ʻO 304 mau pahu capillary Nanocomposites Ma muli o Tungsten Oxide / Fullerene ma ke ʻano he Electrocatalysts a me nā Inhibitors o Parasitic VO2 + / VO2 + Reactions i loko o nā Acids Mixed.

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Kūleʻa kila 304 Coil Tube Chemical Composition

ʻO 304 Stainless Steel Coil Tube kahi ʻano o ka austenitic chromium-nickel alloy.E like me ka mea hao hao 304 Coil Tube Manufacturer, ka mea nui i loko o ia mea Cr (17% -19%), a me Ni (8% -10.5%).I mea e hoʻomaikaʻi ai i kona kūʻē ʻana i ka corrosion, aia nā mea liʻiliʻi o Mn (2%) a me Si (0.75%).

Kuhili 'ole 304 Coil Tube Mechanical Pono

ʻO nā waiwai mechanical o 304 stainless steel coil tube penei:

• Ka ikaika tensile: ≥515MPa
• Ka ikaika hana: ≥205MPa
• Elongation: ≥30%

Nā noi a me ka hoʻohana ʻana i ka paipu kuhili ʻole 304 Coil

ʻO ke kumu kūʻai kiʻekiʻe o ka vanadium redox flow batteries (VRFBs) e kaupalena i kā lākou hoʻohana ākea.Pono e hoʻomaikaʻi ʻia nā kinetics o nā hopena electrochemical i mea e hoʻonui ai i ka nui o ka mana a me ka pono o ka ikehu o ka VRFB, a laila e hōʻemi i ke kumukūʻai kWh o ka VRFB.Ma keia hana, hydrothermally synthesized hydrated tungsten oxide (HWO) nanoparticles, C76 a me C76/HWO, ua waiho ma ka kalapona lole electrodes a ho'āʻo e like me electrocatalysts no ka VO2+/VO2+ redox reaction.ʻO ka microscopy electron scanning field emission scanning electron microscopy (FESEM), ikehu dispersive X-ray spectroscopy (EDX), kiʻekiʻe-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), infrared Fourier hoʻololi i ka Spectroscopy (FTIR) a me nā ana kihi pili.Ua ʻike ʻia ʻo ka hoʻohui ʻana o C76 fullerene i ka HWO hiki ke hoʻonui i nā kinetics o ka electrode e pili ana i ka hopena redox VO2 + / VO2 + ma o ka hoʻonui ʻana i ka conductivity a me ka hāʻawi ʻana i nā hui hana o ka oxygen ma luna o kona ʻili.ʻO ka HWO/C76 composite (50 wt% C76) ka mea kūpono loa no ka hopena VO2+/VO2+ me ΔEp o 176 mV i hoʻohālikelike ʻia me 365 mV no ka lole kalapona i mālama ʻole ʻia (UCC).Eia kekahi, ua hōʻike ka HWO/C76 composite i ka pale nui ʻana i ka hopena chlorine evolution parasitic ma muli o nā hui hana W-OH.
ʻO ka hana ikaika o ke kanaka a me ka wikiwiki o ka ʻenehana i alakaʻi i kahi koi kiʻekiʻe loa no ka uila, e ulu ana ma kahi o 3% i kēlā me kēia makahiki1.No nā makahiki he nui, ʻo ka hoʻohana nui ʻana i nā wahie mōʻalihaku ma ke ʻano he kumu o ka ikehu, ua alakaʻi i ka hoʻokuʻu ʻana i ke kinoea hoʻomehana honua, e alakaʻi ana i ka hoʻomehana honua, ka wai a me ka haumia o ka ea, e hoʻoweliweli ana i nā kaiaola holoʻokoʻa.ʻO ka hopena, ma ka makahiki 2050, manaʻo ʻia ka māhele o ka ikehu maʻemaʻe hou a me ka ikehu lā e hiki i 75% o ka nui o ka uila1.Eia nō naʻe, ke ʻoi aku ka nui o ka ikehu hou ma mua o 20% o ka nui o ka hana ʻana o ka uila, ʻaʻole paʻa ka pahu 1. He mea koʻikoʻi ka hoʻomohala ʻana i nā ʻōnaehana mālama ikehu maikaʻi i kēia hoʻololi, no ka mea, pono lākou e mālama i ka uila nui a me ke kaulike o ka lako a me ke koi.
Ma waena o nā ʻōnaehana mālama ikehu a pau e like me ka hybrid vanadium redox flow batteries2, ʻo nā vanadium redox flow batteries (VRFBs) ka mea kiʻekiʻe loa ma muli o ko lākou mau pono he nui3 a ua manaʻo ʻia ʻo ia ka hopena maikaʻi loa no ka mālama ʻana i ka ikehu lōʻihi (~30 makahiki).Hoʻohana i nā kumu ikehu hou4.ʻO kēia ma muli o ka hoʻokaʻawale ʻana o ka mana a me ka ikaika o ka ikehu, ka pane wikiwiki, ke ola lōʻihi a me nā kumukūʻai haʻahaʻa haʻahaʻa o $ 65 / kWh i hoʻohālikelike ʻia me $ 93-140 / kWh no nā pā Li-ion a me ke alakaʻi-acid a me 279-420 USD / kWh./kWh mau ʻokoʻa 4.
