Ukuhlaziywa kwe-CATL phosphate ukushaja ibhethri ye-lithium ukushisa okuphezulu kwe-attenuation imbangela

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ICatlcatl isebenzisa ibhethri ye-ion ye-lithium iron phosphate ion yezentengiselwano ukuhlola izizathu zayo zokulahlekelwa umthamo wokugcina endaweni kagesi, engu-60 ° C. Indlela yokunciphisa umthamo webhethri kusuka ohlelweni lwebhethri neleveli yesigxobo ngokubonakala kwezinhlamvu ezibonakalayo nokuhlola ukusebenza kwe-electrochemical. I.

Ukuhlolwa kwenqubo yokuhlola kusetshenziswa ukukhiqizwa kwe-CATL kwebhethri le-ion phosphate eliyisikwele elinama-86AH. Ibhethri liyi-positive electrode material ku-LifePO4, i-graphite iyimpahla ye-electrode engalungile, isebenzisa isihlukanisi se-polyethylene kanye ne-electrolyte ye-LiPF6. Khetha amabhethri angu-20 aseduze nenqwaba efanayo nokusebenza kukagesi ozowagcina, hlola ukusebenza kukagesi kwebhethri.

Ibhethri le-SOC elingu-100% elingu-60 ° C ligcinwa emshinini wokunyathelisa ophakathi kuka-2.50 no-3.65V, ukukhishwa okungu-0.

Ukukhulisa i-5C - umjikelezo wokushaja. Bese ibhethri elishajekayo eligcwele ligcinwa ku-60 ° C. Okuphindaphindiwe okunjalo, ukurekhoda inqubo yokunciphisa umthamo webhethri.

Phakathi nokuhlolwa komthamo ngakunye, ukumelana kwangaphakathi kwe-DC (DCR) kwebhethri engu-5C/30S kuyahlolwa. Thatha ibhethri ngezikhathi zesitoreji ezihlukene futhi isesimweni sokushajwa ngokuphelele, ihlakazwe ebhokisini legilavu ​​yegesi ye-AR. Sebenzisa isibonakhulu se-electron emission scanning ukuze ubuke i-polar morphology, sebenzisa i-surface analyzer ethile ukuhlola indawo ethile.

Ebhokisini lamagilavu, ucezu lwe-electrode luvalwe ngetheyiphu esobala, futhi impahla ye-electrode ihlaziywa kusetshenziswa i-X-ray diffractometer. Isiqephu se-polar ngemva kokuhlakazwa kwebhethri i-electrode esebenzayo, ishidi le-lithium liyi-electrode ephikisayo, futhi lifakwe ibhethri le-CR2032 buckle, kanye nezakhiwo ze-electrochemical ze-yin nepuleti eliphansi. I-Electrochemical impedance spectrum yebhethri ye-buckle ene-electrochemical workstation.

Ukuhlaziywa kokuqukethwe okuyisisekelo kweshidi le-electrode kusetshenziswa i-spectrometer yokuhlangana kwe-plasma emission spectrometer. Okwesibili, imiphumela yaxoxisana ngoku-1. Ukuhlaziywa kokusebenza kwebhethri Umfanekiso 1 ukuncishiswa komthamo webhethri nokusebenza kokushaja nokukhipha.

Ngokunwetshwa kwesikhathi sokulondoloza, umthamo webhethri uwohloka kancane kancane. Uma isikhathi sokulondoloza sifinyelela ku-575d, ukuncishiswa komthamo webhethri kungu-85.8% womthamo wokuqala.

Ibhethri ishajwa futhi ikhishwe ku-0.02 C, futhi ijika le-voltage yebhethri eliphakathi nendawo liqukethe i-lithium ions eshumekwe kusukela ebuningini bezingxenyekazi ezibangelwa i-graphite, okubonisa ukuthi ukukhulisa kwe-0.02c kunikezwe isakhiwo se-graphite esakhiweni se-graphite ngesikhathi senqubo ye-lithium ion.

Kwanele. , Ukuqeda ngempumelelo imiphumela ye-polarization emijikelezweni. Umfanekiso 1 Ukunciphisa umthamo webhethri nokusebenza kokushaja nokukhipha kuqhathaniswa no-0.

5, isilinganiso sokushaja nokukhipha sehlisiwe sibe ngu-0.02c, esingakhuphula kuphela isilinganiso sokugcina umthamo wesitoreji esingu-181 namabhethri angu-575d siye ku-0.8% no-1.

4%. Ngakho-ke, ukuncishiswa komthamo webhethri okubangelwa ukugcinwa kwezinga lokushisa eliphezulu kwesikhathi eside kuwukuncisha umthamo ongenakulungiseka. Ngaphezu kwalokho, kuboniswa ukuthi i-amplitude yokumelana kwangaphakathi kwebhethri ye-DC iyanda futhi ayibaluleki, futhi okubonisa ukuthi ukuhlukaniswa kwangaphakathi kwebhethri akuyona imbangela ebalulekile yomthamo webhethri wesitoreji sekhalenda ukuncishana okungenakulungiseka.

