructures ishingiye kuri graphene14,15,16,17, carbone nanofibers18 nibindi 19,20,21,22,23, usibye umuryango wa fullerene .Mu bushakashatsi twabanje kuri C76, twatangaje ku nshuro ya mbere ibikorwa byiza bya electrocatalytic yiyi fullerene yerekeza kuri VO2 + / VO2 +, ugereranije n’imyenda ya karubone itunganijwe kandi itavuwe, kurwanya amafaranga byagabanutseho 99.5% na 97% 24.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, 38 zikoreshwa kubera ubwinshi bw’amazi menshi hamwe na ogisijeni nyinshi.amatsinda.Imbonerahamwe S2 yerekana imikorere ya catalitiki yiyi oxyde yicyuma muri reaction ya VO2 + / VO2 +.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, WO3 yerekanye iterambere rito muri cathode kinetics.Kunoza imikorere ya WO3, ingaruka zo gukoresha tungsten yagabanutse (W18O49) kubikorwa byiza bya electrode byageragejwe38.Hydrated tungsten oxyde (HWO) ntabwo yigeze igeragezwa mubikorwa bya VRFB, nubwo yerekanye ibikorwa byinshi mubisabwa na supercapacitor kubera gukwirakwiza cation byihuse ugereranije na WOx39,40.Igisekuru cya gatatu bateri yose ya vanadium redox ikoresha ikoresha aside ivanze ya electrolyte 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 mubibi byigisekuru cya gatatu, bityo rero gushaka uburyo bwo guhagarika reaction ya chlorine byabaye inshingano zitsinda ryinshi.
Hano, ibizamini bya VO2 + / VO2 + byakorewe kuri compte ya HWO / C76 yashyizwe kuri electrode yimyenda ya karubone kugirango haboneke uburinganire hagati yumuriro wamashanyarazi yibintu hamwe na redox reaction kinetics hejuru ya electrode mugihe cyo guhagarika parasitike ya chlorine.reaction (KVR).Hydrated tungsten oxyde (HWO) nanoparticles yashizwemo nuburyo bworoshye bwa hydrothermal.Ubushakashatsi bwakorewe muri electrolyte ivanze (H2SO4 / HCl) kugirango bigane igisekuru cya gatatu VRFB (G3) kugirango byoroherezwe no gukora iperereza ku ngaruka HWO yagize kuri parasitike ya chlorine ya parasitike42.
Vanadium (IV) sulfate oxyde hydrat (VOSO4, 99,9%, Alfa-Aeser), aside sulfurike (H2SO4), aside hydrochloric (HCl), dimethylformamide (DMF, Sigma-Aldrich), fluoride polyvinylidene (PVDF, Sigma-Aldrich), sodium Tungsten oxyde dihydrate (Na2WO4, 99%, Sigma-Aldrich) hamwe nigitambaro cya hydrophilique karubone ELAT (Ububiko bwa Fuel Cell) yakoreshejwe muri ubu bushakashatsi.
Hydrated tungsten oxyde (HWO) yateguwe na hydrothermal reaction aho g 2 yumunyu wa Na2WO4 yashongeshejwe muri ml 12 ya HO kugeza habonetse igisubizo kitagira ibara, hanyuma ml 12 ya 2 M HCl yongerwaho ibitonyanga kugeza ihagarikwa ryumuhondo ryoroheje yabonetse.guhagarikwa.Amazi ya hydrothermal yakorewe muri Teflon yometseho ibyuma bitagira umuyonga autoclave mu ziko kuri 180 ºC mumasaha 3.Ibisigarira byakusanyirijwe mu kuyungurura, gukaraba inshuro 3 hamwe na Ethanol n'amazi, byumishwa mu ziko kuri 70 ° C kuri ~ 3 h, hanyuma hasi kugirango ubone ifu ya HWO yubururu.
