Abstract
Amabhethri e-lithium-ion (LIBs) athathwa njengobunye bobuchwepheshe obubaluleke kakhulu bokugcina amandla.Njengoba ukuminyana kwamandla amabhethri kukhula, ukuphepha kwebhethri kuba bucayi kakhulu uma amandla ekhishwe kungahlosiwe.Izingozi ezihlobene nemililo nokuqhuma kwama-LIB zenzeka kaningi emhlabeni jikelele.Ezinye ziye zabangela usongo olukhulu empilweni nempilo yomuntu futhi ziye zaholela ekukhunjuzweni kwemikhiqizo eminingi ngabakhiqizi.Lezi zehlakalo ziyizikhumbuzo zokuthi ukuphepha kuyisidingo sangaphambili samabhethri, futhi izindaba ezibucayi zidinga ukuxazululwa ngaphambi kokusetshenziswa kwesikhathi esizayo kwamasistimu ebhethri anamandla amakhulu.Lesi sibuyekezo sihlose ukufingqa izisekelo zemisuka yezinkinga zokuphepha ze-LIB nokugqamisa inqubekelaphambili yakamuva ebalulekile ekwakhiweni kwezinto zokwakha ukuze kuthuthukiswe ukuphepha kwe-LIB.Silindele ukuthi lokhu kubuyekeza kuzogqugquzela ukuthuthuka okuqhubekayo ekuphepheni kwebhethri, ikakhulukazi kuma-LIB asafufusa anokuminyana kwamandla aphezulu.
IMVELAPHI YEZINDABA ZOKUPHEPHA KWE-LIB
I-organic liquid electrolyte ngaphakathi kwe-LIBs ivutha kalula.Okunye ukwehluleka okuyinhlekelele kakhulu kwesistimu ye-LIB umcimbi we-thermal runnaway, othathwa njengembangela enkulu yokukhathazeka ngokuphepha kwebhethri .Ngokuvamile, ukubaleka okushisayo kwenzeka lapho ukusabela kwe-exothermic kungalawuleki.Njengoba izinga lokushisa lebhethri likhuphuka libe ngaphezu kuka-~80°C, izinga lokusabela kwamakhemikhali ashisayo ngaphakathi kwamabhethri liyakhuphuka futhi lishise iseli, okuholela kumjikelezo wempendulo omuhle.Amazinga okushisa alokhu ekhuphuka angase abangele imililo nokuqhuma, ikakhulukazi kumaphakethe amakhulu ebhethri.Ngakho-ke, ukuqonda izimbangela nezinqubo zokubaleka okushisayo kungaqondisa ukwakheka kwezinto ezisebenzayo ukuze kuthuthukiswe ukuphepha nokuthembeka kwama-LIB.Inqubo yokubaleka okushisayo ingahlukaniswa izigaba ezintathu, njengoba kufingqiwe kuzoUmdwebo 1.
Umfanekiso 1 Izigaba ezintathu zenqubo yokubaleka okushisayo.
Isigaba 1: Ukuqala kokushisa ngokweqile.Amabhethri ashintsha ukusuka kwejwayelekile ukuya kwesingajwayelekile, futhi izinga lokushisa langaphakathi liqala ukwanda.Isiteji sesi-2: Ukunqwabelana kokushisa nenqubo yokukhishwa kwegesi.Izinga lokushisa langaphakathi liyenyuka ngokushesha, futhi ibhethri iba nokusabela okushisayo.Isiteji sesi-3: Ukuvutha nokuqhuma.I-electrolyte evuthayo iyavutha, okuholela emililo ngisho nokuqhuma.
Ukuqala kokushisa ngokweqile (isigaba 1)
Ukushisa okushisayo kuqala kusukela ekushiseni ngokweqile kwesistimu yebhethri.Ukushisa ngokweqile kokuqala kungase kwenzeke ngenxa yokushajwa kwebhethri ngaphezu kwamandla kagesi aklanyelwe (ukushajwa ngokweqile), ukuchayeka emazingeni okushisa adlulele, amasekhethi amafushane angaphandle ngenxa yezintambo ezingalungile, noma amasekhethi amafushane angaphakathi ngenxa yokukhubazeka kwamaseli.Phakathi kwazo, ukushoda kwangaphakathi kuyisizathu esiyinhloko sokubaleka okushisayo futhi kunzima ukukulawula.Ukushoda kwangaphakathi kungenzeka ezimeni zokuchotshozwa kweseli njengokungena kwemfucumfucu yensimbi yangaphandle;ukushayisana kwezimoto;ukwakheka kwe-lithium dendrite ngaphansi kokushaja okuphezulu kwamanje, ngaphansi kwezimo zokushaja ngokweqile noma emazingeni okushisa aphansi;nezihlukanisi ezinamaphutha ezidalwe ngesikhathi sokuhlanganisa ibhethri, ukubala okumbalwa.Isibonelo, ekuqaleni kuka-Okthoba 2013, imoto yakwaTesla eduze kwase-Seattle yashayisa imfucumfucu yensimbi eyabhoboza isihlangu kanye nephakethe lebhethri.Imfucumfucu yangena ezihlukanisi ze-polymer futhi yaxhuma ngokuqondile i-cathode ne-anode, okubangela ukuthi ibhethri ihambe kancane futhi ibambe umlilo;ngo-2016, ukusha kwebhethri le-Samsung Note 7 kwakungenxa yesihlukanisi esinamandla esinamandla esilinyazwe kalula ukucindezela kwangaphandle noma ama-burrs okushisela ku-electrode ephozithivu, okubangele ukuthi ibhethri lihambe kancane .
Phakathi nesiteji 1, ukusebenza kwebhethri kushintsha kusuka kwesivamile kuya kwesingajwayelekile, futhi zonke izinkinga ezibalwe ngenhla zizobangela ukuthi ibhethri lishise ngokweqile.Lapho izinga lokushisa langaphakathi liqala ukwanda, isigaba 1 siyaphela futhi isigaba sesi-2 siqala.
Ukuqoqwa kokushisa nenqubo yokukhishwa kwegesi (isigaba 2)
Njengoba isigaba sesi-2 siqala, izinga lokushisa langaphakathi liyakhuphuka ngokushesha, futhi ibhethri lenze lokhu kusabela okulandelayo (lokhu kusabela akwenzeki ngokulandelana okunikiwe; okunye kwakho kungenzeka kanyekanye):
(1) Ukubola kwe-Solid electrolyte interphase (SEI) ngenxa yokushisa ngokweqile noma ukungena ngokomzimba .Isendlalelo se-SEI ngokuyinhloko siqukethe izinto ezizinzile (ezifana ne-LiF ne-Li2CO3) kanye nezingxenye ze-metastable [njengama-polymers, ROCO2Li, (CH2OCO2Li)2, kanye ne-ROLi].Kodwa-ke, izakhi ze-metastable zingabola ngendlela exakile cishe ku->90°C, zikhiphe amagesi avuthayo nomoya-mpilo.Thatha (CH2OCO2Li)2 njengesibonelo
(CH2OCO2Li)2→Li2CO3+C2H4+CO2+0.5O2
(2) Ngokubola kwe-SEI, izinga lokushisa liyakhula, futhi insimbi ye-lithium noma i-lithium ehlanganisiwe ku-anode izosabela nge-solvents ephilayo ku-electrolyte, ikhiphe amagesi e-hydrocarbon avuthayo (i-ethane, i-methane, nabanye) .Lokhu ukusabela kwe-exothermic okunyusa izinga lokushisa liye phezulu.
(3) NiniT> ~ 130 ° C, isihlukanisi se-polyethylene (PE)/polypropylene (PP) siqala ukuncibilika, okuqhubekisela phambili ukuwohloka kwesimo futhi kubangele ukujikeleza okufushane phakathi kwe-cathode ne-anode.
(4) Ekugcineni, ukushisa kubangela ukubola kwe-lithium metal oxide cathode futhi kubangele ukukhululwa komoyampilo.Thatha i-LiCoO2 njengesibonelo, engabola iqale ku-~180°C ngendlela elandelayo
Ukuwohloka kwe-cathode nakho kuyingozi kakhulu, kwandisa izinga lokushisa nokucindezela futhi, ngenxa yalokho, kusheshisa ukusabela.