2. Ukuhlaziywa Kwendlela Yokunciphisa Umthamo Webhethri Ukuhlaziya umthombo womthamo webhethri, ibhethri ishajwa ku-100% SOC noma ishajwe ku-100% DOD ngemva kokukhuliswa kwe-1C. Ukuhlaziywa kwesigxobo esihlakaziwe ukuhlola imiphumela yokugcinwa kwezinga lokushisa eliphezulu esakhiweni, ukwakheka okuyisisekelo kanye nezakhiwo ze-electrochemical ze-yin kanye nezinto ezisebenzayo ezingaphansi.

Ukuhlaziywa kokucwiliswa kwesilayidi esihlukile sesikhathi sokugcina izinga lokushisa eliphezulu kwebhethri i-cathode kumephu engu-100% ye-DOD XRD. Uma kuqhathaniswa nobubanzi obujwayelekile be-XRD be-LifePO4 ne-FEPO4, zonke iziqongo ze-diffraction zesilayidi se-polar ziyahambelana, azikho isigaba esixubile. Umfanekiso 2 XRD spectrum yebhethri ye-cathode yezikhathi ezihlukene zokulondoloza Izinga lokushisa eliphakeme lenkumbulo yangemuva yeshidi le-electrode Izakhiwo ze-electrochemical zinciphisa izikhathi zokulondoloza ezihlukene ngo-100% SOC, lapho i-electrode isetshenziswa njenge-electrode esebenzayo Ibhethri, ukuhlola ukushaja nokukhipha ngo-0.

1C ukukhulisa. Isilinganiso sokuqala sokukhishwa kwe-cathode esebenzayo yamabhethri esikhathi sokugcina ahlukene singaphezu kuka-155 mAh / g, futhi umthamo othize we-cathode esebenzayo esebenzayo ngaphandle kwebhethri yesitoreji iseduze nokugcinwa kwesakhiwo se-LIFEPO4 ngaphandle kokulimala okusobala. Ukushaja okungaguquki kwe-voltage yebhethri yebhakede kuMfanekiso 3 (c) yengezwe kancane, kodwa inani eliphelele lokushaja liseseduze nomthamo othile wento esebenzayo ye-cathode ngaphandle kwebhethri eliwugcinayo.

I-polarization ye-cathode yebhethri ngemva kwe-575D inyukile, kodwa umthamo wokugcina we-lithium we-cathode material awuthinteki, futhi ukufakwa komkhiqizo wokubola kwe-electrolyte kunqubo egciniwe kungase kuhlotshaniswe. Fig. I-3 ibhethri eligoqiwe lapho ukushajwa nokukhipha ijika lebhethri lebhakede lihlanganiswa yi-electrode yasendlini yebhethri engaxazululiwe isuka ku-181 kanye ne-575d, ngokulandelanayo, ne-335.

6 kanye 327.1 mAh / g, ngokulandelana, ngokulandelana. Ibhethri ye-buckle ye-anode yebhethri egciniwe iguqulelwe ekubeni ngu-0.

8% no-3.0%, okubonisa ukuthi izinga lokushisa eliphezulu lokugcina i-lithium graphite nalo lincane kakhulu. Ngombono wokuphepha kwebhethri, inani eliphelele le-anode kulo lonke ibhethri ngokuvamile lingaphezu kuka-10% wengqikithi yomthamo we-cathode, ngakho-ke ukuncishiswa kwe-anode okungenakuhlehliswa okubangelwa ukugcinwa kwezinga lokushisa okuphezulu akuthinti umthamo webhethri lonke.

Isitoreji esingu-181 no-575D I-anode iwumthamo wokuqala wesilinganiso sokushaja yenani elingavimbeki elingu-90.4% no-84.5% wesilinganiso sokuqala sokushaja se-anode, ngokulandelana, futhi izinga lokugcinwa komthamo webhethri langempela liseduze.

Ngakho-ke, isizathu esibalulekile sokunciphisa umthamo webhethri ukulahleka kwe-lithium ion esebenzayo kuwo wonke amabhethri. Ngamafuphi, isitoreji esiphezulu sokushisa ngeke sithinte kakhulu ukuhlukaniswa kwe-LIFEPO4 nama-electrode e-graphite. Ibhethri engu-100% ye-DOD yokugcina izinga lokushisa eliphezulu I-cathode ye-pell ubukhona, imbangela yenani le-lithium ion ekwazi ukuthola i-anode akulona ushintsho olubalulekile ekukwazini ukushintsha kancane kancane into esebenzayo ye-electrode, kodwa ngenxa yebhethri ebhethri.