Imyenda ya karubone yabonetse (itavuwe) electrode (CCTs) yakoreshejwe muburyo babonye cyangwa bakorerwa ubushyuhe mu itanura rya tube kuri 450 ° C kuri 10 h ku bushyuhe bwa 15 ° C / min mu kirere kugeza kubona UCC (TCC) ivurwa, s Kimwe nakazi kambere 24. UCC na TCC zaciwe muri electrode hafi cm 1.5 z'ubugari na cm 7 z'uburebure.Ihagarikwa rya C76, HWO, HWO-10% C76, HWO-30% C76 na HWO-50% C76 ryateguwe hongerwaho mg 20 zifu yifu yibikoresho na 10 wt% (~ 2.22 mg) ya PVDF ihuza ~ 1 ml ya DMF yateguye kandi yerekana amasaha 1 kugirango atezimbere uburinganire.Noneho mg 2 za C76, HWO na HWO-C76 zikoreshwa kuri cm 1.5 zumwanya wa UCC ikora electrode.Catalizator zose zashyizwe kuri electrode ya UCC kandi TCC yakoreshejwe mugereranya gusa, kuko akazi kacu kambere kerekanye ko kuvura ubushyuhe bidasabwa 24.Gutanga ibitekerezo byagezweho mugukaraba 100 µl yo guhagarikwa (umutwaro 2 mg) kugirango uburinganire bumwe.Hanyuma electrode zose zumishijwe mu ziko ijoro ryose kuri 60 ° C.Electrode ipimwa mbere na nyuma kugirango yizere neza ko imizigo yuzuye.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.
Umwanya wo gusohora ibyuka bisikana electron microscope (FESEM, Zeiss SEM Ultra 60.5 kV) byakoreshejwe kugirango harebwe morfologiya ya HWO.Gukwirakwiza ingufu za X-ray spectroscopy ifite Feii8SEM (EDX, Zeiss AG) 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 kugirango haboneke amashusho y’ibisubizo bihanitse hamwe nimpeta zo gutandukanya ibice bya HWO.Koresha porogaramu ya Crystallographic Tool Box (CrysTBox) kugirango usesengure impeta zitandukanya HWO ukoresheje imikorere ya ringGUI hanyuma ugereranye ibisubizo na moderi ya XRD.Imiterere no gushushanya UCC na TCC byagenwe 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.(Icyitegererezo 3600).XRD yerekana imiterere ya kristu hamwe nicyiciro cya KABIRI.Porogaramu ya PANalytical X'Pert HighScore yakoreshejwe mu guhuza impinga ya HWO ku ikarita ya tungsten oxyde iboneka muri data base45.Gereranya ibisubizo BIBIRI 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.Ibipimo bya Fourier bihindura infragre ya spekitroscopi (FTIR, hifashishijwe icyiciro cya Perkin Elmer KBr FTIR spectrometer) byakozwe kugirango hamenyekane amatsinda yimikorere ya HWO na HWO-50% C76.Gereranya ibisubizo 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.Tekinoroji zombi zikoresha selile ya electrode eshatu hamwe na electrolyte ya 0.1 M VOSO4 (V4 +) yashonga muri 1 M H2SO4 + 1 M HCl (aside ivanze).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, ibipimo byo gusikana (ν) bya 5, 20, na 50 mV / s byakoreshejwe ku idirishya rishobora kuba (0–1) V ugereranije na SCE kuri VO2 + / VO2 +, hanyuma bikosorwa ku gipimo cya SHE kugirango utegure (VSCE = 0.242 V ugereranije na HSE).Kugira ngo hakorwe iperereza ku kugumya ibikorwa bya electrode, hakozwe CV kuri UCC, TCC, UCC-C76, UCC-HWO na UCC-HWO-50% C76 kuri ν bingana na 5 mV / s.Kubipimo bya EIS kubisubizo bya VO2 + / VO2 + redox, hakoreshejwe intera ya 0.01-105 Hz hamwe na voltage yumuzunguruko ufunguye (OCV) ihungabana rya 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 buke 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 = γ = 90 °), bihuye n'ibara ryacyo ry'ubururu bigaragara (Ishusho 1b) 48,49.Izindi mpinga zigera kuri 20.5 °, 27.1 °, 28.1 °, 30.8 °, 35.7 °, 36.7 ° na 52.7 ° ziri kuri (140), (620), (350), (720), (740), (560).na (970) indege zitandukanya, 49, orthorhombic WO2.63.Songara n'abandi.43 yakoresheje uburyo bumwe bwogukora kugirango abone ibicuruzwa byera, byatewe no kuba WO3 (H2O) 0.333.Nyamara, muriyi mirimo, kubera ibihe bitandukanye, habonetse ibicuruzwa byubururu-imvi, byerekana kubana kwa WO3 (H2O) 0.333 (PDF 087-1203, a = 7.3 Å, b = 12.5 Å, c = 7.7) muri Å , α = β = γ = 90 °) hamwe nuburyo bwagabanutse bwa tungsten oxyde.Isesengura ryibihe hamwe na 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 ya XPS yerekanwe kurwego rwa nucleus, amashusho ya TEM, FTIR yerekanwe na Raman yerekanwe ya C76 ibice byerekanwe mubipapuro byabanjirije 24.Dukurikije Kawada et 50.51, uburyo bwo gutandukanya X-ray ya C76 bwerekana imiterere ya monoclinic ya FCC nyuma yo gukuraho toluene.