Phakathi nesigaba sesi-2, izinga lokushisa liyakhuphuka futhi umoya-mpilo unqwabelana ngaphakathi kwamabhethri.Inqubo yokubaleka okushisayo iqhubeka isuka esigabeni 2 iye esigabeni 3 ngokushesha nje lapho umoya-mpilo nokushisa okwanele sekunqwabelene ukuze kushiswe ibhethri.
Ukushiswa nokuqhuma (isigaba 3)
Esigabeni sesi-3, ukusha kuyaqala.Ama-electrolyte ama-LIB ayi-organic, cishe ayinhlanganisela yendawo yonke yama-alkyl carbonates e-cyclic kanye ne-linear.Zinokuguquguquka okuphezulu futhi ziyavutha kakhulu.Uma sithatha i-carbonate electrolyte esetshenziswa kakhulu [ingxube ye-ethylene carbonate (EC) + dimethyl carbonate (DMC) (1:1 ngesisindo)] njengesibonelo, ikhombisa umfutho womhwamuko ongu-4.8 kPa endaweni yokushisa kanye ne-flash point ephansi kakhulu. engu-25° ± 1°C ngomfutho womoya ongu-1.013 bar.Umoya-mpilo okhululiwe kanye nokushisa esigabeni sesi-2 kunikeza izimo ezidingekayo zokusha kwama-electrolyte ephilayo avuthayo, ngaleyo ndlela kubangele izingozi zomlilo noma ukuqhuma.
Ezigabeni 2 no-3, ukusabela kwe-exothermic kwenzeka ngaphansi kwezimo eziseduze ne-adiabatic.Ngakho, i-accelerated rate calorimetry (ARC) iyindlela esetshenziswa kabanzi elingisa indawo ezungezile ngaphakathi kwama-LIB, esiza ukuqonda kwethu i-thermal runaway reaction kinetics.Umfanekiso 2ibonisa ijika le-ARC elivamile le-LIB elirekhodwe ngesikhathi sokuhlolwa kokuhlukumeza okushisayo .Ukulingisa izinga lokushisa kusigaba sesi-2, umthombo wangaphandle wokushisa unyusa izinga lokushisa lebhethri kuzinga lokushisa lokuqala.Ngaphezu kwaleli zinga lokushisa, i-SEI iyabola, okuzodala ukusabela kwamakhemikhali ayingozi kakhulu.Ekugcineni, isihlukanisi sizoncibilika.Izinga lokuzifudumeza lizokhula ngemva kwalokho, okuholela ekubalekeni okushisayo (lapho izinga lokuzishisa lingaphezu kuka-10°C/min) kanye nokusha kwe-electrolyte (isiteji sesi-3).
I-anode yi-mesocarbon microbead graphite.I-cathode ithi LiNi0.8Co0.05Al0.05O2.I-electrolyte ingu-1.2 M LiPF6 ku-EC/PC/DMC.Kusetshenziswe isihlukanisi se-Celgard 2325 trilayer.Icushwe ngemvume evela ku-Electrochemical Society Inc.
Kufanele kuqashelwe ukuthi ukusabela okuboniswe ngenhla akwenzeki ngokuqondile ngokulandelana ngendlela enikeziwe.Kunalokho, ziyizinkinga eziyinkimbinkimbi futhi ezihlelekile.
IZINTO EZINOKUPHEPHA OKUTHUTHUKISIWE IBHATHRI
Ngokusekelwe ekuqondeni kokubaleka kwebhethri okushisayo, izindlela eziningi ziyacutshungulwa, ngenhloso yokunciphisa izingozi zokuphepha ngomklamo onengqondo wezingxenye zebhethri.Ezigabeni ezilandelayo, sifingqa izindlela zezinto ezihlukile zokuthuthukisa ukuphepha kwebhethri, ukuxazulula izinkinga ezihambisana nezigaba ezihlukene zokubaleka kokushisa.
Ukuxazulula izinkinga esigabeni 1 (ukuqala kokushisisa)
Izinto ezithembekile ze-anode.Ukwakheka kwe-Li dendrite ku-anode ye-LIB kuqala isigaba sokuqala sokubaleka okushisayo.Nakuba le nkinga incishisiwe kuma-anode ama-LIB okuhweba (isibonelo, ama-anode e-carbonaceous), ukwakheka kwe-Li dendrite akuzange kuvinjwe ngokuphelele.Isibonelo, kuma-LIB ezentengiselwano, ukufakwa kwe-dendrite kwenzeka ngokuncanyelwayo emaphethelweni e-electrode ye-graphite uma ama-anode nama-cathode ama-anode amataniswe kahle .Ngaphezu kwalokho, izimo zokusebenza ezingafanele zama-LIB nazo zingaholela ekufakweni kwensimbi ye-Li ngokukhula kwe-dendrite.Kuyaziwa ukuthi i-dendrite ingakhiwa kalula uma ibhethri lishajwa (i) ekuminyaniseni okuphezulu kwamanje lapho ukufakwa kwensimbi ye-Li kushesha kunokusatshalaliswa kwama-Li ion ku-graphite yobuningi;(ii) ngaphansi kwezimo zokushajwa ngokweqile lapho i-graphite igcwele ngokweqile;futhi (iii) emazingeni okushisa aphansi [ngokwesibonelo, izinga lokushisa elingaphansi (~0°C)], ngenxa yokwanda kwe-viscosity ye-electrolyte ewuketshezi kanye nokwenyuka kokumelana nokusakazwa kwe-Li-ion .
Ngokombono wezakhiwo zempahla, imvelaphi yempande enquma ukuqala kokukhula kwe-Li dendrite ku-anode i-SEI engazinzile futhi engavamile, ebangela ukusatshalaliswa kwendawo kwamanje okungalingani .Izingxenye ze-Electrolyte, ikakhulukazi izithasiselo, ziye zaphenywa ukuze kuthuthukiswe ukufana kwe-SEI nokuqeda ukwakheka kwe-Li dendrite.Izithasiselo ezijwayelekile zifaka izinhlanganisela ze-inorganic [isibonelo, i-CO2, i-LiI, njll.] nezinhlanganisela zezinto eziphilayo eziqukethe amabhondi ekhabhoni angagcwalisiwe njenge-vinylene carbonate kanye nezithasiselo ze-maleimide;ama-molecule e-cyclic angazinzile njenge-butyrolactone, i-ethylene sulfite, kanye nokuphuma kwawo;kanye nama-fluorinated compounds afana ne-fluoroethylene carbonate, phakathi kwabanye.Ngisho nasezingeni lezingxenye-ngesigidi, lawa ma-molecule asengathuthukisa i-morphology ye-SEI, ngaleyo ndlela enze i-homogenizing i-Li-ion flux futhi aqede ukuthi kungenzeka ukwakheka kwe-Li dendrite.
Sekukonke, izinselelo ze-Li dendrite zisekhona kuma-anode e-graphite noma e-carbonaceous kanye ne-silicon/SiO equkethe i-anode yesizukulwane esilandelayo.Ukuxazulula inkinga yokukhula kwe-Li dendrite kuyinselele ebalulekile ekuzivumelaniseni nezimo ze-high-energy density Li-ion chemistries esikhathini esizayo esiseduze.Kumele kuqashelwe ukuthi, muva nje, kuye kwanikelwa imizamo emikhulu ekuxazululeni inkinga yokwakhiwa kwe-Li dendrite ku-anode yensimbi ye-Li ehlanzekile ngokwenza i-homogenizing i-Li-ion flux ngesikhathi sokumiswa kwe-Li;isibonelo, ungqimba oluvikelayo , ubunjiniyela bokwenziwa kwe-SEI , njll. Kulesi sici, ezinye zezindlela zingase zisikhanyisele ngendlela yokubhekana nenkinga kuma-anode e-carbonaceous kuma-LIB futhi.
