Abstract
Iibhetri zeLithium-ion (LIBs) zithathwa njengenye yezona zinto zibalulekileyo zokugcina amandla okugcina amandla.Njengoko uxinaniso lwamandla ebhetri lusanda, ukhuseleko lwebhetri lubaluleka ngakumbi ukuba amandla akhutshwe ngempazamo.Iingozi ezinxulumene nomlilo kunye nokudubula kwee-LIB kwenzeka rhoqo kwihlabathi jikelele.Abanye baye babangela izisongelo ezinzulu kubomi kunye nempilo yabantu kwaye bakhokelela ekukhunjulweni kwemveliso emininzi ngabavelisi.Ezi ziganeko zikhumbuza ukuba ukhuseleko luyimfuneko kwiibhetri, kwaye imiba enzulu kufuneka ixazululwe ngaphambi kokusetyenziswa kwenkqubo yebhetri ephezulu yamandla.Olu phononongo lujolise ekushwankatheleni iziseko zemvelaphi yemicimbi yokhuseleko ye-LIB kwaye iqaqambise inkqubela phambili engundoqo yakutsha nje kuyilo lwezixhobo zokuphucula ukhuseleko lwe-LIB.Silindele ukuba olu Phononongo luya kukhuthaza ukuphucuka ngakumbi kukhuseleko lwebhetri, ngakumbi kwii-LIB ezivelayo ezinoxinano lwamandla aphezulu.
IMVELAPHI YEMIBA YOKHUSELEKO LIB
Ulwelo lwe-electrolyte ephilayo ngaphakathi kwe-LIBs lunokutsha ngokwangaphakathi.Olunye lolona kusilela luyintlekele lwenkqubo ye-LIB sisiganeko sokubaleka kwe-thermal, esithathwa njengoyena nobangela wenkxalabo yokhuseleko lwebhetri.Ngokubanzi, ukubaleka kwe-thermal kwenzeka xa i-exothermic reaction iphuma kulawulo.Njengoko ubushushu bebhetri bunyuka ukuya kuthi ga kwi-80 ° C, isantya sokuphendula kweekhemikhali exothermic ngaphakathi kweebhetri siyanda kwaye sifudumeza ngakumbi iseli, okukhokelela kumjikelo wengxelo elungileyo.Ukunyuka kwamaqondo obushushu kunokubangela imililo kunye nokudubula, ngakumbi kwiibhetri ezinkulu.Ke ngoko, ukuqonda izizathu kunye neenkqubo zokubaleka kwe-thermal kunokukhokela ukuyilwa kwezinto ezisebenzayo zokuphucula ukhuseleko kunye nokuthembeka kwe-LIBs.Inkqubo yokubaleka kwe-thermal inokwahlulwa ibe ngamanqanaba amathathu, njengoko ishwankathelweUmzobo 1.
Umzobo 1 Izigaba ezintathu zenkqubo yokubaleka kwe-thermal.
Inqanaba loku-1: Ukuqala kokutshisa.Iibhetri zitshintsha ukusuka kwimeko eqhelekileyo ukuya kwimeko engaqhelekanga, kwaye ukushisa kwangaphakathi kuqala ukunyuka.Inqanaba 2: Ukuqokelelwa kobushushu kunye nenkqubo yokukhutshwa kwegesi.Ubushushu bangaphakathi buphakama ngokukhawuleza, kwaye ibhetri ifumana ukusabela okungaqhelekanga.Inqanaba 3: Ukutsha kunye nokudubula.I-electrolyte enokutsha iyatsha, ikhokelela kwimililo kunye nokudubula.
Ukuqala kobushushu obugqithisileyo (inqanaba 1)
I-Thermal runaway iqala ukusuka ekushiseni okugqithisileyo kwenkqubo yebhetri.Ukufudumala kokuqala kunokuthi kwenzeke ngenxa yokuba ibhetri ihlawuliswe ngaphaya kombane owenziweyo (i-overcharging), ukuvezwa kwamaqondo okushisa aphezulu, iisekethe ezimfutshane zangaphandle ngenxa yocingo oluphosakeleyo, okanye iisekethe ezimfutshane zangaphakathi ngenxa yeziphene zeseli.Phakathi kwazo, ukunqongophala kwangaphakathi sesona sizathu siphambili sokubaleka kwe-thermal kwaye kunzima ukulawula.Ushokoxeko lwangaphakathi lunokwenzeka kwiimeko zokutyunyuzwa kweeseli ezifana nokungena kobutyobo besinyithi;ukungqubana kwesithuthi;Ukwakhiwa kwe-lithium dendrite phantsi kokutshaja okuphezulu koxinano lwangoku, phantsi kweemeko zokutshaja okanye kumaqondo obushushu aphantsi;kunye nezahluli ezingalunganga ezenziwe ngexesha lokudibanisa ibhetri, ukukhankanya ezimbalwa.Umzekelo, ekuqaleni kuka-Okthobha ka-2013, imoto yakwaTesla kufutshane neSeattle yabetha inkunkuma yentsimbi eyagqobhoza ikhaka kunye nepakethe yebhetri.I-debris yangena kwii-polymer separators kwaye idibanisa ngokuthe ngqo i-cathode kunye ne-anode, ibangela ukuba ibhetri ihambe ngokukhawuleza kwaye ibambe umlilo;ngo-2016, i-Samsung Qaphela 7 imililo yebhetri ngenxa yesahluli esinamandla se-ultrathin esonakaliswe lula luxinzelelo lwangaphandle okanye i-welding burrs kwi-electrode ekhangayo, ebangela ukuba ibhetri ihambe ngokukhawuleza.
Ngexesha loku-1, ukusebenza kwebhetri kuyatshintsha ukusuka kwimeko yesiqhelo ukuya kwimeko engaqhelekanga, kwaye yonke imiba edweliswe ngasentla iya kubangela ukuba ibhetri ishushu kakhulu.Xa ubushushu bangaphakathi buqala ukunyuka, isigaba 1 siphela kwaye isigaba sesi-2 siqala.
Ukuqokelelwa kobushushu kunye nenkqubo yokukhutshwa kwegesi (inqanaba lesi-2)
Njengoko inqanaba lesi-2 liqala, iqondo lobushushu langaphakathi liyenyuka ngokukhawuleza, kwaye ibhetri ifumana oku kusabela kulandelayo (ezi mpendulo azenzeki ngendlela echanekileyo; ezinye zazo zinokwenzeka ngaxeshanye):
(1) Ukubola okuqinileyo kwe-electrolyte interphase (SEI) ngenxa yobushushu obugqithiseleyo okanye ukungena emzimbeni.Uluhlu lwe-SEI ikakhulu luqukethe i-stable (efana ne-LiF kunye ne-Li2CO3) kunye ne-metastable [njenge-polymers, i-ROCO2Li, (i-CH2OCO2Li) i-2, kunye ne-ROLi].Nangona kunjalo, iinxalenye ze-metastable zinokubola ngokugqithisileyo kwi-90 ° C, ikhupha iigesi ezinokutsha kunye ne-oxygen.Thatha (CH2OCO2Li)2 njengomzekelo
(CH2OCO2Li)2→Li2CO3+C2H4+CO2+0.5O2
(2) Ngokuchithwa kwe-SEI, ubushushu buyakha, kwaye isinyithi se-lithium okanye i-lithium edibeneyo kwi-anode iya kusabela kunye ne-solvents yezinto eziphilayo kwi-electrolyte, ikhupha iigesi ze-hydrocarbon ezinokutsha (i-ethane, i-methane, kunye nabanye).Oku kusabela kwe-exothermic eyenza ubushushu bunyuke ngakumbi.
(3) NiniT> ~ 130 ° C, i-polyethylene (PE) / i-polypropylene (PP) i-separator iqala ukunyibilika, eyona nto iphazamisa imeko kwaye ibangele isiphaluka esifutshane phakathi kwe-cathode kunye ne-anode.