Eia nō naʻe, hoʻomau ʻia kā lākou hoʻolaha pāʻoihana e ka nui o nā kumukūʻai ʻōnaehana kiʻekiʻe, ʻoi loa ma muli o nā pā pākaukau4,5.No laila, ʻo ka hoʻomaikaʻi ʻana i ka hana pākaukau ma o ka hoʻonui ʻana i nā kinetics o ʻelua mau hopena hapalua-cell hiki ke hōʻemi i ka nui o ka pākaukau a pēlā e hoʻemi ai i ke kumukūʻai.No laila, koi ʻia ka hoʻololi ʻana o ka electron wikiwiki i ka ʻili electrode, ma muli o ka hoʻolālā, haku a me ke ʻano o ka electrode, pono e hoʻopaʻa pono ʻia.ʻOiai ʻo nā electrodes e pili ana i ke kalapona he mau kemika maikaʻi a me ke kūpaʻa electrochemical a me ka conductivity uila maikaʻi, inā haʻalele ʻole ʻia, e lohi kā lākou kinetics ma muli o ka nele o nā hui hana oxygen a me ka hydrophilicity7,8.No laila, hui pū ʻia nā electrocatalysts like ʻole me nā electrodes kalapona, ʻoi aku ka nui o nā nanostructures carbon a me nā oxides metala, e hoʻomaikaʻi i nā kinetics o nā electrodes ʻelua, e hoʻonui ai i nā kinetics o nā electrodes VRFB.
Nui nā mea kalapona i hoʻohana ʻia, e like me carbon paper9, carbon nanotubes10,11,12,13, graphene-based nanostructures14,15,16,17, carbon nanofibers18 and others19,20,21,22,23, koe wale no ka ʻohana fullerene .Ma kā mākou aʻo mua ma C76, ua hōʻike mākou no ka manawa mua i ka hana electrocatalytic maikaʻi loa o kēia fullerene i ka VO2 + / VO2 +, i hoʻohālikelike ʻia me ka lole kalapona i mālama ʻia me ka hoʻomaʻamaʻa ʻole ʻia, ua hoʻemi ʻia ke kūʻē o ka hoʻoili kālā e 99.5% a me 97%24.Hōʻike ʻia ka hana catalytic o nā mea kalapona no ka hopena VO2+/VO2+ i hoʻohālikelike ʻia me C76 ma ka Papa S1.Ma ka lima 'ē aʻe, he nui metala oxides e like me CeO225, ZrO226, MoO327, NiO28, SnO229, Cr2O330 a me WO331, 32, 33, 34, 35, 36, 37, 38 ua hoʻohana 'ia ma muli o ko lakou mahuahua wettability a me ka oxygen kiʻekiʻe.pūʻulu.Hōʻike ka papa S2 i ka hana catalytic o kēia mau ʻokikene metala ma ka hopena VO2+/VO2+.Ua hoʻohana ʻia ʻo WO3 i kahi helu nui o nā hana ma muli o kāna kumu kūʻai haʻahaʻa, kūpaʻa kiʻekiʻe i ka media acidic, a me ka hana catalytic kiʻekiʻe31,32,33,34,35,36,37,38.Eia naʻe, ua hōʻike ʻo WO3 i ka hoʻomaikaʻi liʻiliʻi o nā kinetics cathode.No ka hoʻomaikaʻi ʻana i ka conductivity o WO3, ua hoʻāʻo ʻia ka hopena o ka hoʻohana ʻana i ka tungsten oxide (W18O49) ma ka hana electrode maikaʻi.ʻAʻole i hoʻāʻo ʻia ka Hydrated tungsten oxide (HWO) i nā noi VRFB, ʻoiai ua hōʻike ʻo ia i ka hana kiʻekiʻe ma nā noi supercapacitor ma muli o ka wikiwiki o ka cation diffusion i hoʻohālikelike ʻia me WOx39,40 anhydrous.Ke hoʻohana nei ke kolu o ka hanauna all-vanadium redox flow battery i ka hui ʻana o ka waikawa electrolyte i haku ʻia me HCl a me H2SO4 e hoʻomaikaʻi i ka hana pākaukau a hoʻomaikaʻi i ka solubility a me ka paʻa o nā ion vanadium i ka electrolyte.Eia naʻe, ua lilo ka hopena o ka chlorine evolution i kekahi o nā hemahema o ke kolu o ka hanauna, no laila, ʻo ka ʻimi ʻana i nā ala e hoʻopau ai i ka pane loiloi chlorine ua lilo ia i hana o kekahi mau hui noiʻi.
Maʻaneʻi, ua hoʻokō ʻia nā hoʻokolohua VO2 +/VO2+ ma ka HWO/C76 composites i waiho ʻia ma luna o nā electrodes lole kalapona i mea e ʻike ai i ke kaulike ma waena o ka conductivity uila o nā composites a me nā kinetics reaction redox ma ka ʻili electrode me ka hoʻopaʻa ʻana i ka waiho ʻana o ka chlorine parasitic.pane (KVR).Ua hoʻohui ʻia nā nanoparticles tungsten oxide (HWO) i kahi ʻano hydrothermal maʻalahi.Ua hoʻokō ʻia nā hoʻokolohua i loko o kahi electrolyte waikawa hui pū ʻia (H2SO4/HCl) e hoʻohālike i ke kolu o ka hanauna VRFB (G3) no ka maʻalahi a me ka noiʻi ʻana i ka hopena o ka HWO ma ka 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 Ua hoʻohana ʻia ka Tungsten oxide dihydrate (Na2WO4, 99%, Sigma-Aldrich) a me ka hydrophilic carbon cloth ELAT (Fuel Cell Store) i kēia haʻawina.
Hoʻomākaukau ʻia ka tungsten oxide (HWO) i hoʻomākaukau ʻia e ka hopena hydrothermal kahi i hoʻoheheʻe ʻia ai ka 2 g o ka paʻakai Na2WO4 i 12 ml o H O a hiki i ka loaʻa ʻana o kahi hopena kala ʻole, a laila ua hoʻohui ʻia he 12 ml o 2 M HCl i ka dropwise a hiki i ka hoʻokuʻu ʻana i ka melemele māmā. ua loaa.hoʻopaneʻe.Ua lawe ʻia ka hopena hydrothermal i loko o kahi autoclave kila kila i uhi ʻia ʻo Teflon i loko o ka umu ma 180 ºC no 3 mau hola.ʻO ke koena i hōʻiliʻili ʻia e ka kānana, holoi ʻia i 3 mau manawa me ka ethanol a me ka wai, maloʻo i loko o ka umu ma 70 ° C no ~3 h, a laila e hoʻoheheʻe ʻia e loaʻa i ka pauka HWO polū-hina.