Ama-electrolyte angama-liquid amaningi kanye nezihlukanisi.I-electrolyte ewuketshezi nesihlukanisi zidlala indima ebalulekile ekuhlukaniseni ngokomzimba i-cathode enamandla amakhulu ne-anode.Ngakho-ke, ama-electrolyte amaningi asebenzayo kanye nezihlukanisi angakwazi ukuvikela amabhethri ekuqaleni kwebhethri elishisayo (isigaba 1).
Ukuze kuvikelwe amabhethri ekugayweni komshini, i-electrolyte ewuketshezi eshearyo ejiya itholwe ngokungezwa okulula kwe-silica efuthuzayo ku-carbonate electrolyte (1 M LiFP6 ku-EC/DMC) .Phezu kwengcindezi yemishini noma umthelela, uketshezi lubonisa umphumela wokuqina we-shear ngokukhuphuka kwe-viscosity, ngakho-ke kuhlakaza amandla omthelela nokubonisa ukubekezelela ukuchotshozwa (Umdwebo 3A)
Umdwebo 3 Amasu okuxazulula izinkinga esigabeni 1.
(A) Shear thickening electrolyte.Phezulu: Ku-electrolyte evamile, umthelela womshini ungaholela ekushoneni kwebhethri kwangaphakathi, okubangela imililo nokuqhuma.Ngezansi: Inoveli ye-electrolyte ehlakaniphile enomthelela wokushela ukuqina ngaphansi kwengcindezi noma umthelela ibonisa ukubekezelela okuhle kakhulu kokuchotshozwa, okungathuthukisa kakhulu ukuphepha kwemishini kwamabhethri.(B) Izihlukanisi ezisebenzayo ezimbili zokutholwa kusenesikhathi kwe-lithium dendrites.Ukwakheka kwe-dendrite kubhethri ye-lithium yendabuko, lapho ukungena okuphelele kwesihlukanisi nge-lithium dendrite kutholwa kuphela lapho ibhethri lehluleka ngenxa yesifunda esifushane sangaphakathi.Uma kuqhathaniswa, ibhethri ye-lithium ene-separator esebenza kabili (ehlanganisa ungqimba oluqhutshwayo oluphakathi kwezihlukanisi ezimbili ezivamile), lapho i-lithium dendrite ekhule ngokweqile ingena kusihlukanisi futhi ithintane nongqimba lwethusi oluqhubayo, okuholela ekwehleniVI-Cu−Li, esebenza njengesexwayiso sokwehluleka okuzayo ngenxa yesifunda esifushane sangaphakathi.Nokho, ibhethri eligcwele lihlala lisebenza ngokuphephile linamandla e-nonzero.(A) kanye no-(B) ashintshwa noma akhiqizwa kabusha ngemvume evela ku-Springer Nature.(C) Isihlukanisi se-Trilayer ukuze sisebenzise ama-Li dendrites ayingozi futhi sandise impilo yebhethri.Kwesobunxele: I-lithium anode ingakha kalula amadiphozithi e-dendritic, angakhula kancane kancane abe mkhulu futhi angene kusihlukanisi se-polymer engasebenzi.Lapho ama-dendrite egcina exhuma i-cathode ne-anode, ibhethri liyajikeleza futhi liyahluleka.Kwesokudla: Ungqimba lwama-silica nanoparticles luhlanganiswe izendlalelo ezimbili zezihlukanisi ze-polymer ezentengiselwano.Ngakho-ke, lapho i-lithium dendrites ikhula futhi ingena kusihlukanisi, izothintana ne-silica nanoparticles kungqimba oluhlanganisiwe futhi isetshenziswe nge-electrochemically.(D) Iskena i-electron microscopy (SEM) isithombe se-silica nanoparticle sandwiched isihlukanisi.(E) Amandla kagesi ajwayelekile uma kuqhathaniswa nesikhathi sebhethri le-Li/Li elinesihlukanisi esivamile (ijika elibomvu) kanye nesihlukanisi se-silica nanoparticle sandwiched trilayer separator (ijika elimnyama) ihlolwe ngaphansi kwezimo ezifanayo.(C), (D), kanye no-(E) akhiqizwa kabusha ngemvume evela ku-John Wiley and Sons.(F) Umdwebo wohlelo lwezinqubo zezithasiselo ze-shuttle redox.Endaweni egcwele ukushajwa kwe-cathode, isithasiselo se-redox sikhishwa nge-oxid sibe kwifomu elithi [O], kamuva elizoncishiswa libuyele esimweni salo sangempela [R] ebusweni be-anode ngokusakazwa nge-electrolyte.Umjikelezo we-electrochemical we-oxidation-diffusion-reduction-diffusion ungagcinwa unomphela futhi ngaleyo ndlela ukhiye amandla e-cathode ekushajweni okuyingozi kakhulu.(G) Izakhiwo zamakhemikhali ezijwayelekile zezithasiselo ze-shuttle redox.(H) Indlela yokuvala izithasiselo zokukhokhiswa ngokweqile ezingase zenze i-electrochemically polymerize ngamandla aphezulu.(I) Izakhiwo zamakhemikhali ezijwayelekile zezithasiselo zokushajwa kokushajwa ngokweqile.Amandla okusebenza ezithasiselo afakwe ohlwini ngaphansi kwesakhiwo ngasinye samangqamuzana ku-(G), (H), kanye (I).
Izihlukanisi zingakwazi ukuvalela i-cathode ne-anode nge-elekthronikhi futhi zidlale indima ebalulekile ekuqapheni isimo sezempilo sebhethri endaweni ukuze kuvinjelwe ukuwohloka okwengeziwe esikhathini esidlule isigaba 1. Isibonelo, "isihlukanisi esisebenza kabili" esinokulungiswa kwe-polymer-metal-polymer trilayer (Umfanekiso 3B) inganikeza umsebenzi omusha wokuzwa amandla kagesi.Lapho i-dendrite ikhula futhi ifinyelela ungqimba oluphakathi, izoxhuma ungqimba lwensimbi kanye ne-anode ngendlela yokuthi ukwehla kwe-voltage kungazelelwe phakathi kwazo kungatholwa ngokushesha njengokuphumayo.
Ngaphandle kokutholwa, isihlukanisi se-trilayer saklanywa ukusebenzisa ama-Li dendrites ayingozi futhi sehlise isivinini sokukhula kwawo ngemva kokungena kusihlukanisi .Ungqimba lwama-silica nanoparticles, ahlanganiswe izingqimba ezimbili zezihlukanisi ze-polyolefin ezentengiselwano (Umdwebo 3, C no-D), ingasebenzisa noma iyiphi i-Li dendrite eyingozi engena, ngaleyo ndlela ithuthukise ngempumelelo ukuphepha kwebhethri.Ukuphila kwebhethri elivikelwe kwanwetshwa kakhulu cishe izikhathi ezinhlanu uma kuqhathaniswa naleyo enezihlukanisi ezivamile (Umfanekiso 3E).
Ukuvikelwa kokushajwa ngokweqile.Ukushaja ngokweqile kuchazwa njengokushaja ibhethri ngaphezu kwamandla kagesi aklanyelwe wona.Ukushajwa ngokweqile kungase kuqaliswe ukuminyana okuphezulu okukhethekile kwamanje, amaphrofayili wokushaja anolaka, njll., okungaletha uchungechunge lwezinkinga, okuhlanganisa (i) ukufakwa kwensimbi ye-Li ku-anode, okuthinta kabi ukusebenza nokuphepha kwebhethri kagesi kagesi;(ii) ukubola kwe-cathode material, ukukhulula umoya-mpilo;kanye (iii) nokubola kwe-organic electrolyte, ukukhipha ukushisa nemikhiqizo yegesi (H2, ama-hydrocarbon, i-CO, njll.), okuyimbangela yokubaleka okushisayo .Ukusabela kwe-electrochemical ngesikhathi sokubola kuyinkimbinkimbi, okunye kwakho okubalwe ngezansi.
Inkanyezi (*) isho ukuthi igesi ye-hydrogen isuka ku-protic, ishiya amaqembu akhiqizwa ngesikhathi se-oxidation yama-carbonates ku-cathode, abese esakaza ku-anode ezoncishiswa futhi akhiqize i-H2.
