Ibisobanuro
Batteri ya Litiyumu-ion (LIBs) ifatwa nkimwe mu buhanga bukomeye bwo kubika ingufu.Nkuko ingufu za bateri ziyongera, umutekano wa bateri urakomera cyane iyo ingufu zirekuwe utabishaka.Impanuka zijyanye numuriro no guturika kwa LIBs bikunze kugaragara kwisi yose.Bamwe bateje akaga gakomeye ubuzima bwabantu nubuzima kandi byatumye ibicuruzwa byinshi byibutswa nababikora.Ibi bintu byibutsa ko umutekano ari ikintu gisabwa kuri bateri, kandi ibibazo bikomeye bigomba gukemurwa mbere yigihe kizaza cyo gukoresha sisitemu ya batiri ifite ingufu nyinshi.Iri suzuma rigamije kuvuga mu ncamake ishingiro ryinkomoko yibibazo byumutekano wa LIB no kwerekana iterambere ryibanze mubikorwa byo kunoza umutekano wa LIB.Turateganya ko iri suzuma rizatera imbaraga kurushaho kurushaho guteza imbere umutekano wa batiri, cyane cyane kuri LIB zigaragara zifite ingufu nyinshi.
INKOMOKO Z'IBIBAZO BY'UMUTEKANO
Amazi kama ya electrolyte imbere muri LIBs arashya.Kimwe mu bintu byananiranye cyane muri sisitemu ya LIB ni ikintu gishimishije cyo guhunga ubushyuhe, bufatwa nkimpamvu nyamukuru itera umutekano wa batiri.Muri rusange, guhunga ubushyuhe bibaho iyo reaction ya exothermic reaction itagaragaye.Mugihe ubushyuhe bwa bateri buzamutse hejuru ya ~ 80 ° C, igipimo cyimiti ya exothermic reaction imbere muri bateri cyiyongera kandi kigashyushya selile, bikavamo ibitekerezo byiza.Ubushyuhe bukomeje kwiyongera bushobora kuvamo umuriro no guturika, cyane cyane kumapaki manini.Kubwibyo, gusobanukirwa ibitera nuburyo bwo gutwarwa nubushyuhe burashobora kuyobora igishushanyo mbonera cyibikorwa kugirango utezimbere umutekano no kwizerwa bya LIBs.Inzira yumuriro yumuriro irashobora kugabanywamo ibice bitatu, nkuko byavuzwe muriIgishushanyo 1.
Igishushanyo 1 Ibyiciro bitatu kubikorwa byo gutwarwa nubushyuhe.
Icyiciro cya 1: Intangiriro yo gushyuha.Batteri ihinduka kuva mubisanzwe ikajya muburyo budasanzwe, kandi ubushyuhe bwimbere butangira kwiyongera.Icyiciro cya 2: Gukusanya ubushyuhe hamwe no gusohora gaze.Ubushyuhe bwimbere burazamuka vuba, kandi bateri ikora reaction zidasanzwe.Icyiciro cya 3: Gutwika no guturika.Amashanyarazi ya electrolyte yaka, biganisha ku muriro ndetse no guturika.
Intangiriro yo gushyuha (icyiciro 1)
Guhunga ubushyuhe bitangirira ku bushyuhe bwa sisitemu ya bateri.Ubushyuhe bwambere bushobora kubaho nkigisubizo cya bateri yishyuwe hejuru yumubyigano wabigenewe (kurenza urugero), guhura nubushyuhe bukabije, imiyoboro migufi yo hanze kubera insinga zitari nziza, cyangwa imiyoboro migufi imbere kubera inenge ya selile.Muri byo, kugabanuka kwimbere nimpamvu yiganjemo guhunga ubushyuhe kandi biragoye kubigenzura.Kugabanuka kwimbere birashobora kubaho mugihe cyo kumenagura selile nkibikoresho byo hanze byinjira;impanuka y'imodoka;Gukora lithium dendrite munsi yumuriro mwinshi, mugihe kirenze urugero cyangwa mubushyuhe buke;no gutandukanya inenge byakozwe mugihe cyo guteranya bateri, kuvuga amazina make.Kurugero, mu ntangiriro z'Ukwakira 2013, imodoka ya Tesla hafi ya Seattle yagonze imyanda yatoboye ingabo hamwe na batiri.Imyanda yinjiye mu bitandukanya polymer hanyuma igahita ihuza cathode na anode, bituma bateri iba mugufi kandi ifata umuriro;muri 2016, umuriro wa batiri ya Samsung Note 7 watewe no gutandukanya ultrathin ikabije yangijwe byoroshye nigitutu cyo hanze cyangwa gusudira kuri electrode nziza, bigatuma bateri iba muke.
Mugihe cyicyiciro cya 1, imikorere ya bateri ihinduka kuva mubisanzwe ikajya muburyo budasanzwe, kandi ibibazo byose byavuzwe haruguru bizatera bateri gushyuha.Iyo ubushyuhe bwimbere butangiye kwiyongera, icyiciro cya 1 kirangira nicyiciro cya 2 gitangira.
Gukusanya ubushyuhe no gusohora gazi (icyiciro cya 2)
Mugihe icyiciro cya 2 gitangiye, ubushyuhe bwimbere burazamuka vuba, kandi bateri ihura nibi bikurikira (ibyo bitekerezo ntibibaho muburyo bwatanzwe; bimwe murimwe bishobora kubaho icyarimwe):
(1) Kwangirika kwa electrolyte ikomeye (SEI) kubora kubera ubushyuhe bwinshi cyangwa kwinjira mumubiri.Igice cya SEI kigizwe ahanini na stabilite (nka LiF na Li2CO3) hamwe na metastable [nka polymers, ROCO2Li, (CH2OCO2Li) 2, na ROLi].Nyamara, ibice byoroshye bishobora kubora bitarenze hafi 90 ° C, bikarekura imyuka yaka umuriro na ogisijeni.Fata (CH2OCO2Li) 2 nkurugero
(CH2OCO2Li) 2 → Li2CO3 + C2H4 + CO2 + 0.5O2
.Iyi ni reaction idasanzwe itera ubushyuhe hejuru.
