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byatangajwe kuri electrochemic stratifisation ya bor-idakora boron yoroheje.Izi ngaruka zidasanzwe zigerwaho mugushira boron nyinshi muri meshi yicyuma itera amashanyarazi kandi ikingura umwanya wo guhimba boron hamwe niyi ngamba zifatika.Ubushakashatsi bwakozwe muri electrolytite zitandukanye butanga igikoresho gikomeye cyo kubona flake ya borene yibyiciro bitandukanye hamwe nubunini bwa ~ 3-6 nm.Uburyo bwo kurandura amashanyarazi ya boron nabwo bwaragaragaye kandi buraganirwaho.Rero, uburyo buteganijwe bushobora kuba igikoresho gishya cyo gukora umusaruro munini wo gukora ibinini bito kandi byihutisha iterambere ryubushakashatsi bujyanye na burs nibishobora gukoreshwa.
Ibikoresho bibiri-2D (2D) byakiriye inyungu nyinshi mumyaka yashize kubera imiterere yihariye nkumuyoboro wamashanyarazi cyangwa ibintu bigaragara bigaragara.Iterambere ryibikoresho bya graphene ryakwegereye ibitekerezo kubindi bikoresho 2D, bityo ibikoresho bishya 2D birakorwaho ubushakashatsi bwimbitse.Usibye graphene izwi cyane, inzibacyuho ya dichalcogenide (TMD) nka WS21, MoS22, MoSe3, na WSe4 nazo zakozweho ubushakashatsi vuba aha.Nubwo ibikoresho bimaze kuvugwa, nitride ya boron itandatu (hBN), fosifore yumukara na boronene iherutse gukorwa neza.Muri byo, boron yakuruye cyane nkimwe muri sisitemu ntoya ya sisitemu ebyiri.Itondekanye nka graphene ariko irerekana ibintu bishimishije bitewe na anisotropy, polymorphism hamwe na kristu.Ubwinshi bwa boron bugaragara nkibice byibanze byubaka muri B12 icosahedron, ariko ubwoko butandukanye bwa kirisiti ya boron ikorwa muburyo butandukanye bwo guhuza no guhuza muri B12.Nkigisubizo, blok ya boron mubusanzwe ntabwo igizwe nka graphene cyangwa grafite, bigora inzira yo kubona boron.Mubyongeyeho, uburyo bwinshi bwa polymorphique ya borophene (urugero, α, β, α1, pmmm) bituma irushaho kuba ingorabahizi5.Ibyiciro bitandukanye byagezweho mugihe cya synthesis bigira ingaruka kumiterere ya harrows.Kubwibyo, guteza imbere uburyo bwubukorikori butuma bishoboka kubona icyiciro cyihariye cya borocène ifite ibipimo binini byuruhande hamwe nubunini buto bwa flake bisaba ubushakashatsi bwimbitse.