Ngokwesisekelo somehluko emisebenzini yazo, izithasiselo zokuvikela ukukhokhiswa ngokweqile zingahlukaniswa njengezithasiselo ze-redox shuttle kanye nezithasiselo zokuvala shaqa.Owokuqala uvikela iseli ekukhokhisweni ngokweqile ngendlela ebuyela emuva, kuyilapho eyakamuva inqamula ukusebenza kweseli unomphela.
Izithasiselo ze-Redox shuttle zisebenza ngokuvala ngamakhemikhali amandla ebhethri ukushaja okweqile okujovwe ebhethrini lapho ukushajwa ngokweqile kwenzeka.Njengoba kuboniswe kuUmfanekiso 3F, umshini usekelwe esithasiselweni se-redox esinamandla e-oxidation angaphansi kancane kunalelo lokubola kwe-electrolyte anodic.Endaweni egcwele ukushajwa kwe-cathode, isithasiselo se-redox sikhishwa nge-oxid sibe kwifomu elithi [O], kamuva elizoncishiswa libuyele esimweni salo sangempela [R] ebusweni be-anode ngemva kokusabalalisa nge-electrolyte.Ngemuva kwalokho, isithasiselo esincishisiwe singasabalalisa sibuyele ku-cathode, futhi umjikelezo we-electrochemical "we-oxidation-diffusion-reduction-diffusion" ungagcinwa unomphela futhi ngaleyo ndlela ukhiye amandla e-cathode ekuqhubekeni nokushajwa okuyingozi.Ucwaningo luye lwabonisa ukuthi amandla e-redox ezithasiselo kufanele abe cishe ku-0.3 kuya ku-0.4 V ngaphezu kwamandla e-cathode.
Kwakhiwe uchungechunge lwezithako ezinezakhiwo zamakhemikhali eziklanywe kahle namandla e-redox, okuhlanganisa i-organometallic metallocenes , phenothiazines , triphenylamines , dimethoxybenzenes nokuphuma kwazo , kanye ne-2-(pentafluorophenyl) -tetrafluoro-1,3,2-benzodiodioUmfanekiso we-3G).Ngokuhlanganisa izakhiwo zamangqamuzana, amandla e-additive oxidation angashunwa abe ngaphezu kuka-4 V, afanele izinto ezikhula ngokushesha ze-high-voltage cathode nama-electrolyte.Umgomo oyisisekelo wokuklama ubandakanya ukwehlisa i-orbital ye-molecular ematasa kakhulu yesithasiselo ngokungeza izinto ezikhipha ama-electron, okuholela ekwenyukeni kwamandla okukhipha umoya.Ngaphandle kwezithasiselo eziphilayo, abanye usawoti we-inorganic, ongagcini nje ngokusebenza njengosawoti we-electrolyte kodwa futhi ongasebenza njenge-shuttle ye-redox, njengosawoti weqoqo le-perfluoroborane [okungukuthi, i-lithium fluorododecaborates (Li2B12F).xH12−x)], kuphinde kwatholakala ukuthi iyizithasiselo ezisebenza kahle ze-redox shuttle .
Izithasiselo zokukhokhiswa okungaphezu kokuvala shaqa ziyisigaba sezithasiselo ezingahlehliseki zokuvikela ukushajwa ngokweqile.Zisebenza ngokukhipha igesi ngamandla amakhulu, okuthi, bese, zisebenzisa isiphazamisi samanje, noma ngokufaka i-electrochemically polymerizing ngokusemandleni aphezulu ukunqamula ukusebenza kwebhethri ngaphambi kokuba kuvele imiphumela eyinhlekelele (Umfanekiso 3H).Izibonelo zangaphambili zifaka i-xylene , i-cyclohexylbenzene, ne-biphenyl , kuyilapho izibonelo zamuva zifaka i-biphenyl nezinye izinhlanganisela ezinuka kamnandi esikhundleni (Umfanekiso 3I).Imiphumela engemihle yezithasiselo zokuvala shaqa kusewukusebenza kwesikhathi eside nokusebenza kokugcinwa kwama-LIB ngenxa ye-oxidation engabuyiseleki yalezi zinhlanganisela.
Ukuxazulula izinkinga esigabeni 2 (ukuqoqwa kokushisa nenqubo yokukhishwa kwegesi)
Izinto ezithembekile ze-cathode.I-Lithium transition metal oxides, njengama-oxide agqinsile i-LiCoO2, i-LiNiO2, ne-LiMnO2;i-spinel-type oxide LiM2O4;kanye nohlobo lwe-polyanion i-LiFePO4, yizinto ezisetshenziswa kakhulu ze-cathode, okuthi, noma kunjalo, zinezinkinga zokuphepha ikakhulukazi emazingeni okushisa aphezulu.Phakathi kwazo, i-olivine-structured LiFePO4 iphephile uma iqhathaniswa, ezinzile ifike ku-400 ° C, kuyilapho i-LiCoO2 iqala ukubola ku-250 ° C.Isizathu sokuphepha okuthuthukisiwe kwe-LiFePO4 ukuthi wonke ama-ion oksijini enza izibopho eziqinile ze-covalent ne-P5 + ukuze enze i-PO43-tetrahedral polyanions, eqinisa lonke uhlaka lwe-three-dimensional futhi inikeze ukuzinza okuthuthukisiwe uma kuqhathaniswa nezinye izinto ze-cathode, nakuba kusekhona kube nezingozi zomlilo webhethri ezibikiwe.Ukukhathazeka okukhulu kokuphepha kuvela ekuboleni kwalezi zinto ezisetshenziswayo ze-cathode emazingeni okushisa aphakeme kanye nokukhululwa komoyampilo ngesikhathi esisodwa, okungase kuholele ekushisweni nasekuqhumeni, okufaka engcupheni ukuphepha kwebhethri .Isibonelo, isakhiwo sekristalu se-oxide egqinsiwe i-LiNiO2 asizinzile ngenxa yokuba khona kwe-Ni2+, usayizi we-ionic ofana nowe-Li+.U-Li okhubazekilexI-NiO2 (x<1) ijwayele ukuguqulela esigabeni esizinzile sohlobo lwe-spinel i-LiNi2O4 (i-spinel) kanye ne-rocksalt-type NiO, ne-oxygen ekhishwe ku-electrolyte ewuketshezi cishe ku-200 ° C, okuholela ekushisweni kwe-electrolyte.
Kuye kwenziwa imizamo emikhulu yokuthuthukisa ukuzinza kokushisa kwalezi zinto ze-cathode ngokusebenzisa i-athomu ye-athomu kanye nezingubo zokuzivikela ezingaphezulu.
I-Atom doping ingakhuphula kakhulu ukuzinza okushisayo kwezinto ze-oxide ezigqinsiwe ngenxa yezakhiwo zekristalu ezinzile.Ukuzinza okushisayo kwe-LiNiO2 noma i-Li1.05Mn1.95O4 kungathuthukiswa kakhulu ngokufaka ingxenye ye-Ni noma i-Mn namanye ama-cations ensimbi, afana ne-Co, Mn, Mg, ne-Al .Ku-LiCoO2, ukwethulwa kwezakhi ze-doping ne-alloying njenge-Ni ne-Mn kungakhuphula kakhulu izinga lokushisa lokuqalisa kokubola.Tdec, kuyilapho futhi igwema ukusabela nge-electrolyte emazingeni okushisa aphezulu.Kodwa-ke, ukwanda kokuzinza kwe-cathode thermal ngokuvamile kuza nemihlatshelo esezingeni elithile.Ukuze kuxazululwe le nkinga, kusungulwe impahla ye-concentration-gradient cathode yamabhethri e-lithium aphinde ashajwe ngokusekelwe kungqimba lwe-lithium nickel cobalt manganese oxide (Umdwebo 4A).Kulesi sihloko, i-particle ngayinye ine-Ni-rich central bulk kanye ne-Mn-rich yangaphandle ungqimba, ngokunciphisa ukugxila kwe-Ni nokwandisa ukugxila kwe-Mn kanye ne-Co njengoba kusondela indawo.Umfanekiso 4B).Owokuqala uhlinzeka ngomthamo ophezulu, kanti owedlule uthuthukisa ukuzinza kwe-thermal.Le noveli ye-cathode material yaboniswa ukuthuthukisa ukuphepha kwamabhethri ngaphandle kokuphazamisa ukusebenza kwawo kwe-electrochemical (Umfanekiso 4C).