(3) IgiheT> ~ 130 ° C, itandukanya polyethylene (PE) / polypropilene (PP) itangira gushonga, ibyo bikarushaho kwangiza ibintu kandi bigatera uruziga rugufi hagati ya cathode na anode.
(4) Amaherezo, ubushyuhe butera kubora kwa lithium metal oxyde cathode hanyuma bikavamo kurekura ogisijeni.Fata LiCoO2 nk'urugero, rushobora kubora guhera kuri ~ 180 ° C nkuko bikurikira
Isenyuka rya cathode naryo ni exothermic cyane, irusheho kongera ubushyuhe nigitutu kandi, nkigisubizo, byihutisha reaction.
Mugihe cyicyiciro cya 2, ubushyuhe bwiyongera kandi ogisijeni irundanya imbere muri bateri.Uburyo bwo guhunga ubushyuhe buturuka ku cyiciro cya 2 kugeza ku cyiciro cya 3 mugihe ogisijeni ihagije hamwe nubushyuhe byegeranijwe kugirango bitwike.
Gutwika no guturika (icyiciro cya 3)
Ku cyiciro cya 3, gutwika biratangira.Electrolytes ya LIBs ni organic, hafi ya byose hamwe bya karubone ya cyclicale na lineque alkyl.Bafite ihindagurika ryinshi kandi imbere ryaka cyane.Dufashe nk'icyuma gikoreshwa na karubone electrolyte [ivanze rya karubone ya etilene (EC) + dimethyl karubone (DMC) (1: 1 kuburemere)], irerekana umuvuduko wumuyaga wa 4.8 kPa mubushyuhe bwicyumba hamwe na flash point nkeya cyane ya 25 ° ± 1 ° C ku muvuduko w'ikirere wa 1.013.Umwuka wa ogisijeni n'ubushyuhe mu cyiciro cya 2 bitanga ibisabwa kugira ngo utwike amashanyarazi ya elegitoroniki yaka umuriro, bityo bitere umuriro cyangwa guturika.
Mu cyiciro cya 2 nicya 3, reaction ya exothermic ibaho mugihe cya-adiabatic.Rero, umuvuduko wihuse wa calorimetrie (ARC) nubuhanga bukoreshwa cyane bugereranya ibidukikije imbere muri LIBs, bikadufasha gusobanukirwa kubyerekeranye nubushyuhe bwumuriro.Igishushanyo 2yerekana ARC isanzwe ya LIB yanditswe mugihe cyibizamini byo gukoresha ubushyuhe.Kwigana ubushyuhe bwiyongera murwego rwa 2, isoko yubushyuhe bwongera ubushyuhe bwa bateri kugeza ubushyuhe butangiye.Hejuru yubushyuhe, SEI irabora, bizatera imiti myinshi ya chimique.Amaherezo, uwatandukanije azashonga.Igipimo cyo kwishyushya kiziyongera nyuma, biganisha ku guhunga ubushyuhe (mugihe igipimo cyo kwishyushya ari> 10 ° C / min) hamwe no gutwikwa na electrolyte (icyiciro cya 3).
Anode ni mesocarbon microbead grafite.Cathode ni LiNi0.8Co0.05Al0.05O2.Electrolyte ni 1.2 M LiPF6 muri EC / PC / DMC.Celgard 2325 itandukanya trilayer yakoreshejwe.Yahinduwe nu ruhushya rutangwa na Electrochemical Society Inc.
Twabibutsa ko ibisubizo byerekanwe haruguru bitabaho rwose uko byakabaye murutonde rwatanzwe.Nibibazo, bigoye kandi bitunganijwe.
IMIKORESHEREZE HAMWE N'UMUTEKANO WATANZWE
Ukurikije gusobanukirwa na batiri yumuriro wa batiri, inzira nyinshi zirimo kwigwa, hagamijwe kugabanya ingaruka zumutekano hifashishijwe igishushanyo mbonera cyibikoresho bya batiri.Mu bice bizakurikiraho, turavuga muri make ibikoresho bitandukanye byo kunoza umutekano wa bateri, gukemura ibibazo bihuye nibyiciro bitandukanye byo gutwarwa nubushyuhe.
Gukemura ibibazo murwego rwa 1 (gutangira ubushyuhe)
Ibikoresho byizewe bya anode.Imiterere ya Li dendrite kuri anode ya LIB itangiza icyiciro cya mbere cyo guhunga ubushyuhe.Nubwo iki kibazo cyagabanutse muri anode yubucuruzi bwa LIBs (urugero, anode ya karubone), Li dendrite ntabwo yabujijwe rwose.Kurugero, mubucuruzi bwa LIBs, kubika dendrite bibaho cyane cyane kuri graphite electrode kumpande niba anode na cathodes bidahujwe neza.Byongeye kandi, imikorere idakwiye ya LIBs irashobora no kuvamo ibyuma bya Li hamwe no gukura kwa dendrite.Birazwi neza ko dendrite ishobora gukorwa byoroshye mugihe bateri yashizwemo (i) mubucucike buri hejuru aho gushira ibyuma bya Li byihuta kuruta gukwirakwiza Li ion muri grafite nyinshi;(ii) mubihe birenze urugero mugihe grafite irenze;na (iii) ku bushyuhe buke [nk'urugero, ubushyuhe bwo munsi (~ 0 ° C)], bitewe n'ubukonje bwiyongera bwa electrolyte y'amazi hamwe no kurwanya Li-ion ikwirakwizwa.
Urebye kubintu bifatika, inkomoko yumuzi igena itangira rya Li dendrite gukura kuri anode ni SEI idahindagurika kandi idahwitse, itera ikwirakwizwa ryibanze ryaho.Ibice bya electrolyte, cyane cyane inyongeramusaruro, byakozweho ubushakashatsi kugirango tunoze uburinganire bwa SEI no gukuraho Li dendrite.Inyongeramusaruro zisanzwe zirimo ibinyabuzima bidakoreshwa [urugero, CO2, LiI, nibindi] hamwe nibintu kama birimo karubone idahagije nka karubone ya vinylene na malimide;molekile ya cyclicale idahindagurika nka butyrolactone, etylene sulfite, nibiyikomokaho;hamwe na florine yibintu nka karubone ya fluoroethylene, nibindi.Ndetse no mubice-kuri miriyoni, izo molekile zirashobora kunoza imikorere ya SEI, bityo bigahuza Li-ion kandi bigakuraho Li dendrite.