Uburyo bwinshi bwo guhuza ibikoresho 2D bishingiye kubikorwa bya sonochemiki aho ibikoresho byinshi bishyirwa mumashanyarazi, mubisanzwe ibimera, kandi bigakorwa mumasaha menshi.Ranjan n'abandi.6 yatsinze neza boron muri borophene ukoresheje uburyo bwasobanuwe haruguru.Bize ubushakashatsi butandukanye (methanol, Ethanol, isopropanol, acetone, DMF, DMSO) kandi berekana ko sonic exfolisiyoneri ari uburyo bworoshye bwo kubona ibinini binini kandi binini.Mubyongeyeho, berekanye ko uburyo bwa Hummers bwahinduwe bushobora no gukoreshwa mugukuramo boron.Gutondekanya amazi byerekanwe nabandi: Lin n'abandi.7 yakoresheje kristaline boron nkisoko yo gushushanya amabati yo hasi β12-borene hanyuma akayakoresha muri bateri ya lithium-sulfure ishingiye kuri borene, na Li n'abandi.8 yerekanye urupapuro ruto rwa boronene..Irashobora kuboneka na synthesis ya sonochemiki kandi igakoreshwa nka electrode ya supercapacitor.Nyamara, atomic layer deposition (ALD) nayo ni bumwe muburyo bwo hasi-hejuru ya synthesis ya boron.Mannix et al.9 yashyize atome ya boron kumurongo wa feza utunganijwe neza.Ubu buryo butuma bishoboka kubona amabati ya boronene ya ultra-yera, icyakora umusaruro wa laboratoire ya boronene ugarukira cyane kubera imiterere mibi (vacuum ultra-high).Niyo mpamvu, ni ngombwa gushyiraho ingamba nshya zinoze zo gukora boronene, gusobanura uburyo bwo gukura / gutondekanya, hanyuma ugakora isesengura nyaryo ryimiterere yimiterere yaryo, nka polymorphism, amashanyarazi no guhererekanya ubushyuhe.H. Liu n'abandi.10 baganiriye kandi basobanura uburyo bwo gukura kwa boron kuri Cu (111).Byagaragaye ko atome ya boron ikunda gukora ibice 2D byuzuye bishingiye ku bice bitatu bya mpandeshatu, kandi ingufu zo gukora zigenda zigabanuka buhoro buhoro hamwe n’ubunini bwiyongera, byerekana ko ihuriro rya 2D boron ku muringa rishobora gukura ubuziraherezo.Isesengura rirambuye ryimpapuro ebyiri za boron zitangwa na D. Li nabandi.11, ahasobanuwe insimburangingo zitandukanye kandi birashoboka kuganirwaho.Byerekanwe neza ko hari itandukaniro riri hagati yo kubara theoretical nibisubizo byubushakashatsi.Kubwibyo, kubara kubara birakenewe kugirango dusobanukirwe neza imiterere nuburyo bwo gukura kwa boron.Bumwe mu buryo bwo kugera kuri iyi ntego ni ugukoresha kaseti yoroshye yo gukuramo boron, ariko ibi biracyari bito cyane kugirango ukore imitungo yibanze no guhindura imikorere yayo12.
Uburyo butanga ibyiringiro byubwubatsi bwibikoresho 2D biva mubikoresho byinshi ni amashanyarazi.Hano imwe muri electrode igizwe nibikoresho byinshi.Muri rusange, ibimera bisanzwe bigaragazwa nuburyo bwa electrochemicique birayobora cyane.Baraboneka nkibiti bifatanye cyangwa ibinini.Graphite irashobora gutwarwa neza murubu buryo kubera amashanyarazi menshi.Achi nitsinda rye14 basibye neza grafite muguhindura inkoni ya grafite muri grafite ikanda imbere ya membrane yakoreshejwe kugirango birinde kwangirika kwinshi.Izindi laminates nini zirashishwa muburyo busa, kurugero, ukoresheje amashanyarazi ya Janus15.Mu buryo nk'ubwo, fosifore yumukara itondekanye itondekanya amashanyarazi, hamwe na ion ya acide electrolyte ion ikwirakwizwa mumwanya uri hagati yabyo bitewe na voltage ikoreshwa.Kubwamahirwe, uburyo bumwe ntibushobora gukoreshwa muburyo bwa boron muri borophene kubera amashanyarazi make yibikoresho byinshi.Ariko bigenda bite iyo ifu ya boron irekuye ishyizwe mubyuma (nikel-nikel cyangwa umuringa-umuringa) kugirango bikoreshwe nka electrode?Birashoboka gutera imbaraga za boron, zishobora kurushaho kugabanywa amashanyarazi nka sisitemu igizwe nabatwara amashanyarazi?Niki cyiciro cya boronene yateye imbere?
Muri ubu bushakashatsi, turasubiza ibi bibazo kandi twerekana ko ubwo buryo bworoshye butanga uburyo bushya muri rusange bwo guhimba ibibyimba bito, nkuko bigaragara ku gishushanyo 1.