Umdwebo 4 Amasu okuxazulula izinkinga esigabeni 2: Ama-cathodes athembekile.
(A) Umdwebo ohleliwe wezinhlayiyana ze-electrode enomkhombo ocebile we-Ni-rich ozungezwe ungqimba lwangaphandle lwe-concentration-gradient.Uhlamvu ngalunye lunenqwaba emaphakathi e-Ni-rich Li(Ni0.8Co0.1Mn0.1)O2 kanye nongqimba lwangaphandle olucebile Mn [Li(Ni0.8Co0.1Mn0.1)O2] olunokuncipha kokugxilisa ingqondo kuka-Ni nokwandisa ukugxila kwe-Mn ne-Co njengoba kusondela ubuso.Owokuqala uhlinzeka ngomthamo ophezulu, kanti owedlule uthuthukisa ukuzinza kwe-thermal.Ukwakheka okumaphakathi ngu-Li(Ni0.68Co0.18Mn0.18)O2.I-electron micrograph yokuskena yezinhlayiyana ezivamile nayo iboniswa ngakwesokudla.(B) Imiphumela ye-Electron-probe x-ray microanalysis ye-lithiated oxide yokugcina Li(Ni0.64Co0.18Mn0.18)O2.Izinguquko zokugxila kancane kancane kwe-Ni, Mn, kanye ne-Co ku-interlayer ziyabonakala.Ukugxila kwe-Ni kuyehla, futhi ukugxila kwe-Co ne-Mn kukhuphukela phezulu.(C) I-calorimetry yokuskena ehlukile (DSC) ilandelela ebonisa ukugeleza kokushisa okuvela ekuphenduleni kwe-electrolyte enezinto zokugxilisa zegradient Li(Ni0.64Co0.18Mn0.18)O2, into emaphakathi ye-Ni-rich Li(Ni0.8Co0.1Mn0. 1)O2, kanye nongqimba lwangaphandle lwe-Mn-rich [Li(Ni0.46Co0.23Mn0.31)O2].Izinto zokwakha zishajelwe ku-4.3 V. (A), (B), no-(C) ziphinde zakhiqizwa ngemvume evela ku-Springer Nature.(D) Kwesobunxele: Isithombe se-electron microscopy (TEM) esikhanyayo se-AlPO4 nanoparticle–coated LiCoO2;I-spectrometry ye-x-ray ye-energy dispersive iqinisekisa izingxenye ze-Al kanye ne-P kungqimba lokumboza.Kwesokudla: Isithombe se-TEM esinokulungiswa okuphezulu esibonisa ama-nanoparticles e-AlPO4 (~3 nm ububanzi) kungqimba lwe-nanoscale coating;imicibisholo ikhombisa ukuxhumana phakathi kwesendlalelo se-AlPO4 ne-LiCoO2.(E) Kwesokunxele: Isithombe seseli esiqukethe i-LiCoO2 cathode engenalutho ngemva kokuhlolwa kokukhokhiswa ngokweqile okungu-12-V.Iseli lasha laqhuma kuleyo voltage.Kwesokudla: Isithombe seseli esiqukethe i-AlPO4 nanoparticle–coated LiCoO2 ngemva kokuhlolwa kokukhokhiswa ngokweqile okungu-12-V.(D) kanye no-(E) akhiqizwa kabusha ngemvume evela ku-John Wiley and Sons.
Elinye isu lokuthuthukisa ukuzinza kwe-thermal ukugqoka impahla ye-cathode ngongqimba oluncane oluvikelayo lwamakhompiyutha okuqhuba i-Li+ aqinile, angavimbela ukuthintana okuqondile kwezinto ze-cathode nge-electrolyte futhi ngaleyo ndlela kunciphise ukusabela kwe-side kanye nokukhiqizwa kokushisa.Izembatho zingaba amafilimu angaphili [ngokwesibonelo, ZnO , Al2O3, AlPO4 , AlF3 , njll.], angakwazi ukuqhuba ama-Li ions ngemva kokukhishwa kwe-lithiated (Umdwebo 4, D no-E), noma amafilimu ezinto eziphilayo, njenge-poly(diallyldimethylammonium chloride) , amafilimu okuzivikela akhiwe izithasiselo ze-γ-butyrolactone, kanye nezithasiselo ezinezingxenye eziningi (ezihlanganisa i-vinylene carbonate, 1,3-propylene sulfite, ne-dimethylacetamide) .
Ukwethula i-coefficient ene-coefficient yokushisa enhle nakho kuyasebenza ekwandiseni ukuphepha kwe-cathode.Isibonelo, i-poly(3-decylthiophene)–coated LiCoO2 cathodes ingavala ukusabela kwe-electrochemical kanye nokusabela kwezinhlangothi uma izinga lokushisa selikhuphuke lifika ku->80°C, njengoba ungqimba lwe-polymer eqhubayo lungashintsha ngokushesha lube esimweni sokumelana kakhulu .Izembatho zama-oligomer azinqamulelayo anezakhiwo ezinegatsha elikhulu zingaphinda zisebenze njengesendlalelo sokuvimbela esisabela ngokushisa ukuze sivale ibhethri ohlangothini lwe-cathode.
Umqoqi wamanje oshintshwa ngokushisa.Ukuvala ukusabela kwe-electrochemical ngesikhathi sokukhuphuka kwezinga lokushisa kwebhethri esigabeni 2 kungavimbela ngempumelelo izinga lokushisa ukuthi liqhubeke likhula.I-polymer switching (TRPS) esheshayo nehlehlayo ehlehliswayo ifakwe ngaphakathi kumqoqi wamanje (Umdwebo 5A).Ifilimu elizacile le-TRPS liqukethe izinhlayiya ze-graphene-coated spiky nanostructured nickel (GrNi) eziqhutshwayo njengesigcwalisi esihambisayo kanye ne-PE matrix ene-coefficient enkulu yokwandisa okushisayo (α ~ 10−4 K−1).Amafilimu ayinhlanganisela ye-polymer enziwe abonisa ukusebenza okuphezulu (σ) ekamelweni lokushisa, kodwa lapho izinga lokushisa lisondela ezingeni lokushisa elishintshayo (Ts), i-conductivity iyancipha phakathi kwe-1 s ngama-oda ayisikhombisa kuya kwayisishiyagalombili ngenxa yokwanda kwevolumu ye-polymer, ehlukanisa izinhlayiya ze-conductive futhi iphule izindlela zokuqhuba (Umfanekiso 5B).Ifilimu ngokushesha iba yi-insulating futhi ngaleyo ndlela inqamule ukusebenza kwebhethri (Umfanekiso 5C).Le nqubo ibuyiseleka emuva kakhulu futhi ingasebenza ngisho nangemva kwemicimbi eminingi yokushisa ngokweqile ngaphandle kokuphazamisa ukusebenza.
Umdwebo 5 Amasu okuxazulula izinkinga esigabeni sesi-2.