SEM amashusho mugitabo.2a na b byerekana gushira neza HWO na HWO-50% C76 no hagati ya fibre ya karubone ya electrode ya UCC.Ikarita yibanze ya tungsten, karubone na ogisijeni mu ishusho ya SEM ku gishushanyo cya 2c irerekanwa mu mbuto.2d - f yerekana ko tungsten na karubone bivanze kimwe (byerekana isaranganya risa) hejuru ya electrode kandi ikomatanya ntiribikwa neza.kubera imiterere yuburyo bwimvura.
SEM amashusho yabitswe HWO (a) na HWO-C76 ibice (b).Ikarita ya EDX yashyizwe kuri HWO-C76 muri 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 mu gishushanyo cya 3b.Mugukuza nanocube kugirango itandukane ahantu hatoranijwe, imiterere yo gusya hamwe nindege zitandukanya zujuje amategeko ya Bragg birashobora kugaragara nkuko bigaragara ku gishushanyo cya 3c, byemeza ko ibintu bitagaragara.Mu gushiramo ku gishushanyo cya 3c yerekana intera d 3.3 Å ihuye nindege ya (022) na (620) itandukanya indege ya WO3 (H2O) 0.333 na W32O84, 43, 44, 49.Ibi bihuye nisesengura rya XRD ryavuzwe haruguru (Igishusho 1b) kuva intera yagaragaye yindege 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 muburyo bwimpeta ihuye nimpinga ya mbere yagaragaye muburyo bwa x-ray yindege ya (022) cyangwa (620) itandukanya indege.Kuva (022) kugeza kuri (402) impeta, d-intera ya 3.30, 3.17, 2.38, 1.93, na 1.69 Å yabonetse, ibyo bikaba bihuye nagaciro ka XRD ka 3.30, 3.17, 2 .45, 1.93 na 1.66.Å, 44, 45.
(a) Ishusho ya HR-TEM ya HWO, (b) yerekana ishusho nini.Amashusho yindege yo gusya yerekanwa muri (c), hanyuma inset (c) yerekana ishusho nini yindege nintera d 0.33 nm ihuye nindege (002) na (620).(d) Impeta ya KABIRI yerekana 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).Ikirangantego cyagutse cya XPS scan ya synthesize HWO irerekanwa mumashusho.S1, byerekana ko tungsten ihari.XPS ifunguye-scan yerekana urwego nyamukuru W 4f na O 1s rwerekanwe mubishushanyo.4a na b.Ikirangantego cya W 4f kigabanyijemo ibice bibiri bya spin-orbit bikwiranye ningufu zihuza leta ya okiside W. Impinga W 4f5 / 2 na W 4f7 / 2 ku mbaraga zihuza 37.8 na 35.6 eV ni W6 +, naho impinga W 4f5 / 2 na W 4f7 / 2 kuri 36.6 na 34.9 eV biranga leta ya W4 +.Kubaho kwa okiside (W4 +) birashimangira kandi ko hashyizweho WO2.63 itari stoichiometric, naho kuba W6 + byerekana stoichiometric WO3 kubera WO3 (H2O) 0.333.Amakuru yashyizwe ahagaragara yerekanaga ko ijanisha rya atome rya W6 + na W4 + ryari 85% na 15%, ibyo bikaba byari hafi yindangagaciro zagereranijwe kuva muri XRD, ukurikije itandukaniro riri hagati yikoranabuhanga ryombi.Ubwo buryo bwombi butanga amakuru yuzuye hamwe nukuri, cyane cyane XRD.Mubyongeyeho, uburyo bubiri busesengura ibice bitandukanye byibikoresho kuko XRD nuburyo bwinshi mugihe XPS nuburyo bwubuso bwegera nanometero nkeya.Ikirangantego cya O 1s kigabanyijemo 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.
