Graphite igabanyijemo graphite y’ubukorano na graphite karemano, ububiko bwa graphite karemano bwemejwe ku isi mu matoni agera kuri miliyari 2.
Grafiti y'ubukorano iboneka binyuze mu kubora no gutunganya ubushyuhe bw'ibikoresho birimo karuboni munsi y'umuvuduko usanzwe. Iri hinduka risaba ubushyuhe bwinshi n'ingufu nk'imbaraga zikoreshwa, kandi imiterere idakora neza izahinduka imiterere ya kristale ya grafiti ikurikije gahunda.
Gutunganya imiterere y'ibintu bivamo karubone mu buryo bwagutse binyuze mu gutunganya ubushyuhe buri hejuru ya 2000 ℃ hakoreshejwe uburyo bwo kongera gutunganya atome za karubone, ariko bimwe mu bikoresho bya karubone mu bushyuhe buri hejuru ya 3000 ℃, ubwo bwoko bw'ibikoresho bya karubone bwari buzwi nka "amakara akomeye", ku bikoresho byoroshye bya karubone byakozwe mu buryo bwa graphitization, uburyo gakondo bwa graphitization burimo ubushyuhe bwinshi n'umuvuduko mwinshi, graphitization ya catalytic, uburyo bwo gushyiramo umwuka wa chemical, nibindi.
Gukoresha igishushanyo mbonera (graphitization) ni uburyo bwiza bwo gukoresha ibikoresho bifite karubone mu buryo bw’agaciro kanini. Nyuma y’ubushakashatsi bwimbitse bwakozwe n’abahanga, ubu bumaze gukura. Ariko, hari ibintu bibi bibuza ikoreshwa rya graphitization gakondo mu nganda, bityo ni ikintu kidasubirwaho gushakisha uburyo bushya bwo gukoresha igishushanyo mbonera.
Uburyo bwa elegitorolize y’umunyu ushongeshejwe kuva mu kinyejana cya 19 bwari imyaka irenga ijana y’iterambere, inyigisho yabwo y’ibanze n’uburyo bushya buri gihe ni udushya n’iterambere, ubu ntabwo bukigarukira gusa ku nganda gakondo z’ibyuma, mu ntangiriro z’ikinyejana cya 21, icyuma kiri mu buryo bw’umunyu ushongeshejwe gitegurwa kugabanya amashanyarazi ya okiside ikomeye y’ibyuma by’ibanze byabaye intego mu gukora cyane,
Vuba aha, uburyo bushya bwo gutegura ibikoresho bya grafiti hakoreshejwe electrolysis y'umunyu ushongeshejwe bwakuruye abantu benshi.
Binyuze muri polarization ya cathodic na electrodeposition, ubwoko bubiri butandukanye bw'ibikoresho fatizo bya karuboni buhinduka ibikoresho bya nano-grafiti bifite agaciro kongerewe. Ugereranyije n'ikoranabuhanga risanzwe rya graphitization, uburyo bushya bwa graphitization bufite ibyiza byo kuba ubushyuhe buke bwa graphitization n'imiterere ishobora kugenzurwa.
Iyi nyandiko isuzuma iterambere rya graphitization hakoreshejwe uburyo bwa electrochemical, ishyira ahagaragara ubu buryo bushya, isesengura ibyiza n'ibibi byabwo, kandi iteganya uko bizagenda mu iterambere ry'ejo hazaza.
Ubwa mbere, uburyo bwo gupima umunyu ushongeshejwe hakoreshejwe electrolytic cathode
1.1 ibikoresho fatizo
Kugeza ubu, ibikoresho by'ingenzi bya grafiti y'ubukorano ni isale coke na pitch coke bifite urugero rwo hejuru rwa grafitis, ni ukuvuga ibisigazwa by'amavuta na tar y'amakara nk'ibikoresho fatizo bitanga ibikoresho byiza bya karuboni, bifite porosity nke, sulfur nke, ivu rike n'ibyiza byo gukoresha grafitis, nyuma yo kuyitegura muri grafiti ifite ubudahangarwa bwiza ku ngaruka, imbaraga nyinshi za mekanike, ubushobozi buke bwo kuyirwanya,
Ariko, ububiko buke bwa peteroli n'ihindagurika ry'ibiciro bya peteroli byabangamiye iterambere ryayo, bityo gushaka ibikoresho fatizo bishya byabaye ikibazo cyihutirwa kigomba gukemurwa.