(A) Umfanekiso wohlelo wendlela yokushintsha eshisayo yomqoqi wamanje we-TRPS.Ibhethri eliphephile lineqoqo lamanje elilodwa noma amabili ambozwe ngesendlalelo esincane se-TRPS.Isebenza ngokujwayelekile ekamelweni lokushisa.Kodwa-ke, uma izinga lokushisa eliphezulu noma lamanje elikhulu, i-matrix ye-polymer iyanda, ngaleyo ndlela ihlukanise izinhlayiya ze-conductive, ezinganciphisa ukuqhutshwa kwayo, ukwandisa kakhulu ukumelana kwayo nokuvala ibhethri.Isakhiwo sebhethri singavikeleka ngaphandle kokulimala.Lapho ipholisa, i-polymer iyashwabana futhi iphinde ithole izindlela zokuqala zokuqhuba.(B) Izinguquko zokungazweli zamafilimu ahlukene e-TRPS njengomsebenzi wezinga lokushisa, okuhlanganisa i-PE/GrNi enokulayisha okuhlukile kwe-GrNi kanye ne-PP/GrNi enokulayisha okungu-30% (v/v) kwe-GrNi.(C) Isifinyezo somthamo wokuhamba ngebhayisikili okuphephile kwe-LiCoO2 phakathi kuka-25°C nokuvalwa.Umthamo oseduze noziro ku-70°C ubonisa ukuvala shaqa okugcwele.(A), (B), kanye no-(C) akhiqizwe kabusha ngemvume evela ku-Springer Nature.(D) Ukumelwa okuhleliwe komqondo wokuvala shaqa okusekelwe ku-microsphere kuma-LIB.Ama-Electrodes asebenza ngama-microspheres abamba ukushisa okuthi, ngaphezu kwezinga lokushisa elibalulekile lebhethri langaphakathi, adlule ku-thermal (ncibilika).Amakhepsuli ancibilikisiwe amboza indawo ye-electrode, akhe umgoqo ovikela i-ionically futhi avale iseli yebhethri.(E) I-membrane ehlanganisiwe ye-inorganic and self-stand eyakhiwe ngezinhlayiya ze-alumina ezingu-94% kanye ne-6% ye-styrene-butadiene rubber (SBR) binder yalungiswa ngendlela yokukhipha isisombululo.Kwesokudla: Izithombe ezibonisa ukuqina okushisayo kwesihlukanisi esiyinhlanganisela ye-inorganic kanye nesihlukanisi se-PE.Izihlukanisi zigcinwe ku-130 ° C imizuzu engu-40.I-PE inciphe ngokuphawulekayo endaweni ngesikwele esinamachashazi.Nokho, isihlukanisi esiyinhlanganisela asizange sibonise ukuncipha okusobala.Ikhiqizwe kabusha ngemvume evela ku-Elsevier.(F) Isakhiwo se-molecule yamanye ama-polymer okushisa ancibilika kakhulu njengezinto zokuhlukanisa ezinokuncipha okuphansi kwezinga lokushisa eliphezulu.Phezulu: i-polyimide (PI).Phakathi: i-cellulose.Ngezansi: i-poly(butylene) terephthalate.(G) Kwesobunxele: Ukuqhathaniswa kwe-spectra ye-DSC ye-PI nesihlukanisi se-PE ne-PP;isihlukanisi se-PI sibonisa ukuzinza okuhle kakhulu kwezinga lokushisa elisuka ku-30° ukuya ku-275°C.Kwesokudla: Izithombe zekhamera yedijithali eziqhathanisa ukumanzisa kwesihlukanisi sezentengiso kanye nesihlukanisi se-PI esihlanganiswe ne-propylene carbonate electrolyte.Ikhiqizwe kabusha ngemvume evela ku-American Chemical Society.
Izihlukanisi zokuvala shaqa ezishisayo.Elinye isu lokuvimbela amabhethri ukuthi angaphumi ngesikhathi sesiteji sesi-2 ukuvala indlela yokuqhuba yama-Li ions ngesihlukanisi.Izihlukanisi ziyizingxenye ezibalulekile zokuphepha kwama-LIB, njengoba zivimbela ukuthintana okuqondile kukagesi phakathi kwe-cathode yamandla aphezulu kanye nezinto ze-anode ngenkathi zivumela ukuthutha kwe-ionic.I-PP ne-PE yizinto ezisetshenziswa kakhulu, kodwa azinzinzi kahle ezishisayo, ezinamaphoyinti ancibilikayo angu-~165° kanye no-~135°C, ngokulandelana.Ku-LIB yezohwebo, izihlukanisi ezinesakhiwo se-trilayer se-PP/PE/PP sezivele zenzelwe ukuhweba, lapho i-PE iyisendlalelo esimaphakathi esivikelayo.Lapho izinga lokushisa langaphakathi lebhethri likhuphuka ngaphezu kwezinga lokushisa elibalulekile (~ 130 ° C), ungqimba lwe-PE olunezimbobo luncibilika kancane, luvale ama-pores efilimu futhi luvimbele ukufuduka kwama-ion ku-electrolyte ewuketshezi, kuyilapho ungqimba lwe-PP luhlinzeka ngokusekela komshini ukuze kugwenywe ngaphakathi. ukushoda .Okunye, ukuvala shaqa okubangelwa ukushisa kwe-LIB nakho kungafezwa ngokusebenzisa i-PE eshisayo noma ama-microspheres we-parafini wax njengongqimba oluvikelayo lwe-anode yebhethri noma izihlukanisi .Lapho izinga lokushisa langaphakathi lebhethri lifinyelela inani elibalulekile, ama-microspheres ayancibilika futhi amboze i-anode/isihlukanisi ngesithiyo esingafinyeleli, amise ukuthutha kwe-Li-ion futhi avale iseli unomphela (Umdwebo 5D).
Izihlukanisi ezinokuzinza okuphezulu kokushisa.Ukuze kuthuthukiswe ukuqina okushisayo kwezihlukanisi zamabhethri, izindlela ezimbili zenziwe phakathi neminyaka embalwa edlule:
(1) Izihlukanisi ezithuthukisiwe ze-ceramic, ezenziwe ngokunameka okuqondile noma ukukhula okungaphezulu kwezingqimba zobumba ezifana ne-SiO2 ne-Al2O3 endaweni ekhona yesihlukanisi se-polyolefin noma ngokuba nezimpushana zobumba ezishunyekwe ezintweni ze-polymeric (Umfanekiso 5E), bonisa amaphuzu ancibilikayo aphakeme kakhulu namandla aphezulu okusebenza futhi abe nokuhamba okushisayo okuphakeme uma kuqhathaniswa.Ezinye izihlukanisi eziyinhlanganisela ezenziwe ngalelisu zenzelwe ezentengiso, njenge-Separion (igama lokuhweba).
(2) Ukushintsha izinto zesihlukanisi zisuka ku-polyolefin ziye kuma-polymer okushisa ancibilika kakhulu ancipha kancane lapho kushiswa, njenge-polyimide, i-cellulose, i-poly(butylene) terephthalate, namanye ama-poly(esters) afanayo, elinye isu elisebenzayo lokuthuthukisa ukuzinza okushisayo. zabahlukanisi (Umdwebo 5F).Isibonelo, i-polyimide iyi-polymer e-thermosetting ebhekwa kabanzi njengenye indlela ethembisayo ngenxa yokuqina kwayo okuhle kakhulu kokushisa (okuzinzile ngaphezu kuka-400°C), ukumelana namakhemikhali okuhle, amandla okubamba ngamandla, ukumanzisa kahle kwe-electrolyte, kanye nokubambezeleka komlilo (Umdwebo 5G).
Amaphakheji ebhethri anomsebenzi wokupholisa.Amasistimu okulawula ukushisa kwesikali sedivayisi anikwe amandla ngokuzuliswa komoya noma ukupholisa uketshezi asetshenziselwe ukuthuthukisa ukusebenza kwebhethri kanye nokwehlisa izinga lokushisa.Ukwengeza, izinto zokushintsha isigaba ezifana ne-wax kapharafini zihlanganiswe namaphakethe webhethri ukuze zisebenze njengesitha sokushisa ukuze zilawule izinga lokushisa kwazo, ngakho-ke kugwema ukusetshenziswa kabi kwezinga lokushisa.
Ukuxazulula izinkinga esiteji sesi-3 (ukuvutha nokuqhuma)
Ukushisa, umoya-mpilo, nophethiloli, okwaziwa ngokuthi “unxantathu womlilo,” kuyizithako ezidingekayo emililo eminingi.Ngokunqwabelana kokushisa nomoya-mpilo okhiqizwa phakathi nezigaba 1 no-2, uphethiloli (okungukuthi, ama-electrolyte avutha kakhulu) azoqala ukuvutha ngokuzenzakalelayo.Ukunciphisa ukuvutha kwezinyibilikisi ze-electrolyte kubalulekile ekuphepheni kwebhethri nokunye ukusetshenziswa kwesilinganiso esikhulu kwama-LIB.