(4) Ekugqibeleni, ukushisa kubangela ukubola kwe-lithium metal oxide cathode kwaye kubangele ukukhululwa kweoksijini.Thatha i-LiCoO2 njengomzekelo, enokubola ukuqala kwi- ~ 180 ° C ngolu hlobo lulandelayo
Ukuqhekeka kwe-cathode kukwagqithise kakhulu, kwandisa ubushushu kunye noxinzelelo kwaye, ngenxa yoko, ukukhawulezisa ukusabela.
Ngexesha le-2, ubushushu buyanda kwaye ioksijini iqokelela ngaphakathi kweebhetri.Inkqubo yokubaleka kwe-thermal iqhubeka ukusuka kwinqanaba lesi-2 ukuya kwinqanaba le-3 ngokukhawuleza ukuba i-oksijini eyaneleyo kunye nobushushu buqokelele ukutshiswa kwebhetri.
Ukutsha kunye nokudubula (inqanaba lesi-3)
Kwinqanaba lesi-3, ukutshisa kuqala.I-electrolyte ye-LIBs zi-organic, eziphantse zibe yintlanganisela ye-cyclic kunye ne-linear alkyl carbonates.Zinokuguquguquka okuphezulu kwaye zinokutsha kakhulu ngaphakathi.Ukuthatha i-carbonate electrolyte ethandwa kakhulu esetyenziswayo [umxube we-ethylene carbonate (EC) + dimethyl carbonate (DMC) (1: 1 ngobunzima)] njengomzekelo, ibonisa uxinzelelo lomphunga we-4.8 kPa kwiqondo lokushisa kunye neqondo eliphantsi kakhulu. ye-25 ° ± 1 ° C kuxinzelelo lomoya we-1.013 bar.Ioksijini ekhutshiweyo kunye nobushushu kwinqanaba lesi-2 libonelela ngeemeko ezifunekayo zokutsha kwee-electrolyte eziphilayo ezivuthayo, ngaloo ndlela kubangele iingozi zomlilo okanye ukuqhuma.
Kwinqanaba lesi-2 kunye nelesi-3, ukusabela kwe-exothermic kwenzeka phantsi kweemeko ezikufutshane ne-adiabatic.Ke, i-accelerated rate rate calorimetry (ARC) yindlela esetyenziswa ngokubanzi elinganisa okusingqongileyo ngaphakathi kwee-LIBs, eququzelela ukuqonda kwethu i-thermal runaway reaction kinetics.Umfanekiso wesi-2ibonisa igophe eqhelekileyo ye-ARC ye-LIB erekhodiweyo ngexesha lovavanyo lokuxhatshazwa kwe-thermal.Ukulinganisa ukunyuka kweqondo lokushisa kwinqanaba le-2, umthombo wangaphandle wokushisa unyusa ubushushu bebhetri ukuya kwiqondo lokushisa lokuqala.Ngaphezulu kolu bushushu, i-SEI iyabola, nto leyo eya kubangela ukusabela kweekhemikhali ezingaphezulu.Ekugqibeleni, umahluli uya kunyibilika.Izinga lokuzifudumeza liya kunyuka emva koko, likhokelela ekubalekeni kwe-thermal (xa izinga lokuzifudumeza lingaphezulu kwe-10 ° C / min) kunye nokutsha kwe-electrolyte (isigaba 3).
I-anode yi-mesocarbon microbead graphite.I-cathode yi-LiNi0.8Co0.05Al0.05O2.I-electrolyte yi-1.2 M LiPF6 kwi-EC/PC/DMC.Kwasetyenziswa iCelgard 2325 trilayer separator.Ihlengahlengiswe ngemvume evela kwi-Electrochemical Society Inc.
Kufuneka kuqatshelwe ukuba iimpendulo eziboniswe ngasentla azenzeki ngokungqongqo emva kwenye ngokulandelelana kwazo.Yimiba, endaweni yoko, entsonkothileyo kwaye ecwangcisiweyo.
IZINTO EZIPHUCILEYO UKHUSELEKO LWEBHETRI
Ngokusekwe ekuqondeni ukubaleka kwebhetri eshushu, iindlela ezininzi ziyaphononongwa, ngenjongo yokunciphisa iingozi zokhuseleko ngoyilo olunengqiqo lwamalungu ebhetri.Kumacandelo alandelayo, sishwankathela iindlela zemathiriyeli ezahlukeneyo zokuphucula ukhuseleko lwebhetri, ukusombulula iingxaki ezihambelana nezigaba ezahlukeneyo zokubaleka kwe-thermal.
Ukusombulula iingxaki kwisigaba 1 (ukuqala kokutshisa)
Izinto ezithembekileyo ze-anode.Ukwakhiwa kwe-Li dendrite kwi-anode ye-LIB iqalisa inqanaba lokuqala lokubaleka kwe-thermal.Nangona lo mbandela uncitshisiwe kwii-anodes ze-LIBs zorhwebo (umzekelo, i-carbonaceous anodes), i-Li dendrite formation ayizange ivinjwe ngokupheleleyo.Ngokomzekelo, kwii-LIBs zorhwebo, i-dendrite deposition iyenzeka ngokukhethekileyo kwi-graphite electrode edges ukuba i-anodes kunye ne-cathodes ayidityaniswanga kakuhle.Ukongezelela, iimeko zokusebenza ezingafanelekanga ze-LIB nazo zingabangela i-Li metal deposition kunye nokukhula kwe-dendrite.Kuyaziwa ukuba i-dendrite inokubunjwa ngokulula ukuba ibhetri ihlawuliswa (i) kwiindawo ezixinzelelekileyo zangoku apho i-deposition ye-Li metal ikhawuleza kunokusasazwa kwe-Li ions kwi-graphite eninzi;(ii) phantsi kweemeko zokutshaja kakhulu xa igraphite ingaphezulu;kunye (iii) kumaqondo obushushu aphantsi [umzekelo, iqondo lobushushu elingaphantsi (~0°C)], ngenxa yokwanda kwe-viscosity yolwelo lwe-electrolyte kunye nokwanda kokunganyangeki kwe-Li-ion diffusion.
Ukusuka kwindawo yokujonga izinto eziphathekayo, imvelaphi yengcambu emisela ukuqala kokukhula kwe-Li dendrite kwi-anode yi-SEI engazinzanga kunye ne-nonuniform, ebangela ukusabalalisa ngokungafaniyo kwendawo.Amacandelo e-Electrolyte, ngokukodwa izongezo, ziye zaphandwa ukuze kuphuculwe ukufana kwe-SEI kunye nokuphelisa ukubunjwa kwe-Li dendrite.Izongezo eziqhelekileyo ziquka i-inorganic compounds [umzekelo, i-CO2, i-LiI, njl.] kunye ne-organic compounds equkethe iibhondi ze-carbon unsaturated ezifana ne-vinylene carbonate kunye ne-additives maleimide;iimolekyuli ze-cyclic ezingazinzanga ezifana ne-butyrolactone, i-ethylene sulfite, kunye ne-derivatives yazo;kunye ne-fluorinated compounds ezifana ne-fluoroethylene carbonate, phakathi kwabanye.Nangona kwinqanaba lesigidi-ngesigidi, ezi molekyuli zisenokuphucula i-morphology ye-SEI, ngaloo ndlela i-homogenizing i-Li-ion flux kunye nokuphelisa ukuba nokwenzeka kwe-Li dendrite formation.
Ngokubanzi, imingeni ye-Li dendrite isekho kwi-graphite okanye i-carbonaceous anodes kunye ne-silicon / i-SiO equlethe i-anodes yesizukulwana esilandelayo.Ukusombulula umba wokukhula kwe-Li dendrite ngumngeni obaluleke kakhulu ukulungelelaniswa kwe-high-energy density Li-ion chemistries kungekudala.Kufuneka kuqatshelwe ukuba, kutshanje, iinzame ezinkulu ziye zanikezelwa ekusombululeni umba we-Li dendrite ukubunjwa kwi-anode ye-metal ecocekileyo ye-Li nge-homogenizing i-Li-ion flux ngexesha lokufakwa kwe-Li;umzekelo, i-coating layer coating , i-artificial SEI engineering , njl. Kule nkalo, ezinye zeendlela zinokuthi zikhanyise indlela yokujongana nomcimbi kwii-anode ze-carbonaceous kwii-LIB ngokunjalo.