Uburyo gakondo bwo gushushanya bufite imbogamizi, kandi uburyo butandukanye bwo gushushanya bukoresha ibikoresho fatizo bitandukanye. Ku bijyanye na karuboni idashushanyije, uburyo gakondo ntibushobora kuyishushanya, mu gihe formula ya electrochemical y'umunyu ushongeshejwe igabanya imbogamizi ku bikoresho fatizo, kandi ikwiriye ibikoresho hafi ya byose bisanzwe bya karuboni.
Ibikoresho gakondo bya karuboni birimo umukara wa karuboni, karuboni ikora, amakara, nibindi, muri byo amakara akaba ari yo meza cyane. Wino ishingiye ku makara ifata amakara nk'intangiriro hanyuma igategurwamo ibikoresho bya grafiti ku bushyuhe bwinshi nyuma yo kuyatunganya mbere.
Vuba aha, iyi nyandiko itanga uburyo bushya bwo gukoresha electrochemical, nka Peng, hakoreshejwe electrolysis y'umunyu ushongeshejwe, ntabwo bishoboka ko ishobora gutuma karuboni yirabura ihinduka kristali nyinshi ya graphite, electrolysis y'ibipimo bya graphite birimo utwuma twa graphite nanometer two mu ishusho y'urutugu, ifite ubuso bwihariye, iyo ikoreshejwe muri cathode ya bateri ya lithium yagaragaje imikorere myiza ya electrochemical kurusha graphite karemano.
Zhu n'abandi bashyize amakara adasukuye neza yavuwe muri sisitemu y'umunyu washongeshejwe ya CaCl2 kugira ngo akoreshwe muri electrolysis ku bushyuhe bwa 950 ℃, kandi bahinduye neza amakara adasukuye neza mo grafiti ifite kristali nyinshi, yagaragaje imikorere myiza n'ubuzima bw'igihe kirekire iyo yakoreshejwe nk'akantu ka anode ya bateri ya lithiamu ion.
Igerageza ryerekana ko bishoboka guhindura ubwoko butandukanye bw'ibikoresho gakondo bya karuboni mo grafiti hakoreshejwe electrolysis y'umunyu ushongeshejwe, ibi bikaba bifungura uburyo bushya bwa grafiti y'ubukorano mu gihe kizaza.
1.2 uburyo bwo
Uburyo bwo gupima umunyu ushongeshejwe bukoresha ibikoresho bya karuboni nka cathode kandi bukabihinduramo grafiti ifite ubutare bwinshi binyuze muri polarization ya kathodike. Muri iki gihe, inyandiko zihari zivuga ko gukuraho ogisijeni no gukosora atome za karuboni mu ntera ndende mu buryo bushobora guhindura polarization ya kathodike.
Kuba umwuka wa ogisijeni uri mu bikoresho bya karuboni bizabangamira imiterere ya graphitization ku rugero runaka. Mu buryo busanzwe bwo gukoresha graphitization, ogisijeni izakurwaho buhoro buhoro iyo ubushyuhe buri hejuru ya 1600K. Ariko, biroroshye cyane kuyikuraho binyuze mu gutandukanya kato.
Peng, n'abandi mu igerageza rya mbere bashyize imbere uburyo bwo gupima imiterere y'umunyu ushongeshejwe, ari bwo graphitization ahantu henshi ho gutangirira ni ukuba mu mikorosifero ya karuboni ikomeye/electrolyte, habanza gukorwa mikorosifero ya karuboni izengurutse igishishwa cya grafiti cy'umurambararo umwe, hanyuma atome za karuboni za karuboni zidahindagurika zigakwirakwira mu gice cyo hanze cya grafiti kidahindagurika, kugeza igihe gihinduwe burundu.
Uburyo bwo gukoresha graphitization bujyana no gukuraho ogisijeni, ibyo bikaba byemezwa n'igerageza.