Muri rusange, ibibazo bya Li dendrite biracyahari muri grafite cyangwa karubone anode na silicon / SiO irimo anode izakurikiraho.Gukemura ikibazo cyubwiyongere bwa Li dendrite ningorabahizi ningirakamaro muguhuza ingufu nyinshi za Li-ion chemistries mugihe cya vuba.Twabibutsa ko, vuba aha, imbaraga nyinshi zashyizwe mubikorwa byo gukemura ikibazo cya Li dendrite muri anode yicyuma cya Li muguhuza Li-ion mugihe cyo kubitsa Li;kurugero, kurinda igipfundikizo, ubwubatsi bwa SEI bwubukorikori, nibindi. Muri ubu buryo, bumwe muburyo bushobora gutanga urumuri kuburyo byakemura ikibazo kuri anode ya karubone muri LIBs.
Amazi menshi ya electrolytike no gutandukanya.Amazi ya electrolyte nayitandukanya bigira uruhare runini mugutandukanya umubiri imbaraga nyinshi cathode na anode.Rero, byateguwe neza na electrolytike ikora kandi itandukanya irashobora kurinda cyane bateri mugihe cyambere cya batiri yumuriro (icyiciro 1).
Kurinda bateri kumenagura imashini, amashanyarazi ya elegitoronike yuzuye yabonetse hiyongereyeho silika yometse kuri karubone electrolyte (1 M LiFP6 muri EC / DMC).Iyo igitutu cya mashini cyangwa ingaruka, amazi yerekana ingaruka zogukomera hamwe no kwiyongera kwijimye, bityo bikagabanya imbaraga zingaruka no kwerekana kwihanganira kumeneka (Igishushanyo 3A)
Igishushanyo cya 3 Ingamba zo gukemura ibibazo murwego rwa 1.
(A) Gukata amashanyarazi ya electrolyte.Hejuru: Kuri electrolyte isanzwe, ingaruka za mashini zirashobora gutuma bateri igabanuka imbere, bigatera umuriro no guturika.Hasi: Ubuhanga bushya bwa electrolyte ifite imbaraga zo kogoshesha igitutu cyangwa ingaruka byerekana kwihanganira kumeneka, bishobora guteza imbere umutekano wa bateri.(B) Gutandukanya imikorere kugirango tumenye hakiri kare dendrite ya lithium.Ihinduka rya Dendrite muri bateri gakondo ya lithium, aho kwinjira byuzuye bitandukanya na lithium dendrite igaragara gusa mugihe bateri yananiwe kubera umuzenguruko w'imbere.Mugereranije, bateri ya lithium ifite itandukanyirizo (rigizwe nigice cyo kuyobora gishyizwe hagati yabatandukanije basanzwe), aho lithium dendrite ikuze yinjira mubitandukanya kandi igahuza nigitereko cyumuringa, bikaviramo kugabanuka.VCu - Li, ikora nk'umuburo wo gutsindwa byegereje bitewe n'umuzunguruko w'imbere.Ariko, bateri yuzuye ikomeza gukora neza hamwe na nonzero ishobora.(A) na (B) byahinduwe cyangwa byororoka byemewe na Springer Kamere..Ibumoso: Lithium anode irashobora gukora byoroshye kubitsa dendritic, ishobora gukura buhoro buhoro kandi ikinjira muri inert polymer itandukanya.Iyo dendrite amaherezo ihuza cathode na anode, bateri irazunguruka mugihe gito.Iburyo: Igice cya silika nanoparticles yashizwemo ibice bibiri byubucuruzi bwa polymer.Kubwibyo, iyo lithium dendrite ikuze ikinjira mubitandukanya, bazahura na silika nanoparticles murwego rwa sandwiched hanyuma bakoreshe amashanyarazi.(D) Gusikana microscopi ya electron (SEM) ishusho ya silika nanoparticle sandwiched itandukanya..(C), (D), na (E) byororoka byemewe na John Wiley na Sons.(F) Igishushanyo mbonera cyerekana uburyo bwinyongera ya redox.Ku buso bwa cathode burenze urugero, inyongera ya redox ihindurwamo okiside kumiterere [O], hanyuma igahita igabanuka uko yari imeze [R] hejuru ya anode ikwirakwizwa na electrolyte.Inzira ya electrochemicike ya okiside-ikwirakwizwa-kugabanya-gukwirakwiza irashobora kugumaho igihe kitazwi bityo igafunga ubushobozi bwa cathode kubirenze urugero.(G) Imiterere isanzwe yimiti yinyongera ya redox shuttle..(I) Imiterere yimiti isanzwe yo guhagarika inyongera yinyongera.Ubushobozi bwo gukora bwinyongera butondekanijwe munsi ya buri molekulari muri (G), (H), na (I).
Abitandukanya barashobora kwigizayo kuri cathode na anode kandi bakagira uruhare runini mugukurikirana ubuzima bwa bateri aho kugirango hirindwe ko hajyaho ibyiciro byashize 1. Kurugero, "gutandukanya ibintu" hamwe na polymer-metal-polymer trilayer (Igishushanyo 3B) irashobora gutanga imikorere mishya ya voltage-sensing.Iyo dendrite ikuze ikagera murwego rwagati, izahuza icyuma na anode kuburyo kugabanuka gutunguranye gutunguranye hagati yabo bishobora guhita bigaragara nkibisohoka.
Usibye gutahura, itandukanyirizo rya trilayeri ryashizweho kugirango ririnde Li dendrite iteje akaga kandi ridindiza imikurire yabo nyuma yo kwinjira mubitandukanya.Igice cya silika nanoparticles, yashizwemo ibice bibiri byubucuruzi bwa polyolefin (Igishushanyo cya 3, C na D), irashobora kurya ikintu cyose cyangiza Li dendrite, bityo bikazamura neza umutekano wa bateri.Ubuzima bwa bateri irinzwe bwongerewe cyane inshuro zigera kuri eshanu ugereranije no kugira abitandukanya bisanzwe (Igishushanyo 3E).