Ii-electrolyte zolwelo ezisebenzayo kunye nezahluli.I-electrolyte engamanzi kunye ne-separator idlala indima ephambili ekwahluleni ngokwasemzimbeni i-cathode ephezulu yamandla kunye ne-anode.Ngaloo ndlela, i-electrolytes esebenzayo kunye ne-separators eyenzelwe kakuhle inokukhusela ngokuphawulekayo iibhetri kwinqanaba lokuqala le-thermal runaway (isigaba 1).
Ukukhusela iibhetri kwi-mechanical crushing, i-shear thickening liquid electrolyte ifunyenwe ngokongezwa okulula kwe-silica evuthayo kwi-carbonate electrolyte (1 M LiFP6 kwi-EC / DMC) .Phezu koxinzelelo lomatshini okanye impembelelo, ulwelo lubonisa isiphumo sokuchetywa kwe-shear ngokunyuka kwe-viscosity, ngoko ke ukulahla amandla empembelelo kunye nokubonisa ukunyamezela ukutyumza (Isazobe 3A)
Umzobo 3 Amaqhinga okusombulula imiba ekwinqanaba loku-1.
(A) Shear thickening electrolyte.Phezulu: Kwi-electrolyte eqhelekileyo, impembelelo yomatshini inokukhokelela kushokoxeke lwangaphakathi lwebhetri, okubangela imililo kunye nokudubula.Emazantsi: Inoveli ye-smart electrolyte enesiphumo sokucheba ukutyeba phantsi koxinzelelo okanye impembelelo ibonisa unyamezelo olugqwesileyo lokutyumza, olunokuphucula ngokubonakalayo ukhuseleko lomatshini lweebhetri.(B) I-Bifunctional separators ukufumanisa kwangaphambili i-lithium dendrites.Ukwakhiwa kwe-Dendrite kwibhetri ye-lithium yendabuko, apho ukungena okupheleleyo kwesahluli nge-lithium dendrite kuchongwa kuphela xa ibhetri ingaphumeleli ngenxa yesiphaluka esifutshane sangaphakathi.Xa kuthelekiswa, ibhetri ye-lithium ene-bifunctional separator (ebandakanya umaleko oqhubayo phakathi kwezahluli ezimbini eziqhelekileyo), apho i-lithium dendrite ekhule kakhulu ingena kwisahluli kwaye yenza uqhagamshelwano kunye nomgangatho wobhedu oqhubayo, okubangela ukuhla.VCu−Li, esebenza njengesilumkiso sokusilela okuzayo ngenxa yesekethe emfutshane yangaphakathi.Nangona kunjalo, ibhetri epheleleyo ihlala isebenza ngokukhuselekileyo kunye ne-nonzero.(A) kunye no (B) zihlengahlengiswa okanye zenziwe kwakhona ngemvume evela kwiSpringer Nature.(C) Isahluli se-Trilayer ukusebenzisa i-Li dendrites enobungozi kunye nokwandisa ubomi bebhetri.Ekhohlo: I-lithium anode inokwenza ngokulula iidiphozithi ze-dendritic, ezinokukhula ngokuthe ngcembe zibe nkulu kwaye zingene kwisahluli se-polymer engasebenziyo.Xa i-dendrites ekugqibeleni idibanisa i-cathode kunye ne-anode, ibhetri ifutshane kwaye iyasilela.Ekunene: Umaleko we-silica nanoparticles wadityaniswa ngamacandelo amabini eezahluli zepolymer zorhwebo.Ngoko ke, xa i-lithium dendrites ikhula kwaye ingena kwi-separator, iya kuqhagamshelana ne-silica nanoparticles kwi-sandwiched layer kwaye isetyenziswe nge-electrochemically.(D) Ukuskena i-electron microscopy (SEM) umfanekiso we-silica nanoparticle sandwiched separator.(E) I-voltage eqhelekileyo kunye nexesha leprofayili ye-Li / Li yebhetri ene-separator eqhelekileyo (i-curve ebomvu) kunye ne-silica nanoparticle sandwiched trilayer separator (i-black curve) ihlolwe phantsi kweemeko ezifanayo.(C), (D), kunye (E) ziphinda zenziwe kwakhona ngemvume evela kuJohn Wiley kunye noNyana.(F) Umzobo wenkqubo yezongezo ze-redox shuttle.Kumphezulu we-cathode egcwele kakhulu, isongezo se-redox sidityaniswa kwifom [O], eya kuthi emva koko icuthwe ibuyele kwimeko yayo yangaphambili [R] kumphezulu we-anode ngokusasazwa nge-electrolyte.Umjikelo we-electrochemical we-oxidation-diffusion-reduction-diffusion inokugcinwa ngokungenasiphelo kwaye ngenxa yoko itshixa amandla e-cathode ekutshajweni okuyingozi.(G) Izakhiwo zeekhemikhali eziqhelekileyo zezongezo ze-shuttle redox.(H) Inkqubo yokuvalwa kwethaji yongeziweyo enokuthi i-electrochemically polymerize ngesakhono esiphezulu.(I) Ulwakhiwo lwekhemikhali oluqhelekileyo lwezongezo zentlawulo egqithileyo yokuvala.Amandla okusebenza ezongezo adweliswe phantsi kwesakhiwo ngasinye se-molecular (G), (H), kunye (I).
Abahluli banokufaka i-electronic insulate i-cathode kunye ne-anode kwaye badlale indima ebalulekileyo ekubekeni iliso kwimeko yempilo yebhetri kwindawo yokukhusela ukuthintela ukuwohloka okuqhubekayo kwisigaba esidlulileyo 1. Ngokomzekelo, "i-bifunctional separator" kunye ne-polymer-metal-polymer trilayer configuration (Isazobe 3B) inokubonelela ngomsebenzi omtsha wokuva amandla ombane.Xa i-dendrite ikhula kwaye ifikelela kumaleko aphakathi, iya kudibanisa umaleko wesinyithi kunye ne-anode kangangokuba ukuhla kombane ngequbuliso phakathi kwabo kunokubonwa ngokukhawuleza njengemveliso.
Ngaphandle kokuchongwa, isahluli setrilayer yayiyilelwe ukusebenzisa i-Li dendrites eyingozi kwaye icothise ukukhula kwazo emva kokungena kwisahluli.Umaleko we-silica nanoparticles, ehlanganiswe ngamacandelo amabini eezahluli zepololefin yorhwebo (Umzobo 3, C kunye no-D), inokusebenzisa nayiphi na i-Li dendrites eyingozi engena ngaphakathi, ngaloo ndlela iphucula ngokufanelekileyo ukhuseleko lwebhetri.Ubomi bebhetri ekhuselweyo bandiswa kakhulu malunga namaxesha amahlanu xa kuthelekiswa nezahlukanisi eziqhelekileyo (Isazobe 3E).
Ukhuseleko lokuntywila.Ukutshaja ngaphezulu kuchazwa njengokutshaja ibhetri ngaphaya kwamandla ombane ayiliweyo.Ukugqithiswa kwe-overcharging kunokubangelwa nguxinzelelo oluphezulu oluphezulu lwangoku, iiprofayili zokutshaja ezinobundlobongela, njl. njl., ezinokuzisa uluhlu lweengxaki, kubandakanywa (i) ukufakwa kwe-Li metal kwi-anode, echaphazela kakhulu ukusebenza kwebhetri ye-electrochemical kunye nokhuseleko;(ii) ukubola kwesixhobo se-cathode, ukukhulula ioksijini;kunye (iii) nokubola kwe-electrolyte ephilayo, ukukhupha ubushushu kunye neemveliso zegesi (i-H2, ii-hydrocarbons, i-CO, njl. njl.), ezinoxanduva lokubaleka kwe-thermal.Iimpendulo ze-electrochemical ngexesha lokubola ziyinkimbinkimbi, ezinye zazo zidweliswe ngezantsi.