Ua hoʻohana ʻia nā electrodes kalapona kalapona (CCTs) i loaʻa ʻole i ke ʻano i loaʻa ai a i ʻole i hoʻopaʻa ʻia i ka mālama wela i loko o ka umu pahu ma 450 ° C no 10 mau hola ma kahi helu hoʻomehana o 15 ° C / min i ka ea. loaʻa i mālama ʻia ka UCC (TCC), s Like me ka hana mua 24. Ua ʻoki ʻia ʻo UCC a me TCC i nā electrodes ma kahi o 1.5 cm ākea a me 7 cm lōʻihi.Ua hoʻomākaukau ʻia nā hoʻomaha o C76, HWO, HWO-10% C76, HWO-30% C76 a me HWO-50% C76 ma ka hoʻohui ʻana i 20 mg o ka pauka mea ikaika a me 10 wt% (~ 2.22 mg) o PVDF binder i ~1 ml o DMF hoomakaukau i loko o a sonicated no 1 hola e hoʻomaikaʻi uniformity.A laila ua hoʻopili ʻia ka 2 mg o C76, HWO a me HWO-C76 composites ma kahi o 1.5 cm2 o ka UCC active electrode area.Ua hoʻoili ʻia nā catalysts a pau ma luna o nā electrodes UCC a ua hoʻohana ʻia ʻo TCC no nā kumu hoʻohālikelike wale nō, no ka mea, ua hōʻike kā mākou hana mua ʻaʻole koi ʻia ka mālama wela 24 .Ua hoʻokō ʻia ka hoʻonā manaʻo ma ka palaki ʻana i ka 100 µl o ka hoʻokuʻu ʻia (hoʻouka 2 mg) no ka ʻoi aku o ka lokahi.A laila ua maloʻo nā electrodes a pau i ka umu i ka pō ma 60 ° C.Ana ʻia nā electrodes ma mua a ma hope e hōʻoia i ka hoʻouka ʻana i nā waihona.I mea e loaʻa ai kahi ʻāpana geometric (~ 1.5 cm2) a pale i ka piʻi ʻana o ka vanadium electrolyte i nā electrodes ma muli o ka hopena capillary, ua hoʻopili ʻia kahi ʻāpana lahilahi o ka paraffin ma luna o ka mea hana.
Ua hoʻohana ʻia kahi microscope electron scanning field emission scanning (FESEM, Zeiss SEM Ultra 60.5 kV) no ka nānā ʻana i ka morphology surface HWO.Ua hoʻohana ʻia ka ikehu dispersive X-ray spectroscopy me Feii8SEM (EDX, Zeiss AG) no ka palapala ʻana i nā mea HWO-50%C76 ma nā electrodes UCC.Ua hoʻohana ʻia kahi microscope electron transmission hoʻonā kiʻekiʻe (HR-TEM, JOEL JEM-2100) e hana ana ma kahi voli wikiwiki o 200 kV no ka loaʻa ʻana o nā kiʻi hoʻonā kiʻekiʻe a me nā apo diffraction o nā ʻāpana HWO.E hoʻohana i ka lako polokalamu Crystallographic Tool Box (CrysTBox) e kālailai i nā apo diffraction HWO me ka hoʻohana ʻana i ka hana ringGUI a hoʻohālikelike i nā hopena me nā hiʻohiʻona XRD.Ua hoʻoholo ʻia ka hoʻolālā a me ka graphitization o UCC a me TCC e ka X-ray diffraction (XRD) ma ka helu scan o 2.4 ° / min mai 5 ° a i 70 ° me Cu Kα (λ = 1.54060 Å) me ka hoʻohana ʻana i ka Panalytical X-ray diffractometer.(Kōkohu 3600).Hōʻike ʻo XRD i ke ʻano aniani a me nā pae o HWO.Ua hoʻohana ʻia ka polokalamu PANalytical X'Pert HighScore e hoʻohālikelike i nā piko o ka HWO i nā palapala ʻāina tungsten oxide i loaʻa ma ka waihona45.Hoʻohālikelike i nā hopena HWO me nā hopena TEM.Ua hoʻoholo ʻia ke ʻano kemika a me ke kūlana o nā laʻana HWO e ka X-ray photoelectron spectroscopy (XPS, ESCALAB 250Xi, ThermoScientific).Ua hoʻohana ʻia ka polokalamu CASA-XPS (v 2.3.15) no ka deconvolution kiʻekiʻe a me ka ʻikepili ʻikepili.Ua hana ʻia nā ana ʻana o ka Fourier transform infrared spectroscopy (FTIR, me ka Perkin Elmer class KBr FTIR spectrometer) no ka hoʻoholo ʻana i nā pūʻulu hana ili o HWO a me HWO-50%C76.Hoʻohālikelike i nā hopena me nā hopena XPS.Ua hoʻohana pū ʻia nā ana kihi pili (KRUSS DSA25) e ʻike i ka pulu o nā electrodes.