Jin n'abandi nabo bagaragaje iki gitekerezo binyuze mu igerageza. Nyuma yo gushyira glucose muri karubone, hakozwe graphitization (17% by'umusemburo wa ogisijeni). Nyuma yo gushyira graphitization, imiterere ya karubone ikomeye (Ishusho ya 1a na 1c) yakoze igishishwa gifite imyenge kigizwe n'udupapuro twa nano twa graphite (Ishusho ya 1b na 1d).
Binyuze mu gusya imiyoboro ya karuboni (16% ya ogisijeni), imiyoboro ya karuboni ishobora guhindurwamo imiyoboro ya girafiti nyuma yo gusya hakurikijwe uburyo bwo guhindura ibintu bwavuzwe mu nyandiko.
Biringirwa ko, ingendo ndende iri munsi ya polarization ya atome za karuboni, grafiti nini ya kristu kugeza kuri amorphous carbone rerranging igomba gutunganya, graphite y’ubukorikori ifite ishusho yihariye y’amapetali, imiterere mito yungukiye kuri atome za ogisijeni, ariko uburyo bwihariye bwo kugira ingaruka ku miterere ya nanometer ya grafiti ntabwo busobanutse neza, nk'umwuka uturuka mu gitereko cya karuboni nyuma y'uko cathode ikora, nibindi.
Kugeza ubu, ubushakashatsi kuri iyi mikorere buracyari mu cyiciro cya mbere, kandi hakenewe ubundi bushakashatsi.
1.3 Imiterere ya graphite ikoze mu buryo bw'ibishushanyo
SEM ikoreshwa mu kureba imiterere y'ubuso bwa graphite, TEM ikoreshwa mu kureba imiterere y'imiterere iri munsi ya 0.2 μm, XRD na Raman spectroscopy ni bwo buryo bukoreshwa cyane mu kugaragaza imiterere mito ya graphite, XRD ikoreshwa mu kugaragaza amakuru ya kristale ya graphite, naho Raman spectroscopy ikoreshwa mu kugaragaza inenge n'urwego rwa graphite.
Hari imyenge myinshi muri grafiti itegurwa na cathode polarization ya electrolysis y'umunyu ushongeshejwe. Ku bikoresho fatizo bitandukanye, nka electrolysis y'umukara wa karuboni, haboneka imyenge mito imeze nk'uruti rw'umuhondo. Isesengura rya XRD na Raman spectrum rikorwa ku mukara wa karuboni nyuma ya electrolysis.
Ku bushyuhe bwa 827 ℃, nyuma yo kuvurwa na voltage ya 2.6V mu gihe cy'isaha 1, ishusho ya Raman spectral y'umukara wa karuboni iba hafi kimwe n'iya grafiti y'ubucuruzi. Nyuma y'uko umukara wa karuboni uvurwa n'ubushyuhe butandukanye, hapimwa uburebure bwa grafiti buhanitse (002). Agace k'umurambararo (002) kagaragaza urwego rw'icyerekezo cya carbone ihumura muri grafiti.
Uko urwego rwa karuboni rurushaho kuba rutyaye, ni ko rurushaho kwerekeza.
Zhu yakoresheje amakara yasukuwe nk'agace ka katose mu igerageza, maze imiterere mito y'ibicuruzwa bya graphite yahinduwe kuva ku mpandeshatu ijya ku rufatiro runini rwa graphite, kandi urwego rwa graphite rukomeye narwo rwagaragaye hifashishijwe mikorosikopi ya elegitoroniki ikoreshwa mu buryo bwo hejuru.
Muri Raman spectra, hamwe n’impinduka z’imiterere y’igerageza, agaciro ka ID/Ig na ko karahindutse. Iyo ubushyuhe bwa electrolytic bwari 950 ℃, igihe cya electrolytic cyari amasaha 6, naho voltage ya electrolytic yari 2.6V, agaciro ka ID/Ig ko hasi cyane kari 0.3, naho peak ya D yari hasi cyane ugereranyije na peak ya G. Muri icyo gihe, isura ya peak ya 2D yagaragazaga kandi ishyirwaho ry’imiterere ya grafiti itunganyijwe cyane.