Inani lama-ion liba lincane. I-lithium ion esebenzayo ebhethrini idliwe yi-electrode / electrolyte interface ye-electrode / electrolyte interface, futhi imbangela eyinhloko yokulahleka kwe-lithium ion esebenzayo isiza ukujulisa ukuqwashisa ngomshini wokulahlekelwa umthamo wokugcina. Ukuhlaziywa kwe-polar micropatological yezinhlayiya ze-LifePO4 ku-cathode ku-cathode, usayizi wezinhlayiyana cishe u-200 nm; ngemuva kwesitoreji esingu-181D, usayizi ongenalutho phakathi kwezinhlayiya ze-LIFEPO4 awushintshiwe kakhulu; ngemva kokugcinwa kwe-575D, igebe phakathi kwezinhlayiya liyancipha kakhulu.

Ku-graphite anode, njengoba isikhathi sokugcina senyukile, inani lomkhiqizo osebenzayo ohlangothini nalo liyashintshwa [I-Fig. 4 (d), (e), (f)]. Umkhiqizo we-sub-reactive kwinqubo yokugcinwa kwezinga lokushisa eliphezulu ufakwa esigxotsheni, futhi i-morphology yesigxobo iyashintshwa.

Ukuze kubonakale umthelela we-sub-reaction ekulahlekeni kwe-lithium ion okukhulunywe ngakho ngenhla, okuqukethwe kwe-Li ku-yin nesici sowesilisa kuyahlaziywa futhi ukuze kufundwe umsuka wokulahleka kwe-lithium ion esebenzayo. Umfanekiso 4 Ithebula 1 le-Battery pole morphology liwumphumela wokuhlola we-ICP-OES we-100% ye-SOC yebhethri ye-yin anode. Ushintsho kokuqukethwe kwe-Li ku-cathode alubonakali.

Okuqukethwe kwe-LI kwe-anode nakho kugcinwa ezingeni elifanayo, ngakho-ke inani eliphelele lokuqina kwe-yin ne-old pole LI kumabhethri esikhathi sokulondoloza ahlukene alishintshile kakhulu. Ithebula 1 Amabhethri esikhathi sokulondoloza ahlukene (100% SOC) okuqukethwe kwe-polar element Njengoba ishidi le-cathode yebhethri engu-100% SOC liqukethe okuphansi kakhulu, ukulahlekelwa kwe-lithium ion esebenzayo kubalulekile ukufaka ku-anode. Ku-100% SOC isitoreji sokushisa okuphezulu, i-anode isesimweni lapho i-potium isesimweni lapho amandla aphansi kakhulu, futhi i-electrolyte isabela kalula ebusweni bayo, futhi i-lithium ion iyasetshenziswa, kanye nemikhiqizo esebenzayo ehlangene ye-lithium.

Ukuze kunqunywe ukwakheka kwendawo ye-lithium encibilikayo ye-anode, ukuhlakazwa kwebhethri ye-DOD engu-100% kufakwe titrated, futhi imiphumela ikhonjiswe kuThebula 2. Ithebula le-2100% yebhethri ye-DOD I-lithium encibilikayo i-Anode ihlanganisa indawo ye-anode ku-carbonate morphology, ekhuphuka njengoba isikhathi sokulondoloza sandiswa (bheka Ithebula 2), okubonisa ukuthi inqubo yokugcina ibhethri ikhiqiza inani elikhulu lezingxenye zikasawoti ze-lithium ezingaphili. Usawoti we-inorganic ungumkhiqizo obalulekile wokusabela kokunciphisa i-solvent, okubangelwa inani elikhulu lokubola kwe-electrolyte ngesikhathi sokugcinwa kwebhethri.

I-Electrode Reaction Dynamics I-Electrochemical Exhaust Spectroscopy (bheka Umfanekiso 5), nakuba i-RCT ye-cathode ikhula ngesikhathi sokugcina izinga lokushisa eliphezulu [Fig. 5 (a)], kodwa i-cathode RCT incane, ukumelana kwangaphakathi kwebhethri nakho kuncane. I-Anode EIS [I-Fig.

5 (b)] I-RSEi ayibonakali ngesikhathi sokulondoloza, kodwa i-RCT inwetshwa ngesikhathi sokulondoloza. Ngenxa yokubekwa komkhiqizo we-electrolyte sub-reaction ngesikhathi sokugcinwa kwezinga lokushisa eliphezulu, indawo engaphezulu ye-anode ratio iyancipha ngesikhathi sokugcina, kanti indawo ethize ye-anode engu-0, 181 kanye nebhethri engu-575d ingu-3.42, 2.