No nā ana electrochemical a pau, ua hoʻohana ʻia kahi hale hana Biologic SP 300.Ua hoʻohana ʻia ka cyclic voltammetry (CV) a me ka electrochemical impedance spectroscopy (EIS) e aʻo i ka electrode kinetics o ka VO2 +/VO2+ redox reaction a me ka hopena o ka reagent diffusion (VOSO4 (VO2+)) ma ka helu pane.Hoʻohana ʻia nā ʻenehana ʻelua i kahi kelepona ʻekolu-electrode me kahi ʻano electrolyte o 0.1 M VOSO4 (V4+) i hoʻoheheʻe ʻia ma 1 M H2SO4 + 1 M HCl (mixed acid).Hoʻoponopono ʻia nā ʻikepili electrochemical a pau i hōʻike ʻia.Ua hoʻohana ʻia ka saturated calomel electrode (SCE) a me ka platinum (Pt) coil ma ke ʻano he reference a counter electrode.No ka CV, ua hoʻohana ʻia nā helu scan (ν) o 5, 20, a me 50 mV/s i ka puka aniani hiki ke hoʻohālikelike ʻia me SCE no VO2+/VO2+, a laila hoʻoponopono ʻia ma ka pālākiō SHE e hoʻolālā (VSCE = 0.242 V pili iā HSE) .No ka noiʻi ʻana i ka paʻa ʻana o ka hana electrode, ua hana ʻia kahi CV recycle ma UCC, TCC, UCC-C76, UCC-HWO a me UCC-HWO-50% C76 ma ν like me 5 mV/s.No nā ana EIS no ka hopena redox VO2+/VO2+, ua hoʻohana ʻia kahi alapine o ka 0.01-105 Hz a me ka haʻalulu hāmama (OCV) o 10 mV.Ua hana hou ʻia kēlā me kēia hoʻokolohua 2-3 mau manawa e hōʻoia i ka kūlike o nā hopena.Ua loaʻa nā mea hoʻomau heterogeneous rate (k0) e ke ala Nicholson46,47.
Ua hoʻohui maikaʻi ʻia ʻo Hydrated tungsten oxide (HVO) e ke ʻano hydrothermal.Kiʻi SEM ma ka fig.Hōʻike ka 1a i ka HWO i waiho ʻia he mau pūʻulu o nā nanoparticles me ka nui o nā ʻāpana i ka laulā o 25-50 nm.
Hōʻike ke kumu hoʻohālikelike X-ray o HWO i nā piko (001) a me (002) ma ~23.5° a me ~47.5°, kēlā me kēia, he ʻano ia o nonstoichiometric WO2.63 (W32O84) (PDF 077–0810, a = 21.4 Å, b = 17.8 Å, c = 3.8 Å, α = β = γ = 90°), e pili ana i kona kala polū (Fig. 1b)48,49.Aia nā piko ʻē aʻe ma kahi o 20.5°, 27.1°, 28.1°, 30.8°, 35.7°, 36.7° a me 52.7° aia ma (140), (620), (350 ), (720), (740), (560).a me (970) nā mokulele ʻokoʻa, 49 orthorhombic WO2.63.Songara et al.Ua hoʻohana ʻo 43 i ke ʻano hana like ʻole no ka loaʻa ʻana o kahi huahana keʻokeʻo, i hoʻopili ʻia i ka loaʻa ʻana o WO3(H2O)0.333.Eia naʻe, ma kēia hana, ma muli o nā kūlana like ʻole, ua loaʻa kahi huahana polū-hina, e hōʻike ana i ka noho pū ʻana o WO3(H2O)0.333 (PDF 087-1203, a = 7.3 Å, b = 12.5 Å, c = 7.7 ) ma Å , α = β = γ = 90 °) a me ke ʻano hoʻemi o ka tungsten oxide.Ua hōʻike ʻia ka loiloi Semiquantitative me X'Pert HighScore i ka 26% WO3(H2O)0.333: 74% W32O84.No ka mea aia ʻo W32O84 me W6+ a me W4+ (1.67:1 W6+:W4+), ʻo ka maʻiʻo i manaʻo ʻia o W6+ a me W4+ ma kahi o 72% W6+ a me 28% W4+.Nā kiʻi SEM, 1-kekona XPS spectra ma ka pae nucleus, nā kiʻi TEM, FTIR spectra a me Raman spectra o nā mea C76 i hōʻike ʻia ma kā mākou pepa mua24.Wahi a Kawada et al.50,51, X-ray diffraction pattern o C76 hōʻike i ka monoclinic structure o FCC ma hope o ka wehe ʻana o toluene.
Nā kiʻi SEM ma ka fig.Hōʻike ka 2a a me ka b i ka waiho ʻana o HWO a me HWO-50%C76 ma waena a ma waena o nā kaula kalapona o nā electrodes UCC.Hōʻike ʻia ke kiʻi kiʻi SEM ma ke kiʻi 2c ma ka fig.2d–f e hōʻike ana i ka hui like ʻana o ka tungsten a me ke kalapona (e hōʻike ana i ka puʻunaue like) ma luna o ka ʻili electrode a ʻaʻole i waiho like ka composite.ma muli o ke ʻano o ke ʻano o ka ua.
Nā kiʻi SEM o nā ʻāpana HWO i waiho ʻia (a) a me nā ʻāpana HWO-C76 (b).Hoʻouka ʻia ka palapala ʻāina ʻo EDX i HWO-C76 ma UCC me ka hoʻohana ʻana i ka ʻāpana ma ke kiʻi (c) hōʻike i ka puʻunaue ʻana o ka tungsten (d), kalapona (e), a me ka oxygen (f) i ka hāpana.