Izithasiselo ezivimbela amalangabi.Imizamo emikhulu yocwaningo iye yanikelwa ekuthuthukiseni izithasiselo ezingabambezeli ilangabi ukuze kwehliswe ukusha kwama-electrolyte anguketshezi .Iningi lezithasiselo ezingabusheki ilangabi ezisetshenziswa kuma-electrolyte anguketshezi zisekelwe kumakhompiyutha e-organic phosphorus noma ama-organic halogenated compounds.Njengoba ama-halogen eyingozi emvelweni nempilo yabantu, izinhlanganisela ze-organic phosphorus zingamakhandidethi athembisayo njengezithasiselo ezinganqamuki ilangabi ngenxa yekhono lawo eliphezulu lokuvimbezela amalangabi kanye nobungane bemvelo.Izinhlanganisela ezijwayelekile ze-organic phosphorus zihlanganisa 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 (i-phosphate, njll.Umfanekiso 6A).Indlela yemiphumela yokuvimbela ilangabi yalezi zinhlanganisela eziqukethe i-phosphorus ngokuvamile kukholakala ukuthi iyinqubo yokukhipha amakhemikhali.Ngesikhathi sokusha, ama-molecule aqukethe i-phosphorus angabola abe yizinhlobo ze-phosphorus-free-radicals, ezingase ziqede ama-radicals (isibonelo, ama-radicals e-H kanye ne-OH) akhiqizwa ngesikhathi sokusatshalaliswa kwe-chain reaction enesibopho sokuvutha okuqhubekayo (Umdwebo 6, B kanye no-C).Ngeshwa, ukuncipha kokuvutha ngokungezwa kwalezi zinqamuli zomlilo ezine-phosphorus kuza ngezindleko zokusebenza kwe-electrochemical.Ukuze kuthuthukiswe lokhu kuhwebelana, abanye abacwaningi baye benza izinguquko ezithile esakhiweni sabo samangqamuzana: (i) i-fluorination ingxenye yama-alkyl phosphates ingathuthukisa ukuzinza kwawo okuncishiswayo kanye nokusebenza kwawo kokulibaziseka komlilo;(ii) ukusetshenziswa kwezinhlanganisela ezinakho kokubili ukwakheka kwefilimu evikelayo kanye nezakhiwo ezivimbezela ilangabi, njenge-bis(2-methoxyethoxy)methylallylphosphonate, lapho amaqembu ahlangene angakwazi ukwenza i-polymerize futhi akhe ifilimu ye-SEI ezinzile endaweni yegraphite, ngaleyo ndlela avimbele ngokuphumelelayo uhlangothi oluyingozi. ukusabela;(iii) ukushintshwa kwe-P(V) phosphate kuya ku-P(III) phosphite, okwenza kube lula ukwakheka kwe-SEI futhi ekwazi ukuvala i-PF5 eyingozi [ngokwesibonelo, i-tris(2,2,2-trifluoroethyl) phosphite];kanye (iv) nokushintsha izithasiselo ze-organophosphorus nge-cyclic phosphazenes, ikakhulukazi i-fluorinated cyclophosphazene, ethuthukise ukuhambisana kwe-electrochemical.
Umdwebo 6 Amasu okuxazulula izinkinga esigabeni sesi-3.
(A) Izakhiwo zamangqamuzana ezijwayelekile zezithasiselo ezinganqamuki ilangabi.(B) Indlela yemiphumela yokuvinjelwa kwelangabi yalezi zinhlanganisela eziqukethe i-phosphorus ngokuvamile kukholakala ukuthi iyinqubo yokukhipha amakhemikhali eqinile, enganqamula ukusabela okunamandla kweketango okunesibopho sokusabela kokusha esigabeni segesi.I-TPP, i-triphenyl phosphate.(C) Isikhathi sokuzicisha (SET) se-carbonate electrolyte evamile singancishiswa kakhulu ngokungezwa kwe-triphenyl phosphate.(D) Isikimu sesehlukanisi se-electrospun “ehlakaniphile” esinezindawo ezivimbela ilangabi ezishisayo zama-LIB.Isihlukanisi esizimele sakhiwe ngama-microfibers anesakhiwo segobolondo eliyinhloko, lapho i-flame retardant iwumgogodla kanye ne-polymer igobolondo.Lapho i-thermal triggering, igobolondo le-polymer liyancibilika bese i-retardant ye-flame ehlanganisiwe ikhishwa ku-electrolyte, ngaleyo ndlela icindezele ngempumelelo ukuthungela nokushiswa kwama-electrolyte.(E) Isithombe se-SEM sama-microfiber e-TPP@PVDF-HFP ngemva kokushumeka sibonisa ngokusobala ukwakheka kwawo kwegobolondo eliyinhloko.Ibha yesikali, 5 μm.(F) Izakhiwo zamangqamuzana ezivamile zethempelesha ye-ionic liquid esetshenziswa njengama-electrolyte angashi ama-LIB.(G) Ukwakheka kwamangqamuzana e-PFPE, i-analog ye-PEO ene-perfluorinated engashi.Amaqembu amabili e-methyl carbonate ashintshwa kumatheminali amaketanga e-polymer ukuze kuqinisekiswe ukuhambisana kwama-molecule nezinhlelo zebhethri zamanje.
Kufanele kuqashelwe ukuthi kuhlale kunokuhwebelana phakathi kokuncipha kokuvutha kwe-electrolyte nokusebenza kweseli kwezithasiselo ezisohlwini, nakuba lokhu kuvumelana kuye kwathuthukiswa ngemiklamo engenhla yamangqamuzana .Elinye isu elihlongozwayo lokuxazulula le nkinga lihlanganisa ukufaka i-flame retardant ngaphakathi kwegobolondo le-polymer elivikelayo lama-microfibers, aphinde apakishwe ukuze akhe isihlukanisi esingalukiwe.Umfanekiso 6D).Inoveli yesihlukanisi se-electrospun nonwoven microfiber esinezinto ezikwazi ukumelana nelangabi esidalwa ukufudumala senzelwe ama-LIB.Ukufakwa kwe-encapsulation ye-flame retardant ngaphakathi kwegobolondo le-polymer elivikelayo kuvimbela ukuchayeka okuqondile kwe-flame retardant ku-electrolyte, kuvimbele imiphumela engemihle evela kuma-retardants ekusebenzeni kwebhethri ye-electrochemical (Umfanekiso 6E).Nokho, uma kwenzeka ukubaleka okushisayo kwebhethri le-LIB, igobolondo le-poly(vinylidenefluoride-hexafluoro propylene) copolymer (PVDF-HFP) lizoncibilika njengoba izinga lokushisa linyuka.Khona-ke i-encapsulated triphenyl phosphate flame retardant izokhishelwa ku-electrolyte, ngaleyo ndlela icindezele ngempumelelo ukusha kwama-electrolyte avutha kakhulu.
Umqondo othi “i-electrolyte egxile kusawoti” waphinde wasungulwa ukuze kuxazululwe le nkinga .Lawa ma-electrolyte aphilayo acisha umlilo amabhethri aphinde ashajwa aqukethe i-LiN(SO2F)2 njengosawoti kanye ne-flame retardant ethandwayo ye-trimethyl phosphate (TMP) njengesinyibilikisi sodwa.Ukwakheka okuzenzakalelayo kwe-SEI eqinile etholakala kusawoti etholakala kusawoti ku-anode kubalulekile ekusebenzeni okuzinzile kwe-electrochemical.Leli su lenoveli linganwetshwa kwezinye izinqamuleli zamalangabi ezahlukahlukene futhi lingase livule indlela entsha yokwakha izinyibilikisi ezintsha ezibamba amalangabi kuma-LIB aphephile.