97 kanye no-1.84cm2 / g. Indawo engaphezulu yesilinganiso se-anode yehlisa umsebenzi wokusabela we-electrochemical okwenzeka ebusweni be-anode, okuholela ekwenyukeni kokumelana nokudluliswa kwe-RCT ebusweni be-anode / electrolyte.

Fig. 5 ichazwa ku-electrochemical impedance spectrum yebhethri lebhakede. Ngesikhathi senqubo yokugcina izinga lokushisa eliphezulu, i-lithium state anode isesimweni esinamandla aphansi, futhi ukusabela kokunciphisa i-electrolyte kudla i-lithium ion esebenzayo, futhi ekugcineni ikhiqize usawoti we-lithium we-inorganic; izinga lokushisa eliphezulu lenezela i-electrolysis Izinga lokuphendula lokunciphisa uketshezi, okwenza kube nenani elikhulu le-lithium ion (Umfanekiso 6).

Ngaphezu kwalokho, i-anode side reactive product deposits, ifilimu ye-SEI iyaqina, okuholela ekuwohlokeni kokusebenza kwe-electrode kinetic. Umfanekiso wesi-6, umshini wokunciphisa umthamo wokugcina uyaboniswa. 3.

Ukusebenza kwebhethri lokushisa okuphezulu kwebhethri Kuthuthukisiwe ngenxa yokulahlekelwa amandla ebhethri inqubo yokushisa ephezulu yokugcina ukushisa okubalulekile ukulahlekelwa kwe-lithium ion okubangelwa ukusabela okuhlangene okuvela ebusweni be-anode, Kusukela ekungezeni ifilimu ye-SEI izithasiselo eziqinisa i-thermal stabilizing (ASR) zingathuthukisa ukuzinza kwezinga lokushisa eliphezulu kwefilimu ye-SEI, ukunciphisa ukuphinda kusebenze ohlangothini lwe-anode, kunciphise ukulahlekelwa okusebenzayo kwe-lithium ion. Umfanekiso 7 Amajika ahlukene okugcina amabhethri e-electrolyte kanye nengqalasizinda ye-SEI ye-thermostability yengeza u-1% we-ASR ingathuthukisa impilo yokugcina izinga lokushisa eliphezulu lebhethri. Ngemva kokwengeza u-1% ASR, isilinganiso sokugcinwa komthamo we-575D sikhuphuke sisuka ku-85.

8% kuya ku-87.5% [Umdwebo 7 (a)]. I-DCR Rolling Rate iphansi kakhulu kunaleyo yesisekelo se-electrolyte, futhi okuqukethwe kwenhlanganisela ye-lithium encibilikayo ene-anode nakho kwehlile (Ithebula 3).

Ukuhlaziywa kwe-DSC kwenziwa ku-100% SOC yebhethri anode [Amakhiwane. 7 (b)], ukumunca ukushisa kufinyelela phezulu ngaphansi kuka-100 ° C ku-solvent eyinsalela. Ithebula 3 Ngaphambi kwebhethri ye-lithium encibilikayo ye-anode engu-100% ye-DOD, i-lithium e-anode encibilikayo iyengezwa, futhi i-anode engu-90 ° C iqala ukukhipha, eboliswa i-anode surface SEI; Ngemuva kokwengeza i-ASR, izinga lokushisa lokubola liyakhuphuka libe ngu-101 ° C.

Ngemva kokungeza i-ASR, ukuzinza okushisayo kwe-SEI kuthuthukiswa kakhulu, futhi ukulahlekelwa kwe-lithium ion okusebenzayo kungancishiswa ngokuphumelelayo, futhi impilo yokugcina ibhethri ingathuthukiswa. Okwesithathu, isiphetho sokugcina sihlaziya izakhiwo ze-electrochemical, i-polar physics kanye nezakhiwo ze-electrochemical zebhethri ye-phosphate ion eyenzelwe ukugcinwa kwezinga lokushisa eliphezulu, futhi sathola ukuthi ukulahlekelwa kwamandla ebhethri endaweni yokugcinwa kwezinga lokushisa eliphezulu kubalulekile kusukela ku-electrolyte yokunciphisa i-anode emandleni aphansi. , Okuholela ekulahlekeni kwe-lithium ion esebenzayo.

Umkhiqizo ongasebenzi kahle we-electrolyte yokunciphisa i-anode ufakwa ku-anode, futhi ingxenye ye-inorganic ku-diphozithi ivimbela ukusakazeka kwe-lithium ion, ukuze i-anode reaction kinetics yehle. Ngokungeza i-thermostability ye-membrane ye-SEI ku-electrolyte ukuze kuthuthukiswe ngokuphumelelayo ukuzinza okushisayo kwefilimu ye-SEI, ukunciphisa ukusabela kokunciphisa kwe-electrolyte, ukunciphisa ukusetshenziswa okusebenzayo kwe-lithium ion, nokuthuthukisa impilo yokugcina izinga lokushisa.