Ua hoʻohana ʻia ʻo HR-TEM no ke kiʻi kiʻi kiʻekiʻe a me ka ʻike crystallographic (Figure 3).Hōʻike ka HWO i ka morphology nanocube e like me ka hōʻike ʻana ma ka Figure 3a a me ka maopopo loa ma ka Figure 3b.Ma ka hoʻonui ʻana i ka nanocube no ka ʻokoʻa o kahi wahi i koho ʻia, hiki ke ʻike ʻia ke ʻano kuʻi a me nā mokulele ʻokoʻa e hoʻokō ai i ke kānāwai o Bragg e like me ka hōʻike ʻana ma ka Figure 3c, e hōʻoia ana i ka crystallinity o ka mea.Ma ka hoʻokomo ʻana i ka Fig. 3c e hōʻike ana i ka mamao d 3.3 Å e pili ana i nā (022) a me (620) nā mokulele ʻokoʻa ma ka WO3(H2O)0.333 a me W32O84, 43, 44, 49 mau māhele.Kūlike kēia me ka hōʻike XRD ma luna (Fig. 1b) mai ka mamao o ka mokulele grating i ʻike ʻia d (Fig. 3c) pili i ka piko XRD ikaika loa i ka hāpana HWO.Hōʻike ʻia nā apo laʻana ma ka fig.3d, kahi e pili ai kēlā me kēia apo i kahi mokulele ʻokoʻa.ʻO nā mokulele WO3(H2O)0.333 a me W32O84 he keʻokeʻo a me ka uliuli, a ua hōʻike pū ʻia ko lākou mau piko XRD e pili ana i ke kiʻi 1b.ʻO ke apo mua i hōʻike ʻia ma ke ʻano apo e pili ana i ka piko i kaha mua ʻia i ke ʻano x-ray o ka (022) a i ʻole (620) o ka mokulele ʻokoʻa.Mai (022) a i (402) apo, d-mamao o 3.30, 3.17, 2.38, 1.93, a me 1.69 Å i loaa, i kulike me ka XRD waiwai o 3.30, 3.17, 2 .45, 1.93 a me 1.66.Å, 44, 45.
(a) kiʻi HR-TEM o HWO, (b) hōʻike i kahi kiʻi i hoʻonui ʻia.Hōʻike ʻia nā kiʻi o nā mokulele paʻi ma (c), a hōʻike ʻia ka inset (c) i kahi kiʻi i hoʻonui ʻia o nā mokulele a me ka wā d 0.33 nm e pili ana i nā mokulele (002) a me (620).(d) HWO kumu hoʻohālike e hōʻike ana i nā mokulele e pili ana i nā māhele WO3(H2O)0.333 (keʻokeʻo) a me W32O84 (uliuli).
Ua hana ʻia ka loiloi XPS no ka hoʻoholo ʻana i ka kemika o ka ʻili a me ke kūlana oxidation o tungsten (Nā Kiʻi S1 a me 4).Hōʻike ʻia ka spectrum o ka laulā XPS scan o ka HWO synthesized i ka Fig.S1, e hōʻike ana i ke alo o ka tungsten.Hōʻike ʻia nā kikoʻī kikoʻī XPS o nā pae nui W 4f a me O1s ma Fig.4a a me b.Ua māhele ʻia ke kikoʻī W 4f i ʻelua mau ʻōpuni milo-orbit e pili ana i ka ikehu hoʻopaʻa ʻana o ke kūlana oxidation W. ʻO nā piko W 4f5/2 a me W 4f7/2 ma nā ikaika hoʻopaʻa o 37.8 a me 35.6 eV no W6+, a ʻo nā piko W ʻO 4f5/2 a me W 4f7/2 ma 36.6 a me 34.9 eV ke ʻano o ka mokuʻāina W4+.ʻO ka loaʻa ʻana o ke kūlana oxidation (W4 +) e hōʻoia hou i ka hoʻokumu ʻana o ka non-stoichiometric WO2.63, ʻoiai ka hele ʻana o W6 + e hōʻike ana i ka stoichiometric WO3 ma muli o WO3 (H2O) 0.333.Ua hōʻike ʻia nā ʻikepili i hoʻopili ʻia ʻo nā pākēneka atomic o W6 + a me W4 + he 85% a me 15%, kēlā me kēia, kahi kokoke i nā waiwai i manaʻo ʻia mai ka ʻikepili XRD, hāʻawi ʻia ka ʻokoʻa ma waena o nā ʻenehana ʻelua.Hāʻawi nā ʻano ʻelua i ka ʻike nui me ka pololei haʻahaʻa, ʻoi aku ka XRD.Eia kekahi, ʻike nā ʻano ʻelua i nā ʻāpana like ʻole o ka mea no ka mea ʻo XRD kahi ʻano nui a ʻo XPS kahi ala ʻili e hoʻokokoke wale ana i nā nanometer.Hoʻokaʻawale ka spectrum O 1 i ʻelua mau piko ma 533 (22.2%) a me 530.4 eV (77.8%).Ua pili ka mua me OH, a o ka lua me na mea paa o ka oxygen ma ka lattice ma WO.ʻO ka loaʻa ʻana o nā pūʻulu hana OH e kūlike me nā waiwai hydration o HWO.
Ua hana pū ʻia kahi loiloi FTIR ma kēia mau laʻana ʻelua e nānā i ka hiki ʻana mai o nā pūʻulu hana a me nā molekole wai i hoʻonohonoho ʻia i loko o ka hale HWO hydrated.Hōʻike nā hopena i ka like o ka HWO-50% C76 a me nā hopena FT-IR HWO ma muli o ka loaʻa ʻana o HWO, akā ʻokoʻa ka ikaika o nā piko ma muli o nā ʻokoʻa o ka laʻana i hoʻohana ʻia i ka wā hoʻomākaukau no ka nānā ʻana (Fig. 5a ).HWO-50% C76 Hōʻike ʻia nā piko piha piha 24 koe wale nō ka piko o ka tungsten oxide.Mea kiko'ī ma ka fig.Hōʻike ka 5a e hōʻike ana nā laʻana ʻelua i kahi hui ākea ikaika loa ma ~ 710/cm, i pili i ka OWO e hoʻolōʻihi ana i nā haʻalulu ma ka HWO lattice structure, a me kahi poʻohiwi ikaika ma ~ 840/cm, i hāʻawi ʻia iā WO.pili ka hui oi ma ~1610/cm i ka ha'alulu kulou o OH, a o ke kaula ho'ohala ākea ma ~3400/cm e pili ana i ka ha'alulu o OH i loko o ka hui hydroxyl43.Kūlike kēia mau hopena me ka spectrum XPS ma Fig. 4b, kahi e hiki ai i ka hui hana WO ke hāʻawi i nā wahi hana no ka hopena VO2 + / VO2 +.