Kurinda birenze urugero.Kurenza urugero bisobanurwa nko kwishyuza bateri irenze voltage yagenewe.Kurenza urugero birashobora guterwa nubucucike bwihariye buriho, imyirondoro ikarishye, nibindi, bishobora kuzana ibibazo byinshi, harimo (i) gushira ibyuma bya Li kuri anode, bigira ingaruka zikomeye kumikorere ya batiri yumuriro numutekano;(ii) kubora ibikoresho bya cathode, kurekura ogisijeni;na (iii) kubora kwa electrolyte kama, kurekura ubushyuhe nibicuruzwa bya gaze (H2, hydrocarbone, CO, nibindi), bishinzwe guhunga ubushyuhe.Amashanyarazi ya reaction mugihe cyo kubora biragoye, bimwe muribi bikurikira.
Inyenyeri (*) yerekana ko gaze ya hydrogène ikomoka kuri protic, igasiga amatsinda yabyaye mugihe cya okiside ya karubone kuri cathode, hanyuma igakwirakwira kuri anode kugirango igabanuke kandi itange H2.
Ukurikije itandukaniro mumikorere yabo, inyongeramusaruro zirenzeho zishobora gushyirwa mubikorwa nka redox shuttle ninyongera.Iyambere irinda selile kurenza urugero, mugihe iyanyuma ihagarika imikorere ya selile burundu.
Redox shutle yongeramo imikorere mugukoresha amashanyarazi muguhagarika amafaranga arenze yatewe muri bateri mugihe birenze urugero.Nkuko bigaragara muriIgishushanyo 3F, uburyo bushingiye ku nyongeramusaruro ya redox ifite okiside ishobora kuba munsi gato ya electrolyte anodic decomposition.Ku buso bwa cathode burenze urugero, inyongera ya redox ihindurwamo okiside kumiterere [O], hanyuma igahita igabanuka uko yari imeze [R] hejuru ya anode nyuma yo gukwirakwizwa na electrolyte.Nyuma yibyo, inyongeramusaruro yagabanijwe irashobora gukwirakwira kuri cathode, kandi uruziga rwamashanyarazi rwa "okiside-diffuzion-kugabanya-gukwirakwiza" rushobora kugumaho igihe kitazwi bityo rero rugafunga ubushobozi bwa cathode kugirango bikabije.Ubushakashatsi bwerekanye ko ubushobozi bwa redox bwinyongera bugomba kuba hafi 0.3 kugeza 0.4 V hejuru yubushobozi bwa cathode.
Urukurikirane rw'inyongeramusaruro zifite imiterere-karemano ya chimique hamwe na redox ishobora gutezwa imbere, harimo metallocène organometallic, phenothiazines, triphenylamines, dimethoxybenzene n'ibiyikomokaho, na 2- (pentafluorophenyl) -tetrafluoro-1,3,2-benzodioxaborole (Igishushanyo cya 3G).Mu kudoda imiterere ya molekuline, imbaraga za okiside yinyongera irashobora guhuzwa hejuru ya 4 V, ikwiranye niterambere ryihuta ryibikoresho bya cathode na electrolytike.Ihame ryibanze ryibanze ririmo kugabanya molekulire ya orbital ihanitse cyane yinyongera hakoreshejwe uburyo bwo gukuramo insimburangingo, biganisha ku kwiyongera kwa okiside.Usibye inyongeramusaruro, imyunyu ngugu imwe n'imwe, idashobora gukora gusa nk'umunyu wa electrolyte ariko nanone ishobora gukora nka shitingi ya redox, nk'umunyu wa perfluoroborane [ni ukuvuga lithium fluorododecaborates (Li2B12F)xH12−x)], basanze kandi ari inyongera ya redox shuttle inyongera.
Gufunga ibyongeweho birenze urugero ni urwego rwinyongera zidasubirwaho zirengera.Bakora haba mukurekura gaze kubishoboka byinshi, nayo, igakora igikoresho gihagarika, cyangwa mugukoresha amashanyarazi burundu mumashanyarazi menshi kugirango bahagarike imikorere ya bateri mbere yuko ibisubizo byibiza bibaho (Igishushanyo 3H).Ingero zambere zirimo xylene, cyclohexylbenzene, na biphenyl, mugihe ingero zanyuma zirimo biphenyl nibindi bintu byasimbuwe ()Igishushanyo 3I).Ingaruka mbi zinyongera zo guhagarika ziracyari ibikorwa birebire nibikorwa byo kubika LIBs kubera okiside idasubirwaho yibi bikoresho.
Gukemura ibibazo murwego rwa 2 (kwegeranya ubushyuhe nuburyo bwo gusohora gaze)
Ibikoresho byizewe bya cathode.Litiyumu yinzibacyuho ya oxyde, nka oxyde ya LiCoO2, LiNiO2, na LiMnO2;ubwoko bwa spinel yo mu bwoko bwa LiM2O4;n'ubwoko bwa polyanion LiFePO4, bikoreshwa cyane mubikoresho bya cathode, ariko, bifite ibibazo byumutekano cyane cyane mubushyuhe bwinshi.Muri byo, LiFePO4 yubatswe na olivine ifite umutekano ugereranije, ihagaze kugeza kuri 400 ° C, naho LiCoO2 itangira kubora kuri 250 ° C.Impamvu yo kurushaho kunoza umutekano wa LiFePO4 nuko ion zose za ogisijeni zikora imiyoboro ikomeye ya covalent hamwe na P5 + kugirango ikore PO43− tetrahedral polyanion, ihindura urwego rwose rwibice bitatu kandi itanga umutekano muke ugereranije nibindi bikoresho bya cathode, nubwo bikiriho byabaye impanuka yumuriro wa batiri.Impungenge nyamukuru z'umutekano zituruka ku kubora kw'ibi bikoresho bya cathode ku bushyuhe bwo hejuru no kurekura icyarimwe ogisijeni, ibyo bikaba bishobora gutera inkongi y'umuriro no guturika, bikabangamira cyane umutekano wa batiri.Kurugero, imiterere ya kristu ya oxyde ya LiNiO2 idahindagurika kubera kubaho kwa Ni2 +, ubunini bwa ionic busa nubwa Li +.LixNiO2 (x> 1
Hashyizweho ingufu nyinshi zo kuzamura ubushyuhe bwumuriro wibikoresho bya cathode ukoresheje atome doping hamwe nubutaka bwo kurinda hejuru.