Isonga ry’urusobe rw’amatara (002) mu ishusho ya XRD naryo ryemeza ko amakara make yahinduwe neza muri grafiti ifite ubukana bwinshi.
Mu gikorwa cyo gushushanya, kwiyongera k'ubushyuhe n'amashanyarazi bizagira uruhare mu kuzamura ikirere, ariko ingufu nyinshi cyane zigabanya umusaruro wa graphite, kandi ubushyuhe bwinshi cyane cyangwa igihe kirekire cyane cyo gushushanya ibyuma bizatuma umutungo upfa ubusa, bityo ku bikoresho bitandukanye bya karuboni, ni ngombwa cyane gusuzuma imiterere y'amashanyarazi ikwiye, ni nabyo bibandaho kandi bigoye.
Iyi nanostructure isa n'uruti ifite ubushobozi bwiza bwo gukoresha amashanyarazi. Umubare munini w'imyenge ituma iyoni zishyirwamo/zivamo vuba, bigatanga ibikoresho byiza bya cathode kuri bateri, n'ibindi. Kubwibyo, gukoresha electrochemical method graphitization ni uburyo bushoboka cyane bwo gukoresha graphitization.
Uburyo bwo gushyira electrode mu mwanya w'umunyu ushongeshejwe
2.1 Gushyira amashanyarazi muri dioxyde de carbone
Nk’imyuka ihumanya ikirere y’ingenzi cyane, CO2 nayo ni umutungo kamere udahumanya, nta kibazo, ihendutse kandi ishobora kongera gukoreshwa mu buryo bworoshye. Ariko, karuboni muri CO2 iri mu rugero rwo hejuru cyane rw’ingufu zikomoka ku bidukikije, bityo CO2 ifite ubushobozi bwo gupima ubushyuhe bwinshi, bigatuma bigorana kongera kuyikoresha.
Ubushakashatsi bwa mbere ku bijyanye no gushyira electrode ya CO2 mu mwanya wayo bushobora gukurikirwa mu myaka ya 1960. Ingram n'abandi bateguye neza karuboni kuri electrode ya zahabu muri sisitemu y'umunyu washongeshejwe ya Li2CO3-Na2CO3-K2CO3.
Van n'abandi bagaragaje ko ifu ya karuboni iboneka ku buryo butandukanye bwo kugabanya ibintu yari ifite imiterere itandukanye, harimo grafiti, karuboni idafite imvange na nanofibers za karuboni.
Binyuze mu gukusanya umunyu ushongeshejwe no gutegura uburyo bwo gutsinda ibikoresho bya karuboni, nyuma y'igihe kirekire abahanga mu bushakashatsi bibanze ku buryo bwo gushyiraho karuboni n'ingaruka z'imiterere ya electrolysis ku musaruro wa nyuma, harimo ubushyuhe bwa electrolytic, voltage ya electrolytic n'imiterere y'umunyu ushongeshejwe na electrodes, nibindi, gutegura ibikoresho bya grafiti bikora neza kugira ngo CO2 ishyirweho electrodes byashyizeho urufatiro rukomeye.
Mu guhindura electrolyte no gukoresha sisitemu y’umunyu ushongeshejwe ishingiye kuri CaCl2 ifite ubushobozi bwo gufata CO2 bwinshi, Hu n'abandi bateguye neza graphene ifite urwego rwo hejuru rwa graphitization na nanotubes za karuboni n'izindi nyubako za nanografitite biga imiterere ya electrolytic nko mu bushyuhe bwa electrolysis, imiterere ya electrode n'imiterere y'umunyu ushongeshejwe.
Ugereranyije na sisitemu ya karubone, CaCl2 ifite ibyiza byo kuba ihendutse kandi yoroshye kubona, ifite ubushobozi bwo gutwara ibintu bwinshi, yoroshye gushonga mu mazi, ndetse n'ubushobozi bwo gushonga cyane bwa iyoni za ogisijeni, ibyo bikaba bitanga uburyo bwo guhindura CO2 mo ibikomoka kuri grafiti bifite agaciro kongerewe.