ʻIkepili FTIR o HWO a me HWO-50% C76 (a) e hōʻike ana i nā pūʻulu hana a me nā ana kihi pili (b, c).
Hiki i ka hui OH ke hoʻoikaika i ka hopena VO2 + / VO2 +, ma laila e hoʻonui ai i ka hydrophilicity o ka electrode, a laila e hoʻolaha ana i ka diffusion a me nā helu hoʻololi electron.Hōʻike ka laʻana HWO-50% C76 i kahi kiʻekiʻe C76 e like me ka hōʻike ʻana ma ke kiʻi.ʻO nā piko ma ~2905, 2375, 1705, 1607, a me 1445 cm3 hiki ke hāʻawi ʻia i ka CH, O=C=O, C=O, C=C, a me CO stretching vibrations.Ua ʻike ʻia ʻo nā hui hana oxygen C=O a me CO hiki ke lawelawe ma ke ʻano he mau kikowaena ikaika no nā hopena redox o vanadium.No ka ho'āʻo a hoʻohālikelike i ka pulu o nā electrodes ʻelua, ua hoʻohana ʻia nā ana kihi pili e like me ka hōʻike ʻana ma ka Fig. 5b, c.Hoʻopili koke ka HWO electrode i nā kulu wai, e hōʻike ana i ka superhydrophilicity ma muli o nā hui hana OH i loaʻa.ʻOi aku ka hydrophobic HWO-50% C76, me kahi kihi pili ma kahi o 135° ma hope o 10 kekona.Eia nō naʻe, ma nā ana electrochemical, ua pulu ʻia ka electrode HWO-50%C76 ma lalo o hoʻokahi minuke.Ua kūlike nā ana wai me nā hualoaʻa XPS a me FTIR, e hōʻike ana i ka nui o nā pūʻulu OH ma ka ʻili HWO e ʻoi aku ka hydrophilic.
Ua hoʻāʻo ʻia nā hopena VO2 +/VO2+ o nā nanocomposites HWO a me HWO-C76 a ua manaʻo ʻia e hoʻopau ʻo HWO i ka hoʻololi ʻana o ke kinoea chlorine i hana ʻia i ka wā VO2 +/VO2+ i loko o nā ʻakika hui ʻia, ʻoiai ʻo C76 e hoʻoikaika hou i ka VO2 + / VO2+ i makemake ʻia.Hoʻopili ʻia nā hoʻokuʻu HWO me 10%, 30% a me 50% C76 i nā electrodes UCC me ka ukana holoʻokoʻa ma kahi o 2 mg/cm2.
E like me ka hoike ana ma ka fig.6, ua nānā ʻia nā kinetics o ka hopena VO2+/VO2+ ma ka ʻili electrode me ka hoʻohana ʻana i ka CV i nā electrolytes acidic hui ʻia.Hōʻike ʻia nā ʻano he I/Ipa e hoʻohālikelike ai i ka ΔEp a me Ipa/Ipc.Loaʻa pololei nā catalysts mai ke kiʻi.Hōʻike ʻia ka ʻikepili ʻāpana ʻāpana o kēia manawa ma ke Kiʻi 2S.Ma ka fig.Hōʻike ka Figure 6a i ka hoʻonui iki ʻana o ka HWO i ka hoʻololi electron o ka hopena redox VO2+/VO2+ ma ka ʻili electrode a hoʻopaʻa i ka hopena o ka evolution chlorine parasitic.Eia naʻe, hoʻonui nui ʻo C76 i ka helu hoʻololi electron a hoʻopaʻa i ka hopena o ka chlorine evolution.No laila, ʻo kahi paʻakikī me ka haku mele pono ʻana o HWO a me C76 pono e loaʻa ka hana maikaʻi loa a me ka mana kiʻekiʻe loa e kāohi i ka hopena chlorine.Uaʻikeʻia ma hope o ka hoʻonuiʻana i ka mea C76, ua hoʻonuiʻia ka hana electrochemical o ka electrode, e like me ka hōʻikeʻana i ka emiʻana o ka ΔEp a me ka piʻiʻana o ka ratio Ipa / Ipc (Table S3).Ua hōʻoia pū ʻia kēia e nā waiwai RCT i unuhi ʻia mai ka ʻāpana Nyquist ma Fig. 6d (papa S3), kahi i ʻike ʻia ai ua emi nā waiwai RCT me ka hoʻonui ʻana i ka ʻike o C76.Ua kūlike pū kēia mau hopena me kā Lee noiʻi ʻana i hoʻohui ʻia ai ka kalapona mesoporous i ka mesoporous WO3 i hoʻomaikaʻi i nā kinetics hoʻoili kālā ma VO2+/VO2+35.Hōʻike kēia i ka hopena maikaʻi e hilinaʻi hou aku i ka conductivity o ka electrode (C = C bond)18,24,35,36,37.Ma muli o ka hoʻololi ʻana i ka geometry coordination ma waena o [VO(H2O)5]2+ a me [VO2(H2O)4]+, hiki nō hoʻi iā C76 ke hoʻemi i ka overstrain pane ma o ka hoʻemi ʻana i ka ikehu kiko.Eia naʻe, ʻaʻole hiki ke hana me nā electrodes HWO.
(a) Ka hana voltammetric Cyclic o UCC a me HWO-C76 composites me HWO: C76 ratio like ole ma VO2+/VO2+ reactions in 0.1 M VOSO4/1 M H2SO4 + 1 M HCl electrolyte (ma ν = 5 mV/s).(b) ʻO Randles-Sevchik a me (c) ʻO ke ʻano VO2+/VO2+ a Nicholson no ka helu ʻana i ka pono diffusion a loaʻa nā waiwai k0 (d).