Isesengura rya FTIR naryo ryakozwe kuri izi ngero zombi kugira ngo harebwe niba hari amatsinda akora hamwe na molekile y'amazi ihujwe mu miterere ya HWO.Ibisubizo byerekana ko icyitegererezo cya HWO-50% C76 hamwe n ibisubizo bya FT-IR HWO bisa nkaho HWO ihari, ariko ubukana bwimpinga buratandukanye bitewe nubwoko butandukanye bw'icyitegererezo bwakoreshejwe mugihe cyo kwitegura gusesengura (Ishusho 5a ).HWO-50% C76 Impinga zose za fullerene 24 zerekanwe usibye impinga ya tungsten.Ibisobanuro birambuye.5a yerekana ko ingero zombi zigaragaza umurongo mugari cyane kuri ~ 710 / cm, biterwa na OWO irambuye ihindagurika mu miterere ya HWO, hamwe nigitugu gikomeye kuri ~ 840 / cm, bitirirwa WO.umurongo utyaye kuri ~ 1610 / cm ujyanye no kunyeganyega kwa OH, kandi umurongo mugari wa ~ 3400 / cm ujyanye no kunyeganyega kurambuye kwa OH mumatsinda ya hydroxyl43.Ibisubizo birahuye na XPS igaragara ku gishushanyo cya 4b, aho itsinda rya WO rishobora gutanga imbuga zikora kuri VO2 + / VO2 + reaction.
FTIR isesengura HWO na HWO-50% C76 (a) yerekana amatsinda akora hamwe no gupima inguni (b, c).
Itsinda rya OH rishobora kandi guhagarika VO2 + / VO2 +, bityo bikongerera hydrophilique ya electrode, bityo bigatuma ikwirakwizwa ryikwirakwizwa rya elegitoronike.Icyitegererezo cya HWO-50% C76 cyerekana impinga ya C76 yinyongera nkuko bigaragara ku gishushanyo.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, gupima inguni yakoreshejwe nkuko bigaragara ku gishushanyo cya 5b, c.HWO electrode ihita ikurura 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 yatose rwose mugihe kitarenze umunota.Ibipimo bya wettability bihuye nibisubizo bya XPS na FTIR, byerekana ko amatsinda menshi ya OH hejuru yubuso bwa HWO atuma ugereranije hydrophilique.
VO2 + / VO2 + reaction ya HWO na HWO-C76 nanocomposite yapimwe kandi byari byitezwe ko HWO izahagarika ihindagurika rya gaze ya chlorine ibaho mugihe cya VO2 + / VO2 + reaction muri acide ivanze, mugihe C76 yakomeza guhagarika VO2 + / VO2 +.Ihagarikwa rya HWO ririmo 10%, 30% na 50% C76 ryakoreshejwe kuri electrode ya UCC ifite umutwaro wose wa mg / cm2.