2.2 Uburyo bwo guhindura
Gutegura ibikoresho bya karuboni byongerewe agaciro gakomeye hakoreshejwe electrode ya CO2 ikomoka ku munyu ushongeshejwe birimo cyane cyane gufata CO2 no kugabanya mu buryo butaziguye. Gufata CO2 byuzuzwa n'umunyu ushongeshejwe w'ubuntu wa O2- muri, nk'uko bigaragara muri Equation (1):
CO2+O2-→CO3 2- (1)
Kugeza ubu, hatanzwe uburyo butatu bwo kugabanya ibintu mu buryo butaziguye: uburyo bwo kugabanya ibintu mu buryo bw’intambwe imwe, uburyo bwo kugabanya ibintu mu buryo bw’intambwe ebyiri n’uburyo bwo kugabanya ibintu mu buryo bw’icyuma.
Uburyo bwo gukora inyito imwe bwatanzwe bwa mbere na Ingram, nk'uko bigaragara muri Equation (2):
CO3 2-+ 4E – →C+3O2- (2)
Uburyo bwo gusubiza ibintu mu buryo bw'intambwe ebyiri bwatanzwe na Borucka n'abandi, nk'uko bigaragara muri Equation (3-4):
CO3 2- + 2E - → CO2 2- + O2- (3)
CO2 2-+ 2E – →C+2O2- (4)
Uburyo bwo kugabanya ibyuma bwatanzwe na Deanhardt n'abandi. Bemezaga ko iyoni z'icyuma zabanje kugabanywamo icyuma muri cathode, hanyuma icyuma kikagabanywamo iyoni za karubone, nk'uko bigaragara muri Equation (5 ~ 6):
M- + E – →M (5)
4 m + M2CO3 – > C + 3 m2o (6)
Muri iki gihe, uburyo bwo gukora inyito imwe muri rusange bwemewe mu nyandiko zisanzweho.
Yin n'abandi bigaga sisitemu ya karubone ya Li-Na-K hamwe na nikeli nka cathode, dioxyde ya tin nka anode n'insinga y'ifeza nk'igikoresho cy'ingenzi, maze babona ishusho y'ikizamini cya voltammetry ya cyclic iri ku Ishusho ya 2 (igipimo cyo gupima cya 100 mV/s) kuri nikeli kathode, maze basanga hari uburebure bumwe gusa bwo kugabanuka (kuri -2.0V) mu gupima hasi.
Bityo rero, byafatwa umwanzuro ko habayeho igisubizo kimwe gusa mu gihe cyo kugabanya karubone.
Gao n'abandi babonye voltammetry imwe ya cyclic muri sisitemu imwe ya karubone.
Ge n'abandi bakoresheje anode idakora na cathode ya tungsten kugira ngo bafate CO2 muri sisitemu ya LiCl-Li2CO3 maze babona amashusho asa, kandi kugabanuka k'agahenge k'ingufu za karuboni byagaragaye gusa mu gupima nabi.
Mu buryo bw'umunyu washongeshejwe n'icyuma cya alkaline, ibyuma bya alkali na CO bizakorwa mu gihe karuboni ishyirwa muri cathode. Ariko, kubera ko imiterere ya thermodynamic y'uburyo karuboni ishyirwamo ari ntoya ku bushyuhe buri hasi, ni ukugabanuka kwa karuboni muri karuboni gusa bishobora kugaragara mu igerageza.
2.3 Gufata CO2 hakoreshejwe umunyu ushongeshejwe kugira ngo hategurwe ibikoresho bya grafiti
Ibintu bya graphite bifite agaciro gakomeye nka graphene na nanotubes za karuboni bishobora gutegurwa hakoreshejwe electrode ya CO2 iva mu munyu ushongeshejwe binyuze mu kugenzura imiterere y'igerageza. Hu n'abandi bakoresheje icyuma kitagira umugese nk'umunyu ushongeshejwe wa CaCl2-NaCl-CaO hanyuma bagashyirwamo electrolyze mu gihe cy'amasaha 4 munsi y'amashanyarazi ya 2.6V adahinduka ku bushyuhe butandukanye.