I-asterisk (*) ibonisa ukuba igesi ye-hydrogen ivela kwi-protic, ishiya amaqela avelisiweyo ngexesha le-oxidation ye-carbonates kwi-cathode, ethi ke isasazeke kwi-anode ukuba iyancipha kwaye ivelise i-H2.
Ngokwesiseko somahluko kwimisebenzi yabo, izongezo zokukhusela i-overcharge zingahlelwa njengezongezo ze-shuttle redox kunye nezongezo zokuvala.Eyangaphambili ikhusela iseli ekutshajisweni ngokugqithisileyo ngokubuyisela umva, ngelixa le yokugqibela iphelisa ukusebenza kweeseli ngokusisigxina.
Izongezo ze-redox shuttle zisebenza ngokuthintela i-electrochemically charge etofelweyo ebhetrini xa kusenzeka intlawulo egqithisileyo.Njengoko kubonisiwe kwiIsazobe 3F, umatshini usekelwe kwi-additive redox ene-oxidation enokuthi ibe ngaphantsi kancinane kune-electrolyte anodic decomposition.Kumphezulu we-cathode egcwele kakhulu, isongezo se-redox sidityaniswa kwifom [O], eya kuthi emva koko icuthwe ibuyele kwimeko yayo yangaphambili [R] kumphezulu we-anode emva kokusasazwa nge-electrolyte.Emva koko, isongezelelo esincitshisiweyo sinokusasazeka sibuyele kwi-cathode, kwaye umjikelo we-electrochemical "we-oxidation-diffusion-reduction-diffusion" unokugcinwa ngokungenasiphelo kwaye ngenxa yoko uvalela amandla e-cathode ekutshajweni okuyingozi ngakumbi.Uphando lubonise ukuba amandla e-redox yezongezo kufuneka abe malunga ne-0.3 ukuya kwi-0.4 V ngaphezu kwamandla e-cathode.
Uluhlu lwezongezo ezinemichiza elungelelaniswe kakuhle kunye namandla e-redox aphuhlisiwe, kubandakanywa i-organometallic metallocenes, phenothiazines, triphenylamines, dimethoxybenzenes kunye nezinto eziphuma kuzo, kunye ne-2-(pentafluorophenyl) -tetrafluoro-1,3,2-benzodiodioUmzobo 3G).Ngokulungelelanisa izakhiwo ze-molecular, i-additive oxidation potentials inokuthi ifakwe ngaphezulu kwe-4 V, efanelekileyo ekuphuhliseni ngokukhawuleza izixhobo ze-cathode ze-high-voltage kunye ne-electrolytes.Umgaqo osisiseko woyilo ubandakanya ukuthoba eyona orbital yemolekyuli ehlala iphezulu yesongezo ngokongeza izinto ezithatha indawo ye-electron-withdrawing substitutes, okukhokelela ekwandeni kwe-oxidation enokwenzeka.Ngaphandle kwezongezo ze-organic, ezinye iityuwa ze-inorganic, ezingenakusebenza njengetyuwa ye-electrolyte kuphela kodwa zinokusebenza njenge-shuttle ye-redox, njenge-perfluoroborane cluster salts [oko kukuthi, i-lithium fluorododecaborates (Li2B12F)xH12−x)], zikwafunyanwe njengezongezo ezisebenzayo ze-redox shuttle.
Izongezo zokutshajiswa kwentlawulo egqithisileyo ziludidi lwezongezo ezingenakubuyiseka zokhuseleko lokutshajiswa.Zisebenza mhlawumbi ngokukhupha irhasi kumandla aphezulu, athi ke, avule isixhobo sangoku sokuphazamisa, okanye ngokusisigxina i-electrochemically polymerizing kumandla aphezulu okuphelisa ukusebenza kwebhetri ngaphambi kokuba kwenzeke intlekele.Isazobe 3H).Imizekelo yangaphambili ibandakanya i-xylene , cyclohexylbenzene, kunye ne-biphenyl , ngelixa imizekelo yamva iquka i-biphenyl kunye nezinye iikhompawundi ezinuka kamnandi endaweni yazo (Isazobe 3I).Imiphumo emibi yezongezo ezivaliweyo zisengumsebenzi wexesha elide kunye nokusebenza kokugcinwa kwe-LIBs ngenxa ye-oxidation engaguqukiyo yale mixube.
Ukusombulula iingxaki kwisigaba 2 (ukuqokelela ubushushu kunye nenkqubo yokukhutshwa kwegesi)
Izinto ezithembekileyo ze-cathode.Ii-oxide zetsimbi ze-Lithium, ezifana nee-oxides ezicwangcisiweyo ze-LiCoO2, i-LiNiO2, kunye ne-LiMnO2;i-spinel-type oxide LiM2O4;kunye nohlobo lwe-polyanion ye-LiFePO4, zisetyenziswa ngokuxhaphakileyo izixhobo ze-cathode, ezinokuthi, nangona kunjalo, zinemiba yokhuseleko ngakumbi kumaqondo obushushu aphezulu.Phakathi kwabo, i-olivine-structured LiFePO4 ikhuselekile, ezinzileyo ukuya kwi-400 ° C, ngelixa i-LiCoO2 iqala ukubola kwi-250 ° C.Isizathu sokhuseleko oluphuculweyo lwe-LiFePO4 kukuba zonke ii-ion ze-oksijini zenza i-covalent bonds eqinile kunye ne-P5 + ukwenza i-PO43-tetrahedral polyanions, ezinzisa yonke isakhelo se-three-dimensional kunye nokubonelela ngokuzinza okuphuculweyo xa kuthelekiswa nezinye izinto ze-cathode, nangona kusekho. kuye kwachazwa iingozi zomlilo webhetri.Inkxalabo enkulu yokhuseleko ivela ekuhleni kwezi zinto ze-cathode kumaqondo okushisa aphakamileyo kunye nokukhululwa kwe-oksijini ngaxeshanye, oku kunye kunokukhokelela ekutshiseni kunye nokuqhuma, ukuphazamisa kakhulu ukhuseleko lwebhetri.Ngokomzekelo, i-crystal structure ye-oxide elayishiweyo ye-LiNiO2 ayizinzile ngenxa yobukho be-Ni2 +, ubukhulu be-ionic obufana ne-Li +.ULi ophelelwe lithembaxNiO2 (x<1) ithambekele ekuguquleni kwisigaba esizinzile ngakumbi se-spinel-type LiNi2O4 (spinel) kunye ne-rocksalt-type NiO, kunye ne-oksijini ekhutshwe kwi-electrolyte engamanzi malunga ne-200 ° C, ekhokelela ekutshisweni kwe-electrolyte.
Iinzame ezinkulu zenziwe ukuphucula ukuzinza kwe-thermal kwezi zinto ze-cathode nge-athomu ye-doping kunye neengubo zokukhusela ezingaphezulu.
I-Atom doping inokunyusa kakhulu ukuzinza kwe-thermal yezinto ezifakwe kwi-oxide ngenxa yeziphumo ezizinzileyo zekristale.Ukuzinza kwe-thermal ye-LiNiO2 okanye i-Li1.05Mn1.95O4 inokuphuculwa kakhulu ngokufakela indawo ye-Ni okanye i-Mn kunye nezinye ii-cations zetsimbi, ezifana ne-Co, Mn, Mg, kunye ne-Al.Kwi-LiCoO2, ukuqaliswa kwe-doping kunye ne-alloying elements ezifana ne-Ni kunye ne-Mn inokunyusa kakhulu ubushushu bokuqala kokubola.Tdec, ngelixa unqanda ukuphendula nge-electrolyte kumaqondo obushushu aphezulu.Nangona kunjalo, ukwanda kozinzo lwe-cathode thermal ngokubanzi kuza kunye nemibingelelo kwisikhundla esithile.Ukusombulula le ngxaki, i-concentration-gradient cathode material for rechargeable lithium batterys based on a layered lithium nickel cobalt manganese oxide iye yaphuhliswa (Isazobe 4A).Kulo mbandela, i-particle nganye ine-Ni-rich central bulk kunye ne-Mn-rich yangaphandle umaleko, kunye nokunciphisa ugxininiso lwe-Ni kunye nokwandisa i-Mn kunye ne-Co njengoko isondela kumphezulu (Isazobe 4B).Owokuqala ubonelela ngomthamo ophezulu, ngelixa umva uphucula ukuzinza kwe-thermal.Le noveli imathiriyeli ye-cathode yaboniswa ukuphucula ukhuseleko lweebhetri ngaphandle kokuphazamisa ukusebenza kwazo kwe-electrochemical (Umzobo 4C).