Nkuko bigaragara ku gishushanyo.6, kinetics ya reaction ya VO2 + / VO2 + hejuru ya electrode yasuzumwe hifashishijwe CV muri electrolytike ivanze.Inzira zerekanwa nka I / Ipa kugirango byorohereze kugereranya ΔEp na Ipa / Ipc.Catalizaires zitandukanye ziboneka biturutse kumashusho.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, urwego rugizwe neza na HWO na C76 rugomba kugira ibikorwa byiza nubushobozi buhanitse bwo kubuza chlorine reaction.Byagaragaye ko nyuma yo kongera ibirimo C76, ibikorwa byamashanyarazi ya electrode byateye imbere, nkuko bigaragazwa no kugabanuka kwa ΔEp no kwiyongera kwa Ipa / Ipc (Imbonerahamwe S3).Ibi byashimangiwe kandi n’agaciro ka RCT yakuwe mu kibanza cya Nyquist ku gishushanyo cya 6d (imbonerahamwe S3), aho byagaragaye ko indangagaciro za RCT zagabanutse hamwe n’ibirimo C76.Ibisubizo kandi bihuye nubushakashatsi bwa Lee aho kongeramo karubone ya mesoporous kuri mesoporous WO3 byateje imbere uburyo bwo kohereza amafaranga kuri VO2 + / VO2 + 35.Ibi birerekana ko reaction nziza ishobora guterwa cyane nubushobozi bwa electrode (C = C bond) 18,24,35,36,37.Bitewe nimpinduka yo guhuza geometrie hagati ya [VO (H2O) 5] 2+ na [VO2 (H2O) 4] +, C76 irashobora kandi kugabanya igisubizo kirenze mukugabanya ingufu za tissue.Ariko, ibi ntibishoboka hamwe na HWO electrode.
.(b) Randles-Sevchik na (c) Uburyo bwa Nicholson VO2 + / VO2 + bwo kugereranya 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 guhagarika ihindagurika rya gaze ya chlorine ugereranije na C76, nkuko bigaragara ku gishushanyo.6a, usibye kwerekana uruziga ruto muri fig.6g (RCT yo hepfo).C.Imikorere myiza ya HWO-50% C76 iterwa no gukorana hagati ya C76 itwara nabi cyane hamwe nubushuhe bwinshi hamwe na catalitiki ya W-OH kuri HWO.Mugihe imyuka mike ya chlorine izamura imikorere yumuriro wa selile yuzuye, kinetics nziza izamura imikorere ya voltage yuzuye.
Ukurikije ikigereranyo cya S1, kubijyanye na reaction ya quasi-reversible (ugereranije itinda rya elegitoronike yoherejwe) igenzurwa no gukwirakwizwa, impinga ya IP (IP) iterwa numubare wa electron (n), agace ka electrode (A), coefficient de diffuzione (D), umubare ya electroni yohereza coefficient (α) n'umuvuduko wo gusikana (ν).Kugirango twige imyitwarire yagenzuwe ikwirakwizwa ryibikoresho byapimwe, umubano hagati ya IP na ν1 / 2 wateguwe kandi werekanwa 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).Bitewe na coefficient ihoraho ikwirakwizwa (≈ 4 × 10-6 cm2 / s) 52, itandukaniro kumurongo kumurongo ryerekana indangagaciro zitandukanye za α bityo rero ibiciro bitandukanye byo kohereza electron kuri electrode hejuru, hamwe na C76 na HWO -50 % C76, yerekana ahantu hahanamye cyane (igipimo kinini cyo kohereza electron).
Ibiharuro bito byabazwe bya Warburg (W) byerekanwe kumeza S3 (Igishusho 6d) bifite agaciro kegereye 1 kubikoresho byose, byerekana ikwirakwizwa ryuzuye rya redox kandi byemeza imyitwarire yumurongo wa IP na ν1 / 2 kuri CV.ibipimo.Kuri HWO-50% C76, umusozi wa Warburg uva mubumwe ugera kuri 1.32, byerekana uruhare rutatanzwe gusa no gukwirakwiza igice cya kabiri kitagira ingano (VO2 +), ariko nanone birashoboka ko imyitwarire yoroheje muburyo bwo gukwirakwiza bitewe 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 mugutegura ibipimo bitagira urugero bya kinetic Ψ nkibikorwa bya ΔEp nkigikorwa cya ν - 1/2 ukoresheje ikigereranyo cya S2.Imbonerahamwe S4 yerekana ibisubizo Ψ agaciro kuri buri kintu cya electrode.Tegura ibisubizo (Igishusho 6c) kugirango ubone k0 × 104 cm / s (byanditswe kuruhande rwa buri murongo kandi byerekanwe kumeza S4) ukoresheje ikigereranyo S3 kumurongo wa buri kibanza.HWO-50% C76 wasangaga ifite ahantu hahanamye cyane (Igishusho 6c) bityo rero k0 yo hejuru ya 2,47 × 10-4 cm / s.Ibi bivuze ko iyi electrode itanga kinetics yihuse ijyanye na CV na EIS ibisubizo mubishushanyo 6a na d na Imbonerahamwe S3.Mubyongeyeho, indangagaciro za k0 nazo zabonetse mubibanza bya Nyquist (Igishusho 6d) cyo kugereranya S4 ukoresheje indangagaciro za 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 agaciro ka k0 gatandukanye bitewe ninkomoko itandukanye ya buri buryo, iracyerekana gahunda imwe yubunini kandi yerekana guhuzagurika.