Doping ya Atom irashobora kongera cyane ubushyuhe bwumuriro wibikoresho bya oxyde bitewe nububiko bwa kristu butajegajega.Ubushyuhe bwumuriro wa LiNiO2 cyangwa Li1.05Mn1.95O4 burashobora kunozwa cyane mugusimbuza igice Ni cyangwa Mn hamwe nibindi byuma, nka Co, Mn, Mg, na Al.Kuri LiCoO2, kwinjiza ibintu bya doping na alloying nka Ni na Mn birashobora kongera cyane ubushyuhe bwo gutangira kwangirikaTdec, mugihe nanone wirinda reaction hamwe na electrolyte mubushyuhe bwinshi.Ariko, kwiyongera kwa cathode yumuriro muri rusange biza hamwe nibitambo mubushobozi bwihariye.Kugira ngo iki kibazo gikemuke, ibikoresho bya cathode yibanda kuri bateri ya lithium yongeye kwishyurwa hashingiwe kuri lithium ya nikel cobalt manganese oxyde (Igishushanyo 4A).Muri ibi bikoresho, buri kintu cyose gifite Ni-gikungahaye hagati hamwe na Mn ikungahaye cyane, hamwe no kugabanuka kwa Ni no kongera Mn na Co uko ubuso bwegereje (Igishushanyo 4B).Iyambere itanga ubushobozi buhanitse, mugihe iyanyuma itezimbere ubushyuhe bwumuriro.Ibikoresho bishya bya cathode byerekanwe kunoza umutekano wa bateri utabangamiye imikorere yamashanyarazi (Igishushanyo 4C).
Igishushanyo cya 4 Ingamba zo gukemura ibibazo murwego rwa 2: Cathodes yizewe.
.Buri gice kigira Ni-gikungahaye cyane hagati ya Li (Ni0.8Co0.1Mn0.1) O2 hamwe na Mn ikungahaye hanze [Li (Ni0.8Co0.1Mn0.1) O2] hamwe no kugabanya ubukana bwa Ni no kongera Mn na Co nkuko ubuso bwegerejwe.Iyambere itanga ubushobozi buhanitse, mugihe iyanyuma itezimbere ubushyuhe bwumuriro.Impuzandengo ugereranije ni Li (Ni0.68Co0.18Mn0.18) O2.Isikana rya elegitoronike ya micrografi yingingo isanzwe nayo irerekanwa iburyo..Guhindura buhoro buhoro impinduka za Ni, Mn, na Co murirusange biragaragara.Kwibanda kwa Ni kugabanuka, hamwe na Co na Mn byiyongera hejuru yubuso.. 1) O2, hamwe na Mn ikungahaye cyane hanze [Li (Ni0.46Co0.23Mn0.31) O2].Ibikoresho byashizwe kuri 4.3 V. (A), (B), na (C) byororoka byemewe na Springer Kamere..ingufu zikwirakwiza x-ray spectrometry yemeza ibice bya Al na P murwego rwo gutwikira.Iburyo: Ishusho ihanitse ya TEM yerekana AlopO4 nanoparticles (~ 3 nm ya diameter) murwego rwa nanoscale;imyambi yerekana intera iri hagati ya AlPO4 na LiCoO2.(E) Ibumoso: Ishusho ya selile irimo cathode ya LiCoO2 yambaye ubusa nyuma yikizamini cya 12-V kirenze.Akagari karatwitse kandi karaturika kuri iyo voltage.Iburyo: Ishusho y'akagari karimo AlPO4 nanoparticle - yashizwemo LiCoO2 nyuma yikizamini cya 12-V.(D) na (E) byororoka byemewe na John Wiley nabahungu.
Iyindi ngamba yo kunoza ubushyuhe bwumuriro ni ugutwikira ibikoresho bya cathode hamwe nuburinzi bworoshye bwa Li + ikora ibintu, bishobora gukumira guhuza ibikoresho bya cathode hamwe na electrolyte bityo bikagabanya ingaruka ziterwa no kubyara ubushyuhe.Ipitingi irashobora kuba firime idasanzwe [urugero, ZnO, Al2O3, AlPO4, AlF3, nibindi], ishobora kuyobora Li ion nyuma yo guterwa (Igishushanyo 4.
Kumenyekanisha igifuniko hamwe nubushuhe bwiza bwubushuhe nabwo bugira akamaro mukwongera umutekano wa cathode.Kurugero, poly (3-decylthiophene) - cathodes ya LiCoO2 irashobora guhagarika reaction ya electrochemical reaction na reaction iyo ubushyuhe bumaze kuzamuka kugera kuri 80 ° C, kuko polimeri ya polimeri ishobora guhinduka vuba muburyo bukomeye.Ipitingi ya oligomers yonyine hamwe na hyper-ishami ryubwubatsi irashobora kandi gukora nkigikoresho cyo guhagarika ubushyuhe bwo guhagarika bateri kuruhande rwa cathode.
Ubushyuhe bwo guhinduranya ibintu.Guhagarika amashanyarazi ya chimique mugihe ubushyuhe bwa bateri bwiyongera murwego rwa 2 birashobora kubuza neza ubushyuhe kwiyongera.Byihuta kandi bisubirwamo bya termoresponsive polymer guhinduranya (TRPS) byinjijwe imbere mubikusanyirizo (Igishushanyo 5A).Filime yoroheje ya TRPS igizwe na graphene ikozweho na spiky nanostructured nikel (GrNi) nkibintu byuzuza ibintu hamwe na matrike ya PE hamwe na coefficient nini yo kwagura ubushyuhe (α ~ 10−4 K - 1).Amashusho yimyenda ya polymer yerekana ibintu byinshi (σ) mubushyuhe bwicyumba, ariko iyo ubushyuhe bwegereye ubushyuhe bwo guhinduka (T)Igishushanyo 5B).Firime ihita ihinduka insuline bityo igahagarika imikorere ya bateri (Igicapo 5C).Iyi nzira irahindurwa cyane kandi irashobora gukora nubwo nyuma yubushyuhe bwinshi butabangamiye imikorere.
Igishushanyo 5 Ingamba zo gukemura ibibazo murwego rwa 2.
