Iibhetri ezisekelwe kwi-sulphur-i-solid state-state kulindeleke ukuba ithathe indawo yeebhetri ze-lithium-ion zangoku ngenxa yokusebenza kwazo okuphezulu kokhuseleko. Nangona kunjalo, kwinkqubo yokulungiselela yonke i-slurry ye-battery eqinile, kukho i-polarities engahambelaniyo phakathi kwe-solvent, i-binder kunye ne-sulphide electrolyte, ngoko akukho ndlela yokufezekisa imveliso enkulu ngoku. Okwangoku, uphando kwibhetri yelizwe lonke oluqinileyo lwenziwa ikakhulu kwisikali sebhubhoratri, kwaye umthamo webhetri uncinci. Imveliso enkulu yebhetri yelizwe lonke isele ibhekiselele kwinkqubo yokuvelisa ekhoyo, oko kukuthi, into esebenzayo ilungiswe ibe yi-slurry kwaye igqunywe kwaye yomiswe, enokuba neendleko eziphantsi kunye nokusebenza okuphezulu.

Nye

Ubunzima ojongene nabo

Ngoko ke, kunzima ukufumana i-polymer binder efanelekileyo kunye ne-solvent ukuxhasa isisombululo solwelo. Uninzi lwe-electrolyte eqinileyo esekwe kwisulfure inokunyibilika kwizinyibilikisi zepolar, njenge-NMP esiyisebenzisayo ngoku. Ngoko ke ukhetho lwe-solvent lunokuthambekela kuphela kwi-polarity engekho-polar okanye i-polarity ebuthathaka kakhulu ye-solvent, oku kuthetha ukuba ukhetho lwe-binder lukwancinci ngokuhambelanayo – uninzi lwamaqela asebenzayo e-polar yepolymer ayinakusetyenziswa!

Oku akuyongxaki embi kakhulu. Ngokubhekiselele kwi-polarity, izibophelelo ezihambelanayo kunye ne-solvents kunye ne-sulfide electrolyte ziya kukhokelela ekunciphiseni ibhondi phakathi kwezinto ezidibeneyo kunye nezinto ezisebenzayo kunye ne-electrolytes, okuya kuthi ngokungathandabuzekiyo kukhokhelele kwi-impedance ye-electrode egqithisileyo kunye nokubola komthamo okhawulezayo, oyingozi kakhulu ekusebenzeni kwebhetri.

Ukuze kuhlangatyezwane nezi mfuno zingasentla, izinto ezintathu eziphambili (i-binder, i-solvent, i-electrolyte) inokukhethwa, kuphela i-solvents ye-polar engekho-polar okanye ebuthathaka, njenge-para-(P) i-xylene, i-toluene, i-n-hexane, i-anisole, njl. ., usebenzisa i-polar polar binder ebuthathaka, efana ne-butadiene rubber (BR), irabha ye-styrene butadiene (SBR), i-SEBS, i-polyvinyl chloride (PVC), irabha ye-nitrile (NBR), irabha ye-silicone kunye ne-ethyl cellulose, ukwenzela ukuhlangabezana nomsebenzi ofunekayo. .

Mbini

I-in situ polar – iskimu sokuguqulwa kwe-non-polar

Kulo phepha, uhlobo olutsha lwe-binder lungeniswa, olunokutshintsha i-polarity ye-electrode ngexesha lomatshini ngokusebenzisa i-chemistry yokukhusela-de-protection. Amaqela asebenzayo e-polar ale binder akhuselwe ngamaqela asebenzayo e-tert-butyl angekho polar, ukuqinisekisa ukuba i-binder inokuhambelana ne-sulfide electrolyte (kule meko i-LPSCl) ngexesha lokulungiswa kwe-electrode paste. Emva koko ngonyango lobushushu, oko kukuthi inkqubo yokomisa ye-electrode, iqela elisebenzayo le-tert-butyl le-polymer binder liyakwazi ukuhlukana kwe-thermal, ukufezekisa injongo yokukhusela, kwaye ekugqibeleni ufumane i-polar binder. Jonga uMfanekiso A.

Umfanekiso

I-BR (i-rubber ye-butadiene) ikhethwe njenge-polymer binder ye-sulfide yonke ibhetri ye-solid-state ngokuthelekisa i-mechanical and electrochemical properties of the electrode. Ukongeza ekuphuculeni iimpawu zomatshini kunye ne-electrochemical yeebhetri ezizinzileyo zonke, olu phando luvula indlela entsha yoyilo lwe-polymer binder, oluyindlela yokukhusela-ukukhusela-imichiza yokugcina i-electrodes kwindawo efanelekileyo kunye nesimo esinqwenelekayo. izigaba ezahlukeneyo zokwenza i-electrode.