Umzobo 4 Amaqhinga okusombulula imiba kwinqanaba lesi-2: Iikhathodi ezithembekileyo.
(A) I-Schematic diagram ye-electrode particle ene-Ni-rich core ejikelezwe yi-concentration-gradient yangaphandle.Isuntswana ngalinye lineNi-rich central bulk Li(Ni0.8Co0.1Mn0.1)O2 kunye ne-Mn-rich outer layer [Li(Ni0.8Co0.1Mn0.1)O2] ngokuncipha kwe-Ni concentration kunye nokwandisa iMn and Co concentrations njengoko umphezulu usondela.Owokuqala ubonelela ngomthamo ophezulu, ngelixa umva uphucula ukuzinza kwe-thermal.Ukwakheka okuqhelekileyo nguLi (Ni0.68Co0.18Mn0.18) O2.I-electron micrograph yokuskena yesuntswana eqhelekileyo nayo ibonisiwe ngasekunene.(B) Iziphumo ze-Electron-probe x-ray microanalysis ze-lithiated oxide yokugqibela Li (Ni0.64Co0.18Mn0.18) O2.Utshintsho oluthe ngcembe lwe-Ni, Mn, kunye ne-Co kwi-interlayer luyabonakala.I-concentration ye-Ni iyancipha, kwaye i-Co kunye ne-Mn concentrations inyuka ukuya phezulu.(C) I-calorimetry yokuskena eyahlukileyo (i-DSC) ibonisa ukuhamba kobushushu ukusuka kwi-reaction ye-electrolyte kunye ne-concentration-gradient material Li (Ni0.64Co0.18Mn0.18) O2, i-Ni-rich central material Li (Ni0.8Co0.1Mn0. I-1) i-O2, kunye ne-Mn-rich layer yangaphandle [Li (Ni0.46Co0.23Mn0.31) O2].Izixhobo zahlawuliswa kwi-4.3 V. (A), (B), kunye (C) ziphinda zenziwe ngemvume evela kwi-Springer Nature.(D) Ekhohlo: Ukuhanjiswa kwe-electron microscopy (TEM) umfanekiso oqaqambileyo webala le-AlPO4 nanoparticle-coated LiCoO2;I-energy dispersive x-ray spectrometry iqinisekisa iAl kunye ne-P kumaleko wokugquma.Ekunene: Isisombululo esiphezulu se-TEM umfanekiso obonisa i-AlPO4 nanoparticles (~3 nm ububanzi) kwi-nanoscale coating layer;iintolo zibonisa ujongano phakathi kwe AlPO4 layer kunye ne LiCoO2.(E) Ekhohlo: Umfanekiso weseli equlethe i-cathode ye-LiCoO2 engenanto emva kovavanyo lwe-12-V ye-overcharge.Iseli yatsha kwaye yaqhuma kuloo mbane.Ekunene: Umfanekiso weseli equlethe i-AlPO4 nanoparticle-coated LiCoO2 emva kovavanyo lwe-12-V ye-overcharge.(D) kunye no (E) zenziwe kwakhona ngemvume evela kuJohn Wiley kunye noonyana.
Esinye isicwangciso sokuphucula ukuzinza kwe-thermal kukugubungela izinto ze-cathode kunye nokukhusela okucekethekileyo kwe-thermal stable Li + eqhuba iikhompawundi, ezinokuthintela uqhagamshelwano oluthe ngqo lwezinto ze-cathode kunye ne-electrolyte kwaye ngaloo ndlela unciphise ukuphendula kwecala kunye nokuveliswa kobushushu.Iingubo ezinokuthi zibe yifilimu ye-inorganic [umzekelo, i-ZnO, i-Al2O3, i-AlPO4, i-AlF3, njl.], ekwazi ukuqhuba i-Li ions emva kokuba i-lithiated (Umzobo 4, D kunye no-E), okanye iifilimu eziphilayo, ezifana ne-poly (diallyldimethylammonium chloride), iifilimu ezikhuselayo ezenziwe nge-γ-butyrolactone additives, kunye ne-multicomponent additives (ezibandakanya i-vinylene carbonate, i-1,3-propylene sulfite, kunye ne-dimethylacetamide) .
Ukwazisa i-coefficient ye-coefficient yeqondo lokushisa elichanekileyo lisebenza ngokunyusa ukhuseleko lwe-cathode.Umzekelo, i-poly(3-decylthiophene)-coated LiCoO2 cathodes inokuvala i-electrochemical reactions kunye ne-side reactions xa iqondo lobushushu liphakama ukuya kuma->80 ° C, njengoko umaleko wepolymer oqhubayo unokutshintsha ngokukhawuleza ukuya kwimeko yokumelana kakhulu.Iingubo ze-oligomers eziziphelisayo kunye ne-hyper-branched architecture nazo zinokusebenza njengomaleko othinteleyo ophendula ngokufudumeleyo ukuvala ibhetri kwicala le-cathode.
Umqokeleli wangoku oguqukayo ngokushushu.Ukuvalwa kweempendulo ze-electrochemical ngexesha lokunyuka kobushushu bebhetri kwinqanaba lesi-2 kunokuthintela ngokufanelekileyo ubushushu ukuba bunyuke ngakumbi.Ukutshintshwa kwe-polymer ekhawulezayo kunye nokuguqulwa kwe-thermoresponsive (TRPS) ifakwe ngaphakathi kumqokeleli wangoku (Isazobe 5A).Ifilimu encinci ye-TRPS iqulethe i-graphene-coated spiky nanostructured nickel (GrNi) eqhubayo njenge-conductive filler kunye ne-PE matrix ene-coefficient yokwandisa i-thermal (α ~ 10−4 K-1).Iifilimu ezihlanganisiweyo zepolymer ezenziweyo zibonisa ukuhanjiswa okuphezulu (σ) kwiqondo lobushushu begumbi, kodwa xa ubushushu busondela kubushushu bokutshintsha (Ts), i-conductivity iyancipha ngaphakathi kwe-1 nge-7 ukuya kwii-oda ezisibhozo zobukhulu ngenxa yokwandiswa kwevolumu ye-polymer, eyahlula amaqhekeza okuqhuba kunye nokuphula iindlela zokuqhuba (Isazobe 5B).Ifilimu ngoko nangoko iba yi-insulating kwaye iphelisa ukusebenza kwebhetri (Umzobo 5C).Le nkqubo ibuyekezwa kakhulu kwaye inokusebenza nasemva kweziganeko ezininzi zokufudumeza ngaphandle kokuphazamisa ukusebenza.
Umzobo 5 Amacebo okusombulula imiba ekwinqanaba lesi-2.