(A) Igishushanyo mbonera cyerekana uburyo bwo guhinduranya amashyuza ya TRPS ikusanya.Batiyeri itekanye ifite icyegeranyo kimwe cyangwa bibiri byegereye hamwe na TRPS yoroheje.Ikora mubisanzwe mubushyuhe bwicyumba.Ariko, mugihe habaye ubushyuhe bwinshi cyangwa amashanyarazi manini, polymer matrix iraguka, bityo igatandukanya ibice bitwara ibintu, bishobora kugabanya ubwikorezi bwayo, bikongera imbaraga zayo kandi bigahagarika bateri.Imiterere ya batiri irashobora kurindwa nta byangiritse.Mugukonjesha, polymer iragabanuka kandi igarura inzira yumwimerere..(C) Ubushobozi incamake ya batiri ya LiCoO2 itwara amagare hagati ya 25 ° C no guhagarika.Ubushobozi bwa zeru kuri 70 ° C bwerekana guhagarika byuzuye.(A), (B), na (C) byororoka byemewe na Kamere ya Springer.(D) Igishushanyo cyerekana microse ishingiye ku guhagarika igitekerezo cya LIBs.Electrode ikorana na microsperes ya thermoresponsive ko hejuru yubushyuhe bwa bateri bwimbere, bigenda byuzura (gushonga).Capsules yashongeshejwe hejuru ya electrode, ikora bariyeri ikingira kandi igahagarika selile..Iburyo: Amafoto yerekana ituze ryumuriro wa inorganic composite itandukanya na PE itandukanya.Gutandukanya byafashwe kuri 130 ° C muminota 40.PE yagabanutse cyane kuva mukarere hamwe na kare.Ariko, gutandukanya ibintu ntabwo byagaragaje kugabanuka kugaragara.Yabyaye uruhushya rutangwa na Elsevier..Hejuru: polyimide (PI).Hagati: selile.Hasi: poly (butylene) terephthalate.(G) Ibumoso: Kugereranya DSC yerekanwe ya PI hamwe na PE na PP itandukanya;itandukanya PI yerekana ubushyuhe buhebuje bwubushyuhe buri hagati ya 30 ° na 275 ° C.Iburyo: Amafoto ya kamera ya digitale agereranya wettability yubucuruzi butandukanya na as-synthesize PI itandukanya na propylene karubone electrolyte.Yabyaye uruhushya rutangwa na societe yimiti y'Abanyamerika.
Gutandukanya amashyuza.Iyindi ngamba yo kubuza bateri gutwarwa nubushyuhe mugihe cyicyiciro cya 2 ni uguhagarika inzira yo gutwara Li ion ikoresheje itandukanya.Gutandukanya nibintu byingenzi byumutekano wa LIBs, kuko birinda guhuza amashanyarazi hagati ya cathode yingufu nyinshi nibikoresho bya anode mugihe yemerera gutwara ionic.PP na PE nibikoresho bikoreshwa cyane, ariko bifite ubushyuhe buke bwumuriro, hamwe no gushonga ~ 165 ° na ~ 135 ° C.Kubucuruzi bwa LIB, abatandukanya bafite imiterere ya PP / PE / PP barangije gucuruzwa, aho PE irinda urwego rwo hagati.Iyo ubushyuhe bwimbere bwa bateri bwiyongereye hejuru yubushyuhe bukabije (~ 130 ° C), igipande cya PE gishonga igice, gifunga imyenge ya firime no gukumira iyimuka rya ion muri electrolyte yamazi, mugihe PP itanga ubufasha bwububiko kugirango wirinde imbere bigufi.Ubundi, guhagarika ubushyuhe bwa LIB birashobora kandi kugerwaho ukoresheje microsperes ya thermoresponsive PE cyangwa paraffin igishashara nkigice cyo gukingira bateri ya anode cyangwa itandukanya.Iyo ubushyuhe bwa bateri bwimbere bugeze ku gaciro gakomeye, microsperes zishonga hanyuma zigatwikira anode / itandukanya hamwe na bariyeri idashoboka, guhagarika ubwikorezi bwa Li-ion no guhagarika selile burundu (Igishushanyo 5D).
Gutandukanya hamwe nubushyuhe bwo hejuru.Kunoza ubushyuhe bwumuriro utandukanya bateri, inzira ebyiri zateguwe mumyaka myinshi ishize:
.Igishushanyo 5E), werekane ingingo zo hejuru cyane zo gushonga hamwe nubukanishi bukomeye kandi bifite nubushyuhe bwo hejuru bwumuriro.Gutandukanya ibintu bimwe na bimwe byahimbwe binyuze muri izi ngamba byagurishijwe, nka Separion (izina ry'ubucuruzi).
. by'abatandukanya (Igishushanyo 5F).Kurugero, polyimide ni thermosetting polymer ifatwa nkubundi buryo butanga ikizere kubera ubushyuhe bwayo buhebuje (butuje hejuru ya 400 ° C), imiti irwanya imiti, imbaraga zingana, imbaraga za electrolyte, hamwe no kutagira umuriro (Igishushanyo 5G).
Amapaki ya bateri afite imikorere yo gukonjesha.Sisitemu yububiko bwa sisitemu yubushyuhe bushobozwa no gukwirakwiza umwuka cyangwa gukonjesha amazi byakoreshejwe mugutezimbere imikorere ya bateri no kugabanya ubushyuhe bwiyongera.Byongeye kandi, ibikoresho byo guhindura ibyiciro nkibishashara bya paraffin byinjijwe mumapaki ya batiri kugirango bikore nk'ubushyuhe kugirango bigabanye ubushyuhe bwabyo, bityo wirinde gukoresha nabi ubushyuhe.
Gukemura ibibazo murwego rwa 3 (gutwika no guturika)
Ubushyuhe, ogisijeni, na lisansi, bizwi ku izina rya “mpandeshatu y’umuriro,” ni ibintu nkenerwa mu kuzimya umuriro.Hamwe no kwegeranya ubushyuhe na ogisijeni byakozwe mugihe cya 1 nicya 2, lisansi (ni ukuvuga electrolytite yaka cyane) izahita itangira gukongoka.Kugabanya umuriro wumuriro wa electrolyte ningirakamaro kumutekano wa bateri hamwe nibindi binini binini bya LIBs.