Kugirango usobanukirwe neza kinetics nziza ishobora kugerwaho, ni ngombwa kugereranya ibikoresho byiza bya electrode nziza hamwe na electrode ya UCC na TCC.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 byagaragajwe nigabanuka rikabije kuri 1.45 V ugereranije no kubona OHA (Ishusho. 7a).Kubijyanye no gutuza, twatekereje ko HWO-50% C76 ihagaze neza mumubiri kuko catalizator yavanze na pVDF hanyuma igashyirwa kuri electrode yigitambara.Ugereranije na mV 50 kuri UCC, HWO-50% C76 yerekanye ihinduka ryinshi rya mV 44 nyuma yizunguruka 150 (igipimo cyo guta agaciro 0.29 mV / cycle) (Ishusho 7b).Ntabwo bishobora kuba itandukaniro rinini, ariko kinetics ya UCC electrode iratinda cyane kandi itesha agaciro gusiganwa ku magare, cyane cyane kubitekerezo byinyuma.Nubwo guhindurwa kwa TCC ari byiza cyane kurenza UCC, wasangaga TCC ifite impinduka nini ya mV 73 nyuma yizunguruka 150, zishobora guterwa na chlorine nyinshi zasohotse hejuru yacyo.Kugirango umenye neza ko cataliste ikomera neza kuri electrode.Nkuko bigaragara kuri electrode zose zapimwe, ndetse nabatagira catalizator zishyigikiwe bagaragaza urwego rutandukanye rwumutekano muke wo gusiganwa ku magare, byerekana ko impinduka zo gutandukana kwimpinga mugihe cyamagare ziterwa no guta ibikoresho bitewe nimpinduka za chimique aho gutandukana na catalizator.Na none, niba umubare munini wibikoresho bya catalizator byari gutandukana nubuso bwa electrode, ibi byatuma habaho kwiyongera gukomeye kwimiterere yimisozi (ntabwo ari mV 44 gusa), kubera ko substrate (UCC) idakora kuri VO2 + / VO2 + redox reaction.
Kugereranya CV (a) hamwe no gutuza kwa redox reaction VO2 + / VO2 + (b) yibikoresho byiza bya electrode bijyanye na CCC.Muri electrolyte 0.1 M VOSO4 / 1 M H2SO4 + 1 M HCl, CV zose zingana na ν = 5 mV / s.
Kongera ubukungu bushimishije bwa tekinoroji ya VRFB, kunoza 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 ariko yahagaritse cyane ubwihindurize bwa chlorine muri electrolytike ivanze.Ibipimo bitandukanye bya HWO: C76 byakoreshejwe kugirango turusheho kunoza imikorere ya electrode ya HWO.Kongera ibiri muri C76 kuri HWO birashobora kunoza uburyo bwo kohereza electronique ya reaction ya VO2 + / VO2 + kuri electrode yahinduwe, muribo HWO-50% C76 nibikoresho byiza kuko igabanya ubukana bwo kohereza amafaranga kandi bikarwanya ihindagurika rya gaze ya chlorine ugereranije C76.na TCC bararekuwe.Ibi byatewe ningaruka zo guhuza hagati ya C = C sp2 kuvanga, OH na W-OH amatsinda akora.Igipimo cyo kwangirika kwa HWO-50% C76 wasangaga 0.29mV / cycle munsi yamagare menshi mugihe UCC na TCC ari 0.33mV / cycle na 0.49mV / cycle, bigatuma bihagarara neza muri electrolytike ivanze.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 bizamura ingufu za VRFB, bityo bigabanye ibiciro byubucuruzi bwayo.
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