Ama-electrolyte angama-liquid angashi.Isixazululo esikhulu ezindabeni zokuphepha ze-electrolyte kungaba ukuthuthukisa ama-electrolyte angashi.Iqembu elilodwa lama-electrolyte angashi eliye lacutshungulwa kabanzi uketshezi lwe-ionic, ikakhulukazi uketshezi lwe-ionic lokushisa kwegumbi, olungaguquguquki (akukho mfutho womhwamuko otholakalayo ongaphansi kuka-200°C) futhi ezingashi futhi ezinefasitela elibanzi lokushisa.Umfanekiso 6F).Kodwa-ke, ucwaningo oluqhubekayo lusadingeka ukuze kuxazululwe izinkinga zenani eliphansi lekhono elivela ngenxa ye-viscosity yabo ephezulu, inombolo ephansi yokudluliselwa kwe-Li, ukungazinzi kwe-cathodic noma ukunciphisa, kanye nezindleko eziphezulu zoketshezi lwe-ionic.
Ama-hydrofluoroethers anesisindo esiphansi samangqamuzana angesinye isigaba sama-electrolyte anguketshezi angashi ngenxa yephuzu lawo elikhanyayo noma elingenawo, ukungashi, ukungezwani okuphansi kwendawo, i-viscosity ephansi, izinga lokushisa eliphansi eliqandayo, njll.Idizayini efanele yamangqamuzana kufanele yenziwe ukuze ivumelane nezimo zayo zamakhemikhali ukuze ihlangabezane nemibandela yama-electrolyte ebhethri.Isibonelo esithakazelisayo esisanda kubikwa yi-perfluoropolyether (PFPE), i-perfluorinated polyethylene oxide (PEO) analog eyaziwa kakhulu ngokungashi kwayo (Umfanekiso 6G).Amaqembu amabili e-methyl carbonate alungiswa emaqenjini agcinayo amaketango e-PFPE (PFPE-DMC) ukuze kuqinisekiswe ukuhambisana kwama-molecule nezinhlelo zebhethri zamanje.Ngakho-ke, ukungashi kanye nokuzinza okushisayo kwama-PFPE kungathuthukisa ukuphepha kwama-LIB kakhulu ngenkathi kukhulisa inombolo yokudluliselwa kwe-electrolyte ngenxa yomklamo oyingqayizivele wesakhiwo samangqamuzana.
Isiteji sesi-3 yisigaba sokugcina kodwa esibaluleke kakhulu senqubo yokubaleka okushisayo.Kumele kuqashelwe ukuthi nakuba imizamo emikhulu iye yanikelwa ekunciphiseni ukuvutha kwe-electrolyte ye-liquid yesimanje, ukusetshenziswa kwama-electrolyte aqinile angashintshile kubonisa isithembiso esikhulu.Ama-electrolyte aqinile awela ezigabeni ezimbili: ama-electrolyte e-ceramic angaphili [ama-sulfide, ama-oxide, ama-nitride, ama-phosphates, njll.] kanye nama-electrolyte e-polymer aqinile [inhlanganisela kasawoti ka-Li nama-polymers, njenge-poly(ethylene oxide), i-polyacrylonitrile, njll.] .Imizamo yokuthuthukisa ama-electrolyte aqinile ngeke ichazwe lapha, njengoba lesi sihloko sesivele sifinyezwe kahle kuzibuyekezo ezimbalwa zakamuva.
UKUBUKA
Esikhathini esedlule, izinto eziningi ezintsha zenzelwe ukuthuthukisa ukuphepha kwebhethri, nakuba inkinga ingakaxazululwa ngokuphelele.Ukwengeza, izindlela eziyisisekelo zezinkinga zokuphepha ziyahlukahluka kukhemistri yebhethri ehlukene.Ngakho, izinto ezithile eziklanyelwe amabhethri ahlukene kufanele zakhelwe.Sikholelwa ukuthi izindlela ezisebenza kahle kakhulu nezinto eziklanywe kahle zisazotholakala.Lapha, sibala izikhombisi-ndlela ezimbalwa ezingaba khona zocwaningo lwesikhathi esizayo lokuphepha kwebhethri.
Okokuqala, kubalulekile ukuthuthukisa ku-situ noma ezindleleni ze-operando ukuthola nokuqapha izimo zempilo zangaphakathi zama-LIB.Isibonelo, inqubo yokubaleka okushisayo ihlobene eduze nezinga lokushisa langaphakathi noma ukunyuka kwengcindezi ngaphakathi kwama-LIB.Nokho, ukusabalalisa izinga lokushisa ngaphakathi kwamabhethri kuyinkimbinkimbi, futhi izindlela ziyadingeka ukuze kuqashwe ngokunembile amanani ama-electrolyte nama-electrode, kanye nezihlukanisi.Ngakho-ke, ukukwazi ukukala le mingcele yezingxenye ezihlukene kubalulekile ekuxilongeni futhi ngaleyo ndlela kuvinjwe izingozi zokuphepha kwebhethri.
Ukuzinza okushisayo kwezihlukanisi kubalulekile ekuphepheni kwebhethri.Ama-polymers asanda kuthuthukiswa anamaphuzu aphezulu okuncibilika ayasebenza ekwandiseni ubuqotho bokushisa kwesihlukanisi.Kodwa-ke, izakhiwo zabo zemishini zisephansi, zinciphisa kakhulu ukucutshungulwa kwazo ngesikhathi sokuhlanganisa ibhethri.Ngaphezu kwalokho, intengo nayo iyisici esibalulekile okufanele sicatshangelwe ukuze kusetshenziswe izinto ezingokoqobo.
Ukuthuthukiswa kwama-electrolyte aqinile kubonakala kuyisixazululo esikhulu ezindabeni zokuphepha zama-LIB.I-electrolyte eqinile izonciphisa kakhulu ithuba lokushoda kwebhethri kwangaphakathi, kanye nobungozi bomlilo nokuqhuma.Nakuba kuye kwanikelwa imizamo emikhulu ekuthuthukisweni kwama-electrolyte aqinile, ukusebenza kwawo kusaqhubeka kusalele emuva kakhulu kwalokho kwama-electrolyte anguketshezi.Inhlanganisela yama-electrolyte we-inorganic kanye ne-polymer akhombisa amandla amakhulu, kepha adinga ukwakheka nokulungiselela okuntekenteke.Sigcizelela ukuthi idizayini efanele yokuhlangana kwe-inorganic-polymer kanye nobunjiniyela bokuqondanisa kwabo kubalulekile ekuthuthweni kwe-Li-ion okuphumelelayo.
Kufanele kuqashelwe ukuthi i-electrolyte ewuketshezi akuyona ukuphela kwengxenye yebhethri ekwazi ukusha.Isibonelo, uma ama-LIB eshajwe kakhulu, izinto ezivuthayo ze-lithiated anode (isibonelo, i-lithiated graphite) nazo ziwukukhathazeka okukhulu kokuphepha.Ama-flame retardants angakwazi ukunqanda umlilo wezinto eziqinile zezwe afunwa kakhulu ukuze kwandiswe ukuphepha kwawo.I-retardants yomlilo ingase ihlanganiswe ne-graphite ngendlela yama-polymer binders noma izinhlaka eziqhutshwayo.
Ukuphepha kwebhethri kuyinkinga eyinkimbinkimbi futhi eyinkimbinkimbi.Ikusasa lokuphepha kwebhethri lidinga imizamo eyengeziwe ezifundweni zemishini eziyisisekelo zokuqonda okujulile ngaphezu kwezindlela ezithuthuke kakhulu zokuchaza abalingiswa, ezinganikeza ulwazi olwengeziwe ukuqondisa ukwakheka kwezinto.Nakuba lokhu Kubuyekezwa kugxile ekuphepheni kwezinga lezinto ezibonakalayo, kufanele kuqashelwe ukuthi indlela ephelele iyadingeka futhi ukuze kuxazululwe inkinga yokuphepha yama-LIB, lapho izinto zokwakha, izingxenye zeseli nefomethi, kanye nemojula yebhethri namaphakethe kudlala indima elinganayo ukwenza amabhethri athembeke ngaphambili. bakhululwe emakethe.
IZIKHOMBISI NAMANOTHI
Kai Liu, Yayuan Liu, DingchangLin, Allen Pei, Yi Cui, Izinto zokuphepha kwebhethri ye-lithium-ion, I-ScienceAdvances, DOI:10.1126/sciadv.aas9820
Isikhathi sokuthumela: Jun-05-2021