Flame-retardant inyongera.Imbaraga zubushakashatsi zashyizwe mubikorwa byo guteza imbere inyongeramusaruro zigabanya umuriro wa electrolytike.Ibyinshi mu byongeramo flame-retardant bikoreshwa mumazi ya electrolytite bishingiye kubintu bya fosifore kama cyangwa ibinyabuzima bya halogene.Nkuko halogène ibangamira ibidukikije nubuzima bwabantu, ibinyabuzima bya fosifore kama niko bitanga kandidatire nkinyongeramusaruro zumuriro kubera ubushobozi bwabo bwo kwirinda umuriro ndetse no kubungabunga ibidukikije.Ibinyabuzima bisanzwe bya fosifori birimo trimethyl fosifate, triphenyl fosifate, bis (2-mikorerexyethoxy) methylallylphosphonate, tris (2,2,2-trifluoroethyl) fosifite, (ethoxy) pentafluorocyclotriphosphazene, etylene etiline etyl.Igishushanyo 6A).Uburyo bwo gukumira ingaruka ziterwa na fosifore zirimo ibintu bya fosifore muri rusange byitwa ko ari imiti ya radical-scavenging.Mugihe cyo gutwikwa, molekile zirimo fosifore zirashobora kubora kubwoko bwa fosifore burimo ubwoko-bwisanzure-bwisanzure, bushobora noneho guhagarika radicals (urugero, H na OH radicals) zabyaye mugihe cyo gukwirakwiza urunigi rufite inshingano zo gutwika guhoraho (Igishushanyo cya 6, B na C).Kubwamahirwe make, kugabanuka kwokongoka hamwe hiyongereyeho fosifore irimo flame retardants iva kumafaranga yo gukora amashanyarazi.Kugira ngo ubucuruzi bugerweho, abandi bashakashatsi bagize icyo bahindura ku miterere ya molekile yabo: (i) florine igice cya fosifike ya alkyl irashobora kunoza imitekerereze yazo no kutagira umuriro;. reaction;.na (iv) gusimbuza inyongeramusaruro hamwe na fosifike ya cyclicique, cyane cyane fluorine cyclophosphazene, byongereye ingufu za electrochemic.
Igishushanyo cya 6 Ingamba zo gukemura ibibazo murwego rwa 3.
(A) Imiterere isanzwe ya molekulari yinyongera ya flame-retardant..TPP, fosifate ya triphenyl...Gutandukanya-kwidegembya bigizwe na microfibers hamwe na core-shell imiterere, aho flame retardant ari intangiriro na polymer nigikonoshwa.Iyo ubushyuhe bwumuriro, polymer shell irashonga hanyuma flame retardant ikingira ikarekurwa muri electrolyte, bityo igahagarika neza gutwika no gutwika electrolytike..Umwanya munini, 5 mm..(G) Imiterere ya molekulire ya PFPE, igereranya rya PEO igereranya.Amatsinda abiri ya methyl karubone yahinduwe kumurongo wurunigi rwa polymer kugirango barebe ko molekile ihujwe na sisitemu ya batiri.
Twabibutsa ko burigihe habaho gucuruza hagati yo kugabanuka kwumuriro wa electrolyte nigikorwa cya selile kubintu byongeweho kurutonde, nubwo ubwo bwumvikane bwatejwe imbere hifashishijwe ibishushanyo mbonera byavuzwe haruguru.Iyindi ngamba yatanzwe kugirango iki kibazo gikemuke harimo gushyiramo flame retardant imbere yo gukingira polymer shell ya microfibers, zikaba zashyizwe hamwe kugirango habeho gutandukana (Igishushanyo cya 6D).Igitabo gishya cya electrospun kitarimo microfiber itandukanya hamwe nubushyuhe-buterwa na flame-retardant imitungo yahimbwe na LIBs.Kwifunga kwa flame retardant imbere yikingira rya polymer birinda birinda kwangirika kwumuriro kuri electrolyte, bikarinda ingaruka mbi zidindiza kumikorere ya electrochemic ya bateri (Igishushanyo cya 6E).Ariko, niba ubushyuhe bwumuriro wa batiri ya LIB bubaye, poly (vinylidenefluoride-hexafluoro propylene) copolymer (PVDF-HFP) igikonjo kizashonga uko ubushyuhe bwiyongera.Noneho traphenil fosifate flame retardant izasohoka muri electrolyte, bityo igabanye neza umuriro wa electrolytite yaka cyane.
Igitekerezo cya "electrolyte yibanda ku munyu" nacyo cyateguwe kugirango iki kibazo gikemuke.Izi kuzimya umuriro wa electrolytike ya batiri yumuriro urimo LiN (SO2F) 2 nkumunyu hamwe numuriro uzwi cyane wa trimethyl fosifate (TMP) nkigisubizo cyonyine.Ihinduka ryizana ryumunyu ukomoka kuri organic organique SEI kuri anode ningirakamaro mumikorere ihamye yamashanyarazi.Izi ngamba nshyashya zirashobora kwaguka kubandi batandukanya umuriro kandi birashobora gufungura inzira nshya yo guteza imbere ibishashara bya flame-retardant ya LIB itekanye.
Amashanyarazi adafite umuriro.Igisubizo cyibanze kubibazo byumutekano wa electrolyte kwaba uguteza imbere imbere ya electrolytite.Itsinda rimwe rya electrolytite zidacanwa zakozweho ubushakashatsi bwimbitse ni amazi ya ionic, cyane cyane ubushyuhe bwicyumba cya ionic fluid, zidafite ingufu (nta muvuduko ukabije wumuyaga uri munsi ya 200 ° C) kandi zidacana kandi zifite idirishya ryubushyuhe (Igishushanyo cya 6F).Nyamara, ubushakashatsi burakomeje buracyakenewe kugirango hakemurwe ibibazo byubushobozi buke buturuka ku kwiyegereza kwinshi, umubare muto wo kwimura Li, guhungabana kwa catodiki cyangwa kugabanuka, hamwe nigiciro kinini cyamazi ya ionic.