Kubera uburyo icyuma cyakoreshejwe mu gukamura ubutare n'ingaruka za CO hagati y'ibice bya graphite, graphene yabonetse ku buso bwa cathode. Uburyo bwo gutegura graphene bugaragara ku Ishusho ya 3.
Ifoto
Ubushakashatsi bwakurikiyeho bwongeyeho Li2SO4 hashingiwe kuri sisitemu y'umunyu wa CaCl2-NaClCaO ushongeshejwe, ubushyuhe bwa electrolysis bwari 625 ℃, nyuma y'amasaha 4 ya electrolysis, icyarimwe mu ishyirwa rya karuboni ryabonetsemo graphene na nanotubes za karuboni, ubushakashatsi bwagaragaje ko Li+ na SO4 2- bitanga ingaruka nziza kuri graphitization.
Sulfure nayo yinjizwa neza mu mubiri wa karuboni, kandi impapuro za grafiti nto cyane na karuboni ifite imigozi ishobora kuboneka hakoreshejwe kugenzura imiterere y'amashanyarazi.
Ibikoresho nk'ubushyuhe bwa electrolytic bwo hejuru no hasi kugira ngo habeho graphene ni ingenzi cyane, iyo ubushyuhe buri hejuru ya 800 ℃ bworoshye gukora CO aho gukora karuboni, hafi ya byose nta karuboni ishyirwamo iyo iri hejuru ya 950 ℃, bityo kugenzura ubushyuhe ni ingenzi cyane mu gukora graphene na nanotubes za karuboni, no gusubizaho uburyo bwo guhuza CO kugira ngo cathode ikore graphene ihamye.
Iyi mirimo itanga uburyo bushya bwo gutegura ibicuruzwa bya nano-grafiti hakoreshejwe CO2, bifite akamaro kanini mu gukemura imyuka ihumanya ikirere no gutegura graphene.
3. Incamake n'Icyerekezo
Bitewe n’iterambere ryihuse ry’inganda nshya z’ingufu, grafiti karemano ntiyashoboye guhaza ibyifuzo by’ubu, kandi grafiti y’ubukorano ifite imiterere myiza y’umubiri n’imiti kurusha grafiti karemano, bityo gukoresha grafiti ihendutse, ikora neza kandi itangiza ibidukikije ni intego y’igihe kirekire.
Uburyo bwa electrochemical bwo gushyira graphit mu bikoresho fatizo bikomeye n'ibikomoka ku mwuka hakoreshejwe uburyo bwa polarisation ya katodike no gushyiramo electrochemical byavuye mu bikoresho bya graphite bifite agaciro kongerewe, ugereranije n'uburyo gakondo bwo gushyira graphit, uburyo bwa electrochemical bufite imikorere myiza cyane, ingufu nke zikoreshwa, ibidukikije bibungabungwa n'ibidukikije, ku bikoresho bito bigengwa n'ibintu byatoranijwe icyarimwe, hakurikijwe imiterere itandukanye ya electrolysis, bishobora gutegurwa mu buryo butandukanye bw'imiterere ya graphite,
Itanga uburyo bwiza bwo guhindura ubwoko bwose bwa karuboni idafite imvange n'ibyuka bihumanya ikirere mu bikoresho by'agaciro bya grafiti kandi ifite amahirwe menshi yo kuyikoresha.
Kuri ubu, iri koranabuhanga riracyari mu ntangiriro. Hari ubushakashatsi buke ku bijyanye no gushyira mu gaciro hakoreshejwe uburyo bwa electrochemical, kandi haracyari inzira nyinshi zitazwi. Kubwibyo, ni ngombwa gutangirira ku bikoresho fatizo no gukora inyigo yuzuye kandi ihamye ku mashini zitandukanye zidafite ireme, kandi icyarimwe tugasuzuma imiterere ya thermodynamics n'impinduka za graphite mu buryo bwimbitse.
Ibi bifite akamaro kanini ku iterambere ry'inganda za grafiti mu gihe kizaza.
Igihe cyo kohereza: Gicurasi-10-2021