Litiyumu ya chloride (LiCl, 99.0%, CAS: 7447-41-8) hamwe nifu ya boron (B, CAS: 7440-42-8) byaguzwe muri Sigma Aldrich (USA).Sodium sulfate (Na2SO4, ≥ 99.0%, CAS: 7757-82-6) yatanzwe na Chempur (Polonye).Dimethyl sulfoxide (DMSO, CAS: 67-68-5) yo muri Karpinex (Polonye) yakoreshejwe.
Imbaraga za atome microscopi (AFM MultiMode 8 (Bruker)) itanga amakuru kubyerekeranye n'ubunini n'ubunini bwa lattice y'ibikoresho.Ikwirakwizwa ryinshi rya electron microscopi (HR-TEM) ryakozwe hakoreshejwe microscope ya FEI Tecnai F20 kuri voltage yihuta ya 200 kV.Isesengura rya Atomic absorption spekitroscopi (AAS) ryakozwe hifashishijwe Hitachi Zeeman polarized atomic absorption spectrophotometer hamwe na nebulizer ya flame kugirango hamenyekane iyimuka rya ion zicyuma mugisubizo mugihe cyo kuzimya amashanyarazi.Ubushobozi bwa zeta bwa boron yapimwe kandi bukorerwa kuri Zeta Sizer (ZS Nano ZEN 3600, Malvern) kugirango hamenyekane ubushobozi bwubuso bwa boron.Ibigize imiti hamwe na atomic ijanisha ryubuso bwubushakashatsi bwakozwe na X-ray fotoelectron spectroscopy (XPS).Ibipimo byakozwe hifashishijwe imirasire ya Mg Ka (hν = 1253,6 eV) muri sisitemu ya PREVAC (Polonye) ifite ibikoresho bya Scienta SES 2002 isesengura ingufu za elegitoronike (Suwede) ikorera ku mbaraga zihoraho (Ep = 50 eV).Icyumba cyisesengura cyimuwe kumuvuduko uri munsi ya 5 × 10-9 mbar.
Mubisanzwe, 0.1 g yifu ya boron itemba yubusa irabanza gukanda muri disiki yicyuma (nikel cyangwa umuringa) ukoresheje imashini ya hydraulic.Disiki ifite diameter ya mm 15.Disiki zateguwe zikoreshwa nka electrode.Ubwoko bubiri bwa electrolytite bwakoreshejwe: (i) 1 M LiCl muri DMSO na (ii) 1 M Na2SO4 mumazi yimana.Umugozi wa platine wakoreshejwe nka electrode ifasha.Igishushanyo mbonera cyibikorwa byerekanwe ku gishushanyo cya 1. Mu gukuramo amashanyarazi, amashanyarazi yatanzwe (1 A, 0.5 A, cyangwa 0.1 A) akoreshwa hagati ya cathode na anode.Igihe cya buri kigeragezo ni isaha 1.Nyuma yibyo, ndengakamere yarakusanyirijwe, yinjizwamo 5000 rpm hanyuma yozwa inshuro nyinshi (inshuro 3-5) n'amazi ya deioni.
Ibipimo bitandukanye, nkigihe nintera iri hagati ya electrode, bigira ingaruka kumiterere yibicuruzwa byanyuma byo gutandukanya amashanyarazi.Hano turasuzuma ingaruka za electrolyte, ikoreshwa ryamashanyarazi (1 A, 0.5 A na 0.1 A; voltage 30 V) nubwoko bwa gride yicyuma (Ni ukurikije ingano yingaruka).Hapimwe electrolytite ebyiri zitandukanye: (i) 1 M lithium chloride (LiCl) muri dimethyl sulfoxide (DMSO) na (ii) 1 M sodium sulfate (Na2SO4) mumazi ya deioni (DI).Mubwa mbere, lithium cations (Li +) izahuza boron, ifitanye isano nuburyo bubi mubikorwa.Mugihe cyanyuma, anion ya sulfate (SO42-) izahuza na boron yuzuye neza.