ʻAʻole wale ʻo HWO-50% C76 e hōʻike ana i ka hana electrocatalytic like me C76 no ka hopena VO2+/VO2+, akā, ʻoi aku ka hoihoi, ua kāohi ʻo ia i ka hoʻololi ʻana o ke kinoea chlorine i hoʻohālikelike ʻia me C76, e like me ka hōʻike ʻana ma ke kiʻi.6a, ma waho aʻe o ka hōʻike ʻana i ka hapalua pōʻai liʻiliʻi ma ka fig.6g (RCT haʻahaʻa).Ua hōʻike ʻo C76 i kahi Ipa/Ipc kiʻekiʻe aʻe ma mua o HWO-50% C76 (Table S3), ʻaʻole ma muli o ka hoʻomaikaʻi ʻana i ka hoʻohuli ʻana, akā ma muli o ka uhi ʻana me ka chlorine reduction peak ma 1.2 V i hoʻohālikelike ʻia me SHE.Hāʻawi ʻia ka hana maikaʻi loa o HWO-50% C76 i ka synergy ma waena o ka C76 conductive kiʻekiʻe i hoʻopiʻi maikaʻi ʻia a me nā hana hoʻonaninani kiʻekiʻe a me nā catalytic o W-OH ma HWO.ʻOiai ʻo ka liʻiliʻi ʻana o ka chlorine e hoʻomaikaʻi i ka pono o ka hoʻopiʻi ʻana o ke kelepona piha, hoʻomaikaʻi ʻia nā kinetics e hoʻonui i ka pono o ka volta cell piha.
E like me ka hoʻohālikelike S1, no ka hopena quasi-reversible (relatively slow electron transfer) i hoʻomalu ʻia e ka diffusion, pili ka peak current (IP) i ka helu o nā electrons (n), electrode area (A), diffusion coefficient (D), helu. o ka huina hoololi electron (α) a me ka mämä holo kiki (ν).No ke aʻo ʻana i ke ʻano hoʻomākeʻe o nā mea i hoʻāʻo ʻia, ua hoʻolālā ʻia ka pilina ma waena o IP a me ν1/2 a hōʻike ʻia ma Fig. 6b.No ka mea, hōʻike nā mea a pau i ka pilina laina, hoʻomalu ʻia ka hopena e ka diffusion.No ka mea hiki ke hoʻohuli ʻia ka hopena o VO2+/VO2+, pili ka slope o ka laina i ka diffusion coefficient a me ka waiwai o α (equation S1).Ma muli o ke koena o ka diffusion mau (≈ 4 × 10–6 cm2/s)52, ʻo ka ʻokoʻa o ka slope laina e hōʻike pololei i nā waiwai like ʻole o ka α a no laila nā ʻokoʻa like ʻole o ka hoʻoili electron i ka ʻili electrode, me C76 a me HWO -50 % C76, e hōʻike ana i nā pali kiʻekiʻe loa (ke kiʻekiʻe o ka hoʻoili uila uila).
ʻO nā slopes Warburg haʻahaʻa haʻahaʻa i helu ʻia (W) i hōʻike ʻia ma ka Papa S3 (Fig. 6d) he mau waiwai kokoke i ka 1 no nā mea āpau, e hōʻike ana i ka diffusion kūpono o nā ʻāpana redox a me ka hōʻoia ʻana i ke ʻano linear o IP versus ν1/2 no CV.ana ana .No ka HWO-50% C76, ua ha'alele ka pali o Warburg mai ka lokahi a i ka 1.32, e kuhikuhi ana i ka ha'awina 'a'ole wale mai ka diffusion semi-infinite o nā reactants (VO2+), akā, i ka 'ano o ka 'ili lahilahi ma ka 'ano diffusion ma muli o ka electrode porosity.
No ka hoʻopili hou ʻana i ka hoʻololi ʻana (ka hoʻololi uila) o ka hopena redox VO2+/VO2+, ua hoʻohana pū ʻia ka Nicholson quasi-reversible reaction method no ka hoʻoholo ʻana i ka helu maʻamau k041.42.Hana ʻia kēia ma ke kālai ʻana i ka ʻāpana kinetic dimensionless Ψ ma ke ʻano he hana o ΔEp ma ke ʻano he hana o ν−1/2 me ka hoʻohana ʻana i ka hoʻohālikelike S2.Hōʻike ka papa S4 i nā waiwai Ψ no kēlā me kēia mea electrode.E kau i nā hualoaʻa (Figure 6c) no ka loaʻa ʻana o k0 × 104 cm/s (kākau ʻia ma ka ʻaoʻao o kēlā me kēia lālani a hōʻike ʻia ma ka Papa S4) me ka hoʻohana ʻana i ka hoohalike S3 no ka pali o kēlā me kēia pā.Ua ʻike ʻia ʻo HWO-50% C76 ka piʻi kiʻekiʻe loa (Fig. 6c) a no laila ke kumu k0 kiʻekiʻe loa o 2.47 × 10–4 cm/s.'O ia ho'i, hā'awi kēia electrode i nā kinetics wikiwiki loa e like me nā hualoa'a CV a me EIS ma nā Ki'i 6a a me d a me ka Papa S3.Eia kekahi, ua loaʻa pū nā koina k0 mai nā ʻāpana Nyquist (Fig. 6d) o ka Equation S4 me ka hoʻohana ʻana i nā waiwai RCT ​​(Table S3).Ua hōʻuluʻulu ʻia kēia mau hopena k0 mai EIS ma ka Papa S4 a hōʻike pū ʻia ʻo HWO-50% C76 e hōʻike ana i ka nui o ka hoʻololi electron kiʻekiʻe ma muli o ka hopena synergistic.ʻOiai ʻokoʻa ka waiwai o k0 ma muli o ke kumu like ʻole o kēlā me kēia ʻano, hōʻike mau ia i ka ʻano like o ka nui a hōʻike i ke kūlike.