Uburemere buke bwa hydrofluoroethers ni ikindi cyiciro cya electrolytite yaka umuriro kubera hejuru yacyo cyangwa ntigire flash, ntigicanwa, ubushyuhe buke bwo hejuru, ubukonje buke, ubushyuhe buke, nibindi.Igishushanyo mbonera gikwiye gukorwa kugirango gihuze imiterere yimiti kugirango ihuze ibipimo bya electrolytike.Urugero rushimishije ruherutse gutangazwa ni perfluoropolyether (PFPE), ikigereranyo cya polyethylene oxyde (PEO) kizwi cyane kubera kudakongoka (Igishushanyo cya 6G).Amatsinda abiri ya methyl karubone yahinduwe kumatsinda ya terefone ya PFPE (PFPE-DMC) kugirango habeho guhuza molekile na sisitemu ya batiri.Rero, kudakongoka hamwe nubushyuhe bwumuriro wa PFPEs birashobora guteza imbere umutekano wa LIB mugihe wongera umubare wa transfert ya electrolyte bitewe nuburyo bwihariye bwimiterere ya molekile.
Icyiciro cya 3 nicyiciro cyanyuma ariko cyane cyane icyiciro cyo gutwarwa nubushyuhe.Twabibutsa ko nubwo hashyizweho ingufu nyinshi mukugabanya umuriro wa elegitoroniki ya kijyambere ya elegitoronike, ikoreshwa rya electrolytite ikomeye-idafite imbaraga zerekana amasezerano akomeye.Electrolytes ikomeye cyane iri mubyiciro bibiri: ceramic ceramic electrolytes [sulfide, oxyde, nitride, fosifate, nibindi] hamwe na polymer electrolytite ikomeye [ivanga umunyu wa Li hamwe na polymers, nka poly (okiside ya Ethylene), polyacrylonitrile, nibindi].Imbaraga zo kunoza amashanyarazi akomeye ntabwo azasobanurwa hano, kuko iyi ngingo yamaze kuvugwa neza mubisubirwamo byinshi.
HANZE
Mubihe byashize, ibikoresho byinshi bishya byakozwe kugirango bitezimbere umutekano wa batiri, nubwo ikibazo kitarakemuka burundu.Mubyongeyeho, uburyo bwibanze bwibibazo byumutekano biratandukanye kuri chimie ya bateri itandukanye.Rero, ibikoresho byihariye bigenewe bateri zitandukanye bigomba gutegurwa.Twizera ko uburyo bunoze hamwe nibikoresho byateguwe neza bisigaye kuvumburwa.Hano, turondora ibyerekezo byinshi bishoboka kubushakashatsi bwumutekano wa batiri.
Ubwa mbere, ni ngombwa kwiteza imbere muburyo cyangwa muburyo bwa operando kugirango tumenye kandi dukurikirane ubuzima bwimbere muri LIBs.Kurugero, inzira yumuriro yubushyuhe ifitanye isano cyane nubushyuhe bwimbere cyangwa umuvuduko mwinshi muri LIBs.Nyamara, gukwirakwiza ubushyuhe imbere muri bateri biragoye, kandi uburyo burakenewe kugirango ukurikirane neza indangagaciro za electrolytike na electrode, kimwe nabatandukanya.Kubwibyo, gushobora gupima ibipimo byibice bitandukanye nibyingenzi mugupima bityo bikarinda umutekano wa batiri.
Ubushyuhe bwumuriro bwabatandukanya nibyingenzi mumutekano wa bateri.Polimeri nshya yatunganijwe ifite ingingo zo hejuru zishonga zifite akamaro mukwongera ubushuhe bwumuriro wubutandukanya.Nyamara, ibikoresho bya mashini biracyari hasi, bigabanya cyane imikorere yabyo mugihe cyo guteranya bateri.Byongeye kandi, igiciro nacyo ni ikintu cyingenzi kigomba kwitabwaho mubikorwa bifatika.
Iterambere rya electrolytite ikomeye isa nkigisubizo cyanyuma kubibazo byumutekano wa LIBs.Electrolyte ikomeye izagabanya cyane amahirwe yo kugabanuka kwa bateri imbere, hamwe nibibazo byumuriro no guturika.Nubwo imbaraga nyinshi zashyizwe mubikorwa byo guteza imbere amashanyarazi akomeye, imikorere yabo ikomeje gusubira inyuma cyane ya electrolytike.Ibigize ibinyabuzima na polymer electrolytite byerekana imbaraga zikomeye, ariko bisaba igishushanyo mbonera no gutegura.Turashimangira ko igishushanyo mbonera cya inorganic-polymer hamwe nubuhanga bwo guhuza ari ngombwa kugirango Li-ion itwarwe neza.
Twabibutsa ko electrolyte yamazi atariyo yonyine ya batiri ishobora gutwikwa.Kurugero, iyo LIBs zishyuwe cyane, ibicanwa bya lithiated anode ibikoresho (urugero, grafite ya grafite) nabyo bireba umutekano muke.Flame retardants ishobora gukumira neza umuriro wibikoresho bya leta birasabwa cyane kongera umutekano wabo.Flame retardants irashobora kuvangwa na grafite muburyo bwa polymer binders cyangwa uburyo bwo kuyobora.
Umutekano wa Batteri nikibazo gikomeye kandi gikomeye.Ejo hazaza h'umutekano wa bateri harasaba imbaraga nyinshi mubushakashatsi bwibanze bwo gusobanukirwa byimbitse hiyongereyeho uburyo bunoze bwo kuranga, bushobora gutanga andi makuru yo kuyobora ibikoresho.Nubwo iri suzuma ryibanda ku mutekano wo ku rwego rwibikoresho, twakagombye kumenya ko hakenewe ubundi buryo bwo gukemura ikibazo cyumutekano wa LIBs, aho ibikoresho, ibice bigize selile na format, hamwe na moderi ya batiri hamwe nudupaki bigira uruhare runini kugirango bateri yizewe mbere barekurwa ku isoko.
INGINGO N'INGINGO
Kai Liu, Yayuan Liu, DingchangLin, Allen Pei, Yi Cui, Ibikoresho byumutekano wa batiri ya lithium-ion, ScienceAdvances, DOI: 10.1126 / sciadv.aas9820
Igihe cyo kohereza: Jun-05-2021