Mu ikubitiro, ibikorwa bya electrolytite yavuzwe haruguru byerekanwe kumuyoboro wa 1 A. Igikorwa cyafashe isaha 1 hamwe nubwoko bubiri bwibyuma (Ni na Cu).Igishushanyo cya 2 cyerekana imbaraga za atome microscopi (AFM) ishusho yibintu bivamo, kandi uburebure buringaniye bwerekanwe mubishusho S1.Byongeye kandi, uburebure nubunini bwa flake bikozwe muri buri igeragezwa bigaragara mu mbonerahamwe ya 1. Ikigaragara ni uko iyo ukoresheje Na2SO4 nka electrolyte, umubyimba wa flake uba muke cyane iyo ukoresheje gride y'umuringa.Ugereranije na flake yakuweho imbere yikigo cya nikel, umubyimba ugabanuka inshuro zigera kuri 5.Igishimishije, ingano yo gukwirakwiza umunzani yari isa.Nyamara, LiCl / DMSO yagize akamaro mugikorwa cya exfoliation ikoresheje meshes zombi zicyuma, bivamo ibice 5-15 bya borocene, bisa nandi mazi ya exfoliating, bivamo ibice byinshi bya borocene7,8.Kubwibyo, ubundi bushakashatsi buzagaragaza imiterere irambuye yintangarugero muri iyi electrolyte.
AFM amashusho yimpapuro za borocene nyuma yo gusohora amashanyarazi muri Cu_Li + _1 A, B Cu_SO42 - _1 A, C Ni_Li + _1 A, na D Ni_SO42 - _1 A.
Isesengura ryakozwe hakoreshejwe microscopi ya electronique (TEM).Nkuko bigaragara ku gishushanyo cya 3, ubwinshi bwimiterere ya boron ni kristalline, nkuko bigaragazwa namashusho ya TEM ya boron ndetse na boron igororotse, kimwe nuburyo bwihuse bwihuta (FFT) hamwe nuburyo bwatoranijwe bwa Electron Diffraction (SAED).Itandukaniro nyamukuru hagati yintangarugero nyuma yuburyo bwo gusiba bigaragara byoroshye mumashusho ya TEM, aho d-intera ikarishye kandi intera ikaba ngufi cyane (0.35–0.9 nm; Imbonerahamwe S2).Mugihe ibyitegererezo byahimbwe kuri meshi y'umuringa bihuye na β-rhombohedral imiterere ya boron8, ingero zahimbwe hakoreshejwe nikelmeshbihuye nuburyo buhanura bwibipimo bya lattice: β12 na 1717.Ibi byerekanaga ko imiterere ya borocene yari kristaline, ariko ubunini nuburinganire bwa kristu byahindutse nyuma yo kuzimya.Ariko, irerekana neza kwishingikiriza kuri gride yakoreshejwe (Cu cyangwa Ni) kuri kristu ya borene yavuyemo.Kuri Cu cyangwa Ni, irashobora kuba imwe-kristu cyangwa polycristaline.Guhindura Crystal byavumbuwe no mubindi buhanga bwa exfoliation18,19.Ku bitureba, intambwe d nuburyo bwa nyuma biterwa cyane nubwoko bwa gride yakoreshejwe (Ni, Cu).Ihinduka rikomeye murashobora kubisanga muburyo bwa SAED, byerekana ko uburyo bwacu buganisha kumikorere yuburyo bumwe bwa kristu.Mubyongeyeho, gushushanya ibice (EDX) hamwe no gufata amashusho ya STEM byagaragaje ko ibikoresho 2D byahimbwe byari bigizwe na boron (Ishusho S5).Ariko, kugirango usobanukirwe byimazeyo imiterere, birakenewe ko hakorwa ubushakashatsi bwimbitse kumiterere ya borofène artificiel.By'umwihariko, isesengura ry'impande za borene rigomba gukomeza, kuko rifite uruhare runini mu gutuza kw'ibikoresho n'imikorere ya catalitiki20,21,22.