No ka hoʻomaopopo piha ʻana i nā kinetics maikaʻi loa e hiki ke hoʻokō, he mea nui e hoʻohālikelike i ka mea electrode maikaʻi loa me nā electrodes UCC a me TCC ʻole.No ka hopena VO2 +/VO2+, ʻaʻole i hōʻike wale ʻo HWO-C76 i ka haʻahaʻa haʻahaʻa loa a me ka hoʻohuli hou ʻana, akā ua hoʻopaʻa nui ʻia ka hopena chlorine evolution parasitic i hoʻohālikelike ʻia me TCC, e like me ka mea i hōʻike ʻia e kahi hāʻule nui o kēia manawa ma 1.45 V i hoʻohālikelike ʻia i ka OHA (Fig. 7a).Ma ke ʻano o ke kūpaʻa, manaʻo mākou he paʻa kino ka HWO-50% C76 no ka mea ua hui pū ʻia ka catalyst me kahi PVDF binder a laila hoʻopili ʻia i nā electrodes lole kalapona.Hoʻohālikelike ʻia me 50 mV no UCC, ua hōʻike ʻo HWO-50% C76 i kahi hoʻololi kiʻekiʻe o 44 mV ma hope o 150 cycles (degradation rate 0.29 mV/cycle) (Figure 7b).ʻAʻole paha he ʻokoʻa nui, akā lohi loa nā kinetics o nā electrodes UCC a hoʻohaʻahaʻa ʻia me ke kaʻa kaʻa, ʻoi loa no ka hopena hope.ʻOiai ʻoi aku ka maikaʻi o ka hoʻohuli ʻana o TCC ma mua o ka UCC, ua ʻike ʻia ʻo TCC i kahi hoʻololi kiʻekiʻe nui o 73 mV ma hope o 150 cycles, ʻo ia paha ma muli o ka nui o ka chlorine i hoʻokuʻu ʻia mai kona ʻili.No ka hoʻopaʻa pono ʻana o ka catalyst i ka ʻili electrode.E like me ka ʻike ʻia ma nā electrodes a pau i hoʻāʻo ʻia, ʻo ka poʻe i kākoʻo ʻole i nā catalysts e hōʻike ana i nā pae like ʻole o ka paʻa ʻole o ke kaʻa, e hōʻike ana i nā loli o ka hoʻokaʻawale kiʻekiʻe i ka wā kaʻa kaʻa ma muli o ka deactivation mea ma muli o nā loli kemika ma mua o ka hoʻokaʻawale catalyst.Eia kekahi, inā e hoʻokaʻawale ʻia ka nui o nā ʻāpana catalyst mai ka ʻili electrode, e alakaʻi kēia i ka piʻi nui ʻana o ka hoʻokaʻawale kiʻekiʻe (ʻaʻole wale ma 44 mV), no ka mea, ʻaʻohe hana o ka substrate (UCC) no ka VO2+/VO2+ ka hopena redox.
Hoʻohālikelike o CV (a) a me ka paʻa o ka redox reaction VO2+/VO2+ (b) o ka mea electrode maikaʻi loa e pili ana iā CCC.Ma ka electrolyte 0.1 M VOSO4/1 M H2SO4 + 1 M HCl, ua like nā CV a pau me ν = 5 mV/s.
No ka hoʻonui ʻana i ka hoihoi waiwai o ka ʻenehana VRFB, pono ka hoʻomaikaʻi ʻana a me ka hoʻomaopopo ʻana i nā kinetics o ka vanadium redox reaction i ka loaʻa ʻana o ka ikehu kiʻekiʻe.Ua hoʻomākaukau ʻia nā hui HWO-C76 a ua aʻo ʻia kā lākou hopena electrocatalytic ma ka hopena VO2 +/VO2+.Ua hōʻike ʻo HWO i ka hoʻonui kinetic liʻiliʻi akā ua kāohi nui i ka hoʻomohala ʻana o ka chlorine i loko o nā electrolytes acidic hui ʻia.Ua hoʻohana ʻia nā lakio like ʻole o HWO:C76 no ka hoʻonui ʻana i nā kinetics o nā electrodes-hoʻokumu HWO.Hiki i ka hoʻonui ʻana i ka ʻike o C76 a i ka HWO ke hoʻomaikaʻi i nā kinetics hoʻoili electron o ka hopena VO2 +/VO2+ ma ka electrode i hoʻololi ʻia, ma waena o ka HWO-50% C76 ka mea maikaʻi loa no ka mea e hoʻohaʻahaʻa i ke kūʻē ʻana o ka hoʻoili kālā a hoʻopaʻa hou i ka hoʻololi kinoea chlorine i hoʻohālikelike ʻia me C76.a ua hoʻokuʻu ʻia ʻo TCC.Ma muli o ka hopena synergistic ma waena o C=C sp2 hybridization, OH a me W-OH pūʻulu hana.ʻO ka helu hoʻohaʻahaʻa o HWO-50% C76 i ʻike ʻia he 0.29mV/pōkole ma lalo o ke kaʻa uila ʻoiai ʻo UCC a me TCC he 0.33mV/pōkole a me 0.49mV/pōkole kēlā me kēia, e hoʻokūpaʻa loa ia i nā electrolytes acid mix.ʻIke maikaʻi nā hopena i hōʻike ʻia i nā mea electrode hana kiʻekiʻe no ka hopena VO2+/VO2+ me nā kinetics wikiwiki a me ke kūpaʻa kiʻekiʻe.ʻO kēia ka mea e hoʻonui ai i ka voltage puka, a laila e hoʻomaikaʻi ai i ka pono o ka mana o ka VRFB, a laila e hōʻemi ana i ke kumukūʻai o kāna kālepa e hiki mai ana.
Loaʻa nā ʻikepili i hoʻohana ʻia a/a i ʻike ʻia i ka noiʻi o kēia manawa mai nā mea kākau ma muli o ke noi kūpono.
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