(A) Umzobo weskimu wendlela yokutshintsha i-thermal yomqokeleli wangoku we-TRPS.Ibhetri ekhuselekileyo inomqokeleli omnye okanye ezimbini zangoku ezigqunywe ngomaleko obhityileyo weTRPS.Isebenza ngokuqhelekileyo kwiqondo lokushisa.Nangona kunjalo, kwimeko yokushisa okuphezulu okanye umbane omkhulu, i-matrix ye-polymer iyanda, ngaloo ndlela ihlula iinqununu ze-conductive, ezinokunciphisa ukuqhutyelwa kwayo, ukwandisa kakhulu ukuchasana kwayo kunye nokuvala ibhetri.Ulwakhiwo lwebhetri lunokukhuselwa ngaphandle komonakalo.Ekupholiseni, i-polymer iyashwabana kwaye iphinde ibuyisele iindlela zokuqala zokuqhuba.(B) Ukutshintshwa kwe-resistivity yeefilimu ezahlukeneyo ze-TRPS njengomsebenzi weqondo lokushisa, kubandakanywa i-PE / GrNi kunye nokulayisha okuhlukeneyo kwe-GrNi kunye ne-PP / GrNi kunye ne-30% (v / v) yokulayishwa kwe-GrNi.(C) Isishwankathelo somthamo webhayisekile ekhuselekileyo ye-LiCoO2 phakathi kwe-25°C kunye nokuvalwa.Umthamo okufutshane-zero kwi-70 ° C ubonisa ukucinywa ngokupheleleyo.(A), (B), kunye (C) ziphinda zenziwe kwakhona ngemvume evela kwiSpringer Nature.(D) Umelo olucwangcisiweyo lwengqikelelo yokuvala esekwe kwimicrosphere kwiiLIBs.Ii-Electrodes zisebenza kunye ne-microspheres ye-thermoresponsive ukuba, ngaphezu kobushushu obubalulekileyo bebhetri yangaphakathi, idlula kwi-thermal transition (nyibilika).Iicapsules ezityhidiweyo zigqume umphezulu we-electrode, zenza umqobo we-ionically insulating kunye nokuvala iseli yebhetri.(E) I-membrane edibeneyo kunye ne-self-standing inorganic composite eyakhiwe ngamasuntswana angama-94% e-alumina kunye ne-6% ye-rubber ye-styrene-butadiene (i-SBR) i-binder yalungiselelwa yindlela yokuphosa isisombululo.Ekunene: Iifoto ezibonisa uzinzo lwe-thermal ye-inorganic composite isahluli kunye ne-PE isahluli.Abahluli babanjwe kwi-130 ° C kwi-40 min.I-PE icuthe kakhulu ukusuka kwindawo kunye nesikwere esinamachaphaza.Nangona kunjalo, isahluli esiyintlanganisela asizange sibonise ukucutheka okucacileyo.Iveliswe kwakhona ngemvume evela ku-Elsevier.FPhezulu: i-polyimide (PI).Phakathi: i-cellulose.Ezantsi: ipoly(butylene) terephthalate.(G) Ekhohlo: Uthelekiso lwembonakalo ye-DSC ye-PI kunye ne-PE kunye ne-PP isahluli;isahluli sePI sibonisa uzinzo olubalaseleyo lobushushu kuluhlu lobushushu ukusuka kuma-30 ukuya kuma-275°C.Ekunene: Iifoto zekhamera yedijithali ethelekisa ukumanzi kwesahluli sorhwebo kunye ne-as-synthesized PI separator kunye nepropylene carbonate electrolyte.Iveliswe kwakhona ngemvume evela kwiAmerican Chemical Society.
Izahluli zokuvala iThermal.Esinye isicwangciso sokuthintela iibhetri ukusuka ekubalekeni kwe-thermal ngexesha le-2 kukuvala indlela yokuqhuba ye-Li ions ngokusebenzisa isahluli.Abahluli zizinto eziphambili zokhuseleko lwe-LIB, njengoko zithintela uqhagamshelwano oluthe ngqo lombane phakathi kwe-cathode ephezulu yamandla kunye nezixhobo ze-anode ngelixa zivumela ukuthuthwa kwe-ionic.I-PP kunye ne-PE zizona zinto zisetyenziswa ngokuqhelekileyo, kodwa zinozinzo olubi lwe-thermal, kunye neendawo ezinyibilikayo ze-~165 ° kunye ne-135 ° C, ngokulandelanayo.Kwi-LIB yorhwebo, abahluli abane-PP / PE / PP isakhiwo se-trilayer sele sele bethengiswa, apho i-PE iyindawo ephakathi ekhuselayo.Xa ubushushu bangaphakathi bebhetri bunyuka ngaphezu kweqondo lokushisa elibalulekileyo (~ 130 ° C), i-PE ye-porous layer iyancibilika ngokuyinxenye, ivale iipores zefilimu kunye nokuthintela ukufuduka kwee-ion kwi-electrolyte engamanzi, ngelixa i-PP inikezela ngenkxaso yomatshini ukuphepha ngaphakathi. ukushokoxeka .Ngenye indlela, ukuvalwa kwe-LIB okubangelwa ngubushushu kunokufezekiswa ngokusebenzisa i-PE epholileyo okanye i-parafini wax microspheres njengomaleko okhuselayo we-anode yebhetri okanye izahluli.Xa ubushushu bebhetri yangaphakathi bufikelela kwixabiso elibalulekileyo, i-microspheres iyanyibilika kwaye igqoke i-anode / isahluli ngesithintelo esingenakunqandwa, ukumisa ukuthuthwa kwe-Li-ion kunye nokuvala iseli ngokusisigxina (Isazobe 5D).
Abahluli abanozinzo oluphezulu lwe-thermal.Ukuphucula uzinzo lwe-thermal yezahluli zebhetri, iindlela ezimbini ziye zaphuhliswa kule minyaka idlulileyo:
(1) Izahluli ezenziwe nge-ceramic, ezenziwe ngokutyabeka ngokuthe ngqo okanye ngokukhula komphezulu kwiileya ze-ceramic ezifana ne-SiO2 kunye ne-Al2O3 kwimigangatho ekhoyo yokwahlula i-polyolefin okanye ngomgubo we-ceramic ofakwe kwizinto ze-polymeric.Isazobe 5E), bonisa iindawo zokunyibilika eziphezulu kakhulu kunye namandla aphezulu oomatshini kwaye zikwanayo ne-thermal conductivity ephezulu.Ezinye izahluli ezidibeneyo ezenziwe ngeli qhinga ziye zathengiswa, njengeSeparion (igama lorhwebo).
(2) Ukutshintsha izixhobo zokwahlula ukusuka kwi-polyolefin ukuya kwi-polymers zobushushu obunyibilikayo obuphezulu kunye nokuncipha okuphantsi xa kufudunyezwa, njenge-polyimide, i-cellulose, i-poly(butylene) terephthalate, kunye nezinye i-poly (esters) ezifanayo, sesinye isicwangciso esisebenzayo sokuphucula ukuzinza kwe-thermal. yabahluli (Isazobe 5F).Ngokomzekelo, i-polyimide yi-polymer ye-thermosetting ethathwa ngokubanzi njengenye indlela ethembisayo ngenxa yokuzinza kwayo kwe-thermal (izinzile ngaphezu kwe-400 ° C), ukuchasana kakuhle kweekhemikhali, amandla aphezulu okuxinana, ukumanzisa kakuhle kwe-electrolyte, kunye nokubuyiswa komlilo (Umzobo 5G).
Iiphakheji zebhetri ezinomsebenzi wokupholisa.Iisistim zolawulo lwe-thermal yesikali esisetyenziswa kukujikeleza komoya okanye ukupholisa ulwelo zisetyenziselwe ukuphucula ukusebenza kwebhetri kunye nokucotha ukunyuka kobushushu.Ukongeza, izinto zokutshintsha isigaba ezifana neparafini wax zidityanisiwe kwiipakethi zebhetri ukuze zisebenze njengendawo yokutshisa ubushushu ukulawula ubushushu bazo, kuthintelwe ukusetyenziswa kakubi kobushushu.
Ukusombulula iingxaki kwisigaba 3 (ukutsha kunye nokudubula)
Ubushushu, ioksijini, namafutha, aziwa ngokuba “ngunxantathu womlilo,” zizinto eziyimfuneko kwimililo emininzi.Ngokuqokelelwa kobushushu kunye neoksijini eyenziwe ngexesha le-1 kunye ne-2, i-fuel (oko kukuthi, i-electrolyte evuthayo kakhulu) iya kuqala ukutshisa ngokuzenzekelayo.Ukunciphisa ukutsha kwezinyibilikisi ze-electrolyte kubalulekile kukhuseleko lwebhetri kunye nosetyenziso olukhulu lwee-LIBs.