TEM amashusho ya boron A, B Cu_Li + _1 A na C Ni_Li + _1 A hamwe nuburyo SAED ihuye (A ', B', C ');byihuse Fourier ihinduka (FFT) kwinjiza kumashusho ya TEM.
Ifoto ya X-ray yerekana amashanyarazi (XPS) yakozwe kugirango hamenyekane urugero rwa okiside ya borene.Mugihe cyo gushyushya urugero rwa borophene, igipimo cya boron cyiyongereye kiva kuri 6.97% kigera kuri 28.13% (Imbonerahamwe S3).Hagati aho, kugabanuka kwa boron suboxide (BO) bibaho cyane cyane bitewe no gutandukanya okiside yo hejuru no guhindura suboxide ya boron kuri B2O3, nkuko bigaragazwa nubwiyongere bwa B2O3 mubitegererezo.Ku mutini.S8 yerekana impinduka muguhuza ibipimo bya boron na oxyde iyo ushyushye.Igiteranyo rusange cyerekanwe mugitabo.S7.Ibizamini byagaragaje ko boronene ya okiside hejuru kuri boron: igipimo cya oxyde ya 1: 1 mbere yo gushyuha na 1.5: 1 nyuma yo gushyuha.Kubisobanuro birambuye bya XPS, reba Amakuru yinyongera.
Ubushakashatsi bwakurikiyeho bwakozwe kugirango hamenyekane ingaruka zubu zikoreshwa hagati ya electrode mugihe cyo gutandukanya amashanyarazi.Ibizamini byakorewe kumurongo wa 0.5 A na 0.1 A muri LiCl / DMSO.Ibisubizo byubushakashatsi bwa AFM byerekanwe ku gishushanyo cya 4, naho imyirondoro yuburebure ijyanye irerekanwa mu mashusho.S2 na S3.Urebye ko umubyimba wa borophene monolayeri uri kuri 0.4 nm, 12,23 mu bushakashatsi bwakozwe kuri 0.5 A no kuba hari gride y'umuringa, uduce duto cyane duhuye na 5-111 ya borophene ifite uburebure bwa metero 0,6-2,5.Mubyongeyeho, mubigeragezo hamwenikelgride, flake hamwe no gukwirakwiza umubyimba muto cyane (4.82-5.27 nm) byabonetse.Igishimishije, flake ya boron yabonetse muburyo bwa sonochemiki ifite ubunini bwa flake bingana na 1.32-22.32 nm7 cyangwa 1.8-4.7 nm8.Mubyongeyeho, amashanyarazi ya exfoliation ya graphene yatanzwe na Achi nabandi.14 byavuyemo flake nini (> 30 µm), zishobora kuba zifitanye isano nubunini bwibintu byatangiye.Nyamara, flake ya graphene ifite uburebure bwa 2-7 nm.Ibice byubunini buringaniye hamwe nuburebure birashobora kuboneka mugabanya imiyoboro ikoreshwa kuva kuri 1 A kugeza 0.1 A. Kubwibyo, kugenzura ibi bintu byingenzi byimiterere yibikoresho 2D nuburyo bworoshye.Twabibutsa ko ubushakashatsi bwakorewe kuri gride ya nikel hamwe na 0.1 A bitagenze neza.Ibi biterwa n'amashanyarazi make ya nikel ugereranije n'umuringa n'ingufu zidahagije zisabwa kugirango borophene24.Isesengura rya TEM rya Cu_Li + _0.5 A, Cu_Li + _0.1 A, Cu_SO42-_1 A, Ni_Li-_0.5 A na Ni_SO42-_1 A ryerekanwe ku gishushanyo cya S3 n’ishusho S4.
Gukuraho amashanyarazi bikurikirwa no gufata amashusho ya AFM.(A) Cu_I
Hano turasaba kandi uburyo bushoboka bwo gutondekanya imyitozo myinshi mumyitozo yoroheje (Ishusho 5).Ku ikubitiro, ubwinshi bwa bur bwakandagiye muri gride ya Cu / Ni kugirango bitume amashanyarazi muri electrode, yakoresheje neza voltage hagati ya electrode ifasha (Pt wire) na electrode ikora.Ibi bituma ion yimuka binyuze muri electrolyte hanyuma igashyirwa mubintu bya cathode / anode, bitewe na electrolyte yakoreshejwe.Isesengura rya AAS ryerekanye ko nta ion zasohotse muri meshi yicyuma muriki gikorwa (reba Amakuru yinyongera).yerekanye ko ion gusa ziva muri electrolyte zishobora kwinjira mumiterere ya boron.Ubwinshi bwubucuruzi bwa boron bukoreshwa muriki gikorwa bakunze kwita "amorphous boron" kubera gukwirakwizwa kwayo kwingingo zingirabuzimafatizo, icosahedral B12, yashyutswe kugeza kuri 1000 ° C kugirango habeho imiterere β-rhombohedral (Igicapo S6) 25.Dukurikije imibare, lithium cations zinjizwa muburyo bwa boron murwego rwa mbere hanyuma zigashwanyaguza ibice bya batiri B12, amaherezo bigakora imiterere ya boronene-ibiri ifite imiterere itondekanye cyane, nka β-rhombohedra, β12 cyangwa χ3 , bitewe nuburyo bukoreshwa hamwe nameshibikoresho.Kugirango ugaragaze isano Li + kuri boron nyinshi nuruhare rwayo mugikorwa cyo gusiba, ubushobozi bwa zeta (ZP) bwapimwe kuba -38 ± 3.5 mV (reba Amakuru yinyongera).Agaciro ka ZP kubintu byinshi boron yerekana ko intercalation ya lithium nziza nziza ikora neza kurusha izindi ion zikoreshwa muri ubu bushakashatsi (nka SO42-).Ibi biranasobanura uburyo bwiza bwo kwinjira muri Li + muburyo bwa boron, bikavamo gukuraho amashanyarazi neza.
Niyo mpamvu, twateje imbere uburyo bushya bwo kubona boron-buke yo mu bwoko bwa electrochemical stratification ya boron dukoresheje gride ya Cu / Ni muri Li + / DMSO na SO42- / H2O ibisubizo.Birasa kandi no gutanga umusaruro mubyiciro bitandukanye bitewe nubu ikoreshwa hamwe na gride yakoreshejwe.Uburyo bwa exfolisiyoneri nabwo burasabwa kandi bukaganirwaho.Turashobora kwanzura ko boronene igenzurwa nubwiza buke irashobora kubyara byoroshye muguhitamo icyuma kibereye nkicyikorezo cya boron no guhitamo imiyoboro ikoreshwa, ishobora gukoreshwa cyane mubushakashatsi bwibanze cyangwa mubikorwa bifatika.Icyingenzi cyane, iyi niyo yambere igerageza kugerageza amashanyarazi ya boron.Byizerwa ko iyi nzira ishobora gukoreshwa mugutwika ibikoresho bitayobora muburyo bubiri.Nyamara, gusobanukirwa neza imiterere nimiterere ya synthesize yo hasi-burs irakenewe, kimwe nubushakashatsi bwiyongereye.
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Ubu bushakashatsi bwatewe inkunga n'ikigo cy'igihugu gishinzwe ubumenyi (Polonye) ku nkunga no.OPUS21 (2021/41 / B / ST5 / 03279).
Nickel wire mesh ni ubwoko bwinsinga zingandaumwendaikozwe muri nikel.Irangwa nigihe kirekire, amashanyarazi, hamwe no kurwanya ruswa.Bitewe nimiterere yihariye, nikel wire mesh ikoreshwa mubisabwa nko kuyungurura, kuyungurura, no gutandukana mu nganda nko mu kirere, imiti, no gutunganya ibiryo.Iraboneka murwego rwubunini bwa mesh na diameter ya wire kugirango ihuze ibisabwa bitandukanye.