Izongezo ze-flame-retardant.Iinzame ezinkulu zophando ziye zanikelwa kuphuhliso lwezongezo ezikwazi ukumelana nomlilo ukuthoba ukutsha kwe-electrolyte engamanzi .Uninzi lwezongezo ze-flame-retardant ezisetyenziswa kwi-electrolyte engamanzi zisekelwe kwi-organic phosphorus compounds okanye i-organic halogenated compounds.Njengoko i-halogens iyingozi kwindalo kunye nempilo yabantu, iikhompawundi ze-organic phosphorus zingabaviwa abathembisayo njengezongezo ezinqanda amadangatye ngenxa yobuchule babo obuphezulu bokulibaziseka kunye nobuhlobo bendalo.Iikhompawundi eziqhelekileyo ze-organic phosphorus ziquka i-trimethyl phosphate, i-triphenyl phosphate, i-bis (2-methoxyethoxy) i-methylallylphosphonate, i-tris (2,2,2-trifluoroethyl) phosphite, (ethoxy) pentafluorocyclotriphosphazene, i-ethylene ethyl phosphate ( njl.Isazobe 6A).Indlela yokunciphisa idangatye kwezi khompawundi ezine-phosphorus kukholelwa ngokubanzi ukuba yinkqubo yokurhabula imichiza.Ngethuba lokutsha, i-molecule equkethe i-phosphorus inokubola kwiintlobo ze-phosphorus-eziqukethe i-free-radicals, ezinokuthi emva koko ziphelise i-radicals (umzekelo, i-H kunye ne-OH radicals) eyenziwa ngexesha lokusasazwa kwe-chain reaction ejongene nokuvutha okuqhubekayo (Umzobo 6, B kunye no-C).Ngelishwa, ukuncitshiswa kokutsha kunye nokongezwa kwezi zixhobo ze-flame retardants ezine-phosphorus ziza kwiindleko zokusebenza kwe-electrochemical.Ukuphucula oku kurhweba, abanye abaphandi baye benza utshintsho oluthile kwisakhiwo sabo se-molecular: (i) i-fluorination inxalenye ye-alkyl phosphates inokuphucula ukuzinza kwabo kokunciphisa kunye nokusebenza kwe-flame retardancy;(ii) ukusetyenziswa kwee-compounds ezinezixhobo ezikhuselayo zefilimu kunye ne-flame-retading properties, njenge-bis (2-methoxyethoxy) methylallylphosphonate, apho amaqela ahlangeneyo angenza i-polymerize kwaye enze ifilimu ye-SEI ezinzileyo kwiindawo zegraphite, ngaloo ndlela ikhusela ngokufanelekileyo icala eliyingozi. ukusabela;(iii) utshintsho lwe-P(V) phosphate ukuya kwi-P(III) phosphites, eququzelela ukwakheka kwe-SEI kwaye ekwaziyo ukuvala i-PF5 eyingozi [umzekelo, i-tris(2,2,2-trifluoroethyl) phosphite];kunye (iv) nokutshintsha izongezo ze-organophosphorus nge-cyclic phosphazenes, ngakumbi i-cyclophosphazene enefluorinated, eye yaphucula ukuhambelana kwe-electrochemical.
Umzobo 6 Amacebo okusombulula imiba kwinqanaba lesi-3.
(A) Ubume bemolekyuli eziqhelekileyo zezongezo ezingenamlilo.(B) Isixhobo seziphumo zokulibaziseka kwedangatye kwezi khompawundi ezine-phosphorus ngokuqhelekileyo kukholelwa ukuba yinkqubo yekhemikhali ye-radical-scavenging, enokuphelisa iintshukumo zetsheyini ezikhawulezayo ezibangela ukutsha kwinqanaba legesi.TPP, triphenyl phosphate.(C) Ixesha lokuzicima (i-SET) ye-carbonate electrolyte eqhelekileyo ingancitshiswa kakhulu kunye nokongezwa kwe-triphenyl phosphate.(D) I-Schematic ye-"smart" ye-electrospun separator ene-thermal-triggered flame-retardant properties kwii-LIBs.I-separator ekhululekile iqulethwe nge-microfibers ene-core-shell structure, apho i-flame retardant ingundoqo kunye ne-polymer yigobolondo.Kwi-thermal triggering, iqokobhe le-polymer liyanyibilika kwaye emva koko i-retardant efakwe kwi-flame retardant ikhutshelwa kwi-electrolyte, ngaloo ndlela icinezela ngokufanelekileyo ukuvutha kunye nokutshiswa kwe-electrolytes.(E) Umfanekiso we-SEM we-microfibers ye-TPP @ PVDF-HFP emva kokuba u-etching ubonisa ngokucacileyo isakhiwo sabo se-core-shell.Isikali bar, 5 μm.F(G) Ulwakhiwo lwemolekyuli ye-PFPE, i-analog ye-PEO engatshiyo eneperfluorinated.Amaqela amabini e-methyl carbonate aguqulwa kwii-terminals ze-polymer chain chain ukuqinisekisa ukuhambelana kwee-molecule kunye neenkqubo zebhetri zangoku.
Kufuneka kuqatshelwe ukuba kusoloko kukho ukurhweba phakathi kokunciphisa ukutsha kwe-electrolyte kunye nokusebenza kweeseli zezongezo ezidweliswe, nangona le ngqungquthela iphuculwe ngokuyilwa kwe-molecular designs.Esinye isicwangciso esicetywayo sokusombulula le ngxaki kubandakanya ukubandakanya i-flame retardant ngaphakathi kweqokobhe le-polymer ekhuselayo ye-microfibers, ephinda ipakishwe ukwenza isahlukanisi esingalukwanga.Isazobe 6D).Inoveli ye-electrospun nonwoven microfiber separator eneempawu ze-thermal-triggered-retardant flame yenzelwe ii-LIBs.Ukufakwa kwe-encapsulation ye-flame retardant ngaphakathi kwiqokobhe lepolymer ekhuselayo kuthintela ukuvezwa ngokuthe ngqo kwedangatye elibuyiswayo kwi-electrolyte, ukuthintela iziphumo ezingalunganga ezivela kwi-retardants ekusebenzeni kwe-electrochemical yebhetri (Isazobe 6E).Nangona kunjalo, ukuba i-thermal yokubaleka kwebhetri ye-LIB iyenzeka, iqokobhe le-poly(vinylidenefluoride-hexafluoro propylene) copolymer (PVDF-HFP) liya kunyibilika njengoko ubushushu bunyuka.Emva koko i-ecapsulated i-triphenyl phosphate flame retardant iya kukhutshelwa kwi-electrolyte, ngaloo ndlela icinezela ngokufanelekileyo ukutsha kwee-electrolyte ezitsha kakhulu.
Kwaphuhliswa ingcamango “ye-electrolyte enetyuwa” ukuze kulungiswe le ngxaki .Ezi electrolyte eziphilayo ezicima umlilo kwiibhetri ezinokutshajwa kwakhona ziqulethe i-LiN (SO2F) 2 njengetyuwa kunye ne-flame retardant ethandwayo ye-trimethyl phosphate (TMP) njenge-solvent kuphela.Ukwakheka okuzenzekelayo kwe-SEI eyomeleleyo evela kwityuwa ye-inorganic kwi-anode ibalulekile ekusebenzeni okuzinzileyo kwe-electrochemical.Esi sicwangciso sinoveli sinokwandiswa kwezinye izinto ezahlukeneyo ezibuthisa amadangatye kwaye sinokuvula indlela entsha yokuphuhlisa izinyibilikisi ezibukwa ngamadangatya kwiiLIBs ezikhuselekileyo.
Ulwelo lwe-electrolyte olungatshiyo.Isisombululo sokugqibela kwimiba yokhuseleko ye-electrolyte iya kuba kukuphuhlisa i-electrolyte engenakutsha.Elinye iqela leeelectrolyte ezingatshayo eliye laphononongwa ngokubanzi lulwelo lwe-ionic, ngakumbi ulwelo lwe-ionic lobushushu begumbi, olungaguquguqukiyo (akukho mphunga ubonwayo ungaphantsi kwama-200°C) nolungenakutsha kwaye lunobushushu obubanzi befestile.Isazobe 6F).Nangona kunjalo, uphando oluqhubekayo lusafuneka ukuxazulula imiba yezinga eliphantsi lokukwazi ukuvela kwi-viscosity yabo ephezulu, inombolo ephantsi yokudluliselwa kwe-Li, ukungazinzi kwe-cathodic okanye ukunciphisa, kunye neendleko eziphezulu ze-ionic liquids.
I-Low-molecular weight hydrofluoroethers yenye iklasi ye-electrolytes engamanzi angatshangayo ngenxa yomgangatho ophezulu okanye ongenawo umbane, ukuvutha, ukuxinezeleka okuphantsi komhlaba, i-viscosity ephantsi, ukushisa okuphantsi kweqhwa, njl.Uyilo olufanelekileyo lwemolekyuli kufuneka lwenziwe ukulungelelanisa iimpawu zabo zeekhemikhali ukuhlangabezana nemilinganiselo ye-electrolyte yebhetri.Umzekelo onomdla oye waxelwa mva nje yi-perfluoropolyether (PFPE), i-analog ye-polyethylene oxide (PEO) ene-perfluorinated eyaziwa kakhulu ngokungatsha kwayo (Umzobo 6G).Amaqela amabini e-methyl carbonate alungiswa kumaqela esiphelo samatyathanga e-PFPE (PFPE-DMC) ukuqinisekisa ukuhambelana kweeathom kunye neenkqubo zebhetri zangoku.Ke, ukungatsha kunye nokuzinza kwe-thermal ye-PFPE kunokuphucula ukhuseleko lwee-LIBs kakhulu ngelixa isonyusa inani lokudluliselwa kwe-electrolyte ngenxa yoyilo olulodwa lwemolekyuli.
Inqanaba lesi-3 linqanaba lokugqibela kodwa elibaluleke kakhulu kwinkqubo yokubaleka ngokushushu.Kufuneka kuqatshelwe ukuba nangona iinzame ezinkulu zinikezelwe ekunciphiseni ukutsha kwe-electrolyte yolwelo lwe-state-of-art, ukusetyenziswa kwe-electrolyte eqinile engabonakaliyo ibonisa isithembiso esikhulu.Ii-electrolyte eziqinileyo ziwela ikakhulu kwiindidi ezimbini: i-electrolytes ye-inorganic ceramic [i-sulfides, i-oxides, i-nitrides, i-phosphates, njl.Iinzame zokuphucula i-electrolyte eqinile ayiyi kuchazwa apha, njengoko esi sihloko sele sishwankathelwe kakuhle kwiiphononongo zakutshanje.
UMBONO
Kwixesha elidlulileyo, izixhobo ezininzi zenoveli ziye zaphuhliswa ukuphucula ukhuseleko lwebhetri, nangona ingxaki ingekasonjululwa ngokupheleleyo.Ukongeza, iindlela ezisisiseko semiba yokhuseleko ziyahluka kwikhemistry yebhetri nganye.Ke, izinto ezithile ezilungiselelwe iibhetri ezahlukeneyo kufuneka zenziwe.Sikholelwa ukuba iindlela ezisebenza ngempumelelo kunye nezinto eziyilwe kakuhle zisaza kufunyanwa.Apha, sidwelisa iindlela ezininzi ezinokubakho zophando lokhuseleko lwebhetri kwixesha elizayo.
Okokuqala, kubalulekile ukuphuhlisa kwi-situ okanye kwiindlela ze-operando zokubona nokubeka iliso kwiimeko zempilo zangaphakathi ze-LIB.Umzekelo, inkqubo yokubaleka kwe-thermal inxulumene ngokusondeleyo nobushushu bangaphakathi okanye ukunyuka koxinzelelo ngaphakathi kwe-LIB.Nangona kunjalo, ukuhanjiswa kweqondo lokushisa ngaphakathi kweebhetri kunzima kakhulu, kwaye iindlela ziyafuneka ukujonga ngokuchanekileyo amaxabiso e-electrolytes kunye nee-electrodes, kunye nezahluli.Ke, ukukwazi ukulinganisa ezi parameters kumacandelo ahlukeneyo kubalulekile ekuxilongeni kwaye ngaloo ndlela kuthintelwe iingozi zokhuseleko lwebhetri.
Uzinzo olushushu lwezahluli lubalulekile kukhuseleko lwebhetri.Iipolymers ezisanda kuphuhliswa ezineendawo eziphezulu zokunyibilika zisebenza kakuhle ekwandiseni ukunyaniseka kwe-thermal ye-separator.Nangona kunjalo, iipropathi zabo zoomatshini zisephantsi, zinciphisa kakhulu ukwenzeka kwazo ngexesha lokuhlanganisa ibhetri.Ngaphezu koko, ixabiso likwayinto ebalulekileyo ekufuneka ithathelwe ingqalelo kwizicelo ezisebenzayo.
Ukuphuhliswa kwee-electrolyte eziqinileyo kubonakala kuyisisombululo esiphezulu kwimiba yokhuseleko lwe-LIBs.I-electrolyte eqinileyo iya kunciphisa kakhulu amathuba okuba nokwenzeka kwebhetri yangaphakathi, kunye nomngcipheko womlilo kunye nokudubula.Nangona iinzame ezinkulu zinikelwe ekuqhubeleni phambili kwee-electrolyte eziqinileyo, ukusebenza kwazo kusaqhubeka kushiyeka emva kakhulu kuleyo ye-electrolyte engamanzi.Imidibaniso ye-electrolyte ye-inorganic kunye ne-polymer ibonisa amandla amakhulu, kodwa ifuna uyilo olubuthathaka kunye nokulungiswa.Sigxininisa ukuba uyilo olufanelekileyo lwe-inorganic-polymer interfaces kunye nobunjineli bokulungelelaniswa kwazo zibalulekile kuthutho lwe-Li-ion olusebenzayo.
Kufuneka kuqatshelwe ukuba i-electrolyte engamanzi ayilona candelo kuphela lebhetri elinokutsha.Ngokomzekelo, xa ii-LIB zihlawuliswa kakhulu, izinto ezivuthayo ze-lithiated anode (umzekelo, i-lithiated graphite) nazo ziyinkxalabo enkulu yokhuseleko.Iiretadants ezinomlilo ezinokuthi zithintele ngokufanelekileyo umlilo wezinto eziqinileyo zifunwa kakhulu ukwandisa ukhuseleko lwazo.I-retardants yomlilo inokuxutywa kunye negraphite ngendlela ye-polymer binders okanye i-conductive frameworks.
Ukhuseleko lwebhetri yingxaki entsonkothileyo nentsonkothileyo.Ikamva lokhuseleko lwebhetri lifuna iinzame ezithe kratya kwizifundo ezingundoqo zoomatshini ukuqonda okunzulu ukongezelela kwiindlela eziphucukileyo zokuchaza iimpawu, ezinokunika ulwazi olongezelelweyo ukukhokela uyilo lwemathiriyeli.Nangona olu Phononongo lujolise kukhuseleko lwenqanaba lezixhobo, kufuneka kuqatshelwe ukuba indlela ebanzi iyafuneka ngakumbi ukusombulula umba wokhuseleko we-LIBs, apho izinto, iinxalenye zeseli kunye nefomathi, kunye nemodyuli yebhetri kunye neepakethi zidlala indima elinganayo ukwenza iibhetri zithembeke ngaphambili. bakhululwa basiwe emarikeni.
IZIQINISEKISO KUNYE NAMANQAKU
Kai Liu, Yayuan Liu, DingchangLin, Allen Pei, Yi Cui, Izixhobo zokhuseleko lwebhetri ye-lithium-ion, i-ScienceAdvances, i-DOI: 10.1126/sciadv.aas9820
Ixesha lokuposa: Jun-05-2021