Emva koko, i-polytert-butylacrylate (i-TBA) kunye ne-block copolymer, i-polytert-butylacrylate – i-b-poly 1, i-4-butadiene (i-TBA-B-BR), amaqela ayo asebenzayo e-carboxylic acid akhuselwe yiqela le-T-butyl e-thermolyzed, akhethwa kuyo. umfuniselo. Enyanisweni, i-TBA yi-precursor ye-PAA, esetyenziswa ngokuqhelekileyo kwiibhetri ze-lithium ion zangoku, kodwa ayikwazi ukusetyenziswa kwi-sulfide-based all-solid lithium iibhetri ngenxa yokungafani kwayo kwe-polarity. I-polarity enamandla ye-PAA inokusabela ngobundlobongela kunye ne-sulfide electrolytes, kodwa kunye neqela elikhuselayo le-carboxylic acid esebenzayo ye-T-butyl, i-polarity ye-PAA ingancitshiswa, ivumela ukuba ichithe kwi-polar okanye i-polar solvents ebuthathaka. Emva kokunyanga ukushisa, iqela le-t-butyl ester lichithwa ukukhulula i-isobutene, okubangelwa ukubunjwa kwe-carboxylic acid, njengoko kuboniswe kuMfanekiso B. Iimveliso ze-polymer ezimbini ezikhutshiweyo zimelwe yi-TBA (ekhutshiweyo) kunye (ekhutshiweyo) i-TBA- B-BR.

Umfanekiso

Ekugqibeleni, i-paA-like binder inokubambisana kakuhle ne-NCM, ngelixa yonke inkqubo yenzeke kwindawo. Kuyaqondwa ukuba eli lixesha lokuqala iskimu sokuguqulwa kwe-situ polarity sisetyenziswe kwibhetri ye-lithium yonke.

Ngokubhekiselele kwiqondo lobushushu bonyango lobushushu, akukho lahleko ibonakalayo yabonwa kwi-120℃, ngelixa ubunzima obuhambelanayo beqela le-butyl lalahleka emva kwe-15h kwi-160 ℃. Oku kubonisa ukuba kukho ubushushu obuthile apho i-butyl ingasuswa khona (kwimveliso yangempela, eli xesha lobushushu lide kakhulu, nokuba kukho ubushushu obufanelekileyo okanye imeko yokuphucula ukusebenza kakuhle kwemveliso kufuna uphando olongezelelweyo kunye nengxoxo). Iziphumo ze-Ft-ir zezixhobo ngaphambi nangemva kokukhuselwa kwakhona kwabonisa ukuba i-electrolyte eqinile ayizange iphazamise inkqubo yokukhusela. Ifilimu yokuncamathelisa yenziwe nge-adhesive ngaphambi nangemva kokukhutshwa, kwaye isiphumo sabonisa ukuba i-adhesive emva kokukhuselwa yayinokubambisana okunamandla kunye nomqokeleli we-fluid. Ukuze kuvavanywe ukuhambelana kwe-binder kunye ne-electrolyte phambi nasemva kokukhuselwa, uhlalutyo lwe-XRD kunye ne-Raman luye lwenziwa, kwaye iziphumo zabonisa ukuba i-electrolyte eqinileyo ye-LPSCl yayinokuhambelana kakuhle nesibophelelo esivavanyiweyo.

Okulandelayo, yenza ibhetri yelizwe lonke kwaye ubone ukuba isebenza njani. Ukusebenzisa i-NCM711 74.5%/ LPSCL21.5% /SP2%/ i-binder 2%, amandla okuqhawula i-pole sheet abonisa ukuba amandla okuhlutha awona makhulu xa kusetyenziswa i-binder tBA-B-BR (njengoko kuboniswe kuMfanekiso 1). Okwangoku, ixesha lokuhluba likwachaphazela amandla okuhluba. Ishidi le-electrode ye-TBA ekhutshiweyo i-brittle kwaye kulula ukuphuka, ngoko i-TBA-B-BR enokuguquguquka okulungileyo kunye namandla aphezulu e-peel ikhethwa njenge-binder eyintloko yokuvavanya ukusebenza kwebhetri.

Umzobo 1. Amandla e-Peel kunye nezibophelelo ezahlukeneyo

Isibophelelo ngokwaso si-ionic insulating. Ukuze ufunde umphumo wokongezwa kwe-binder kwi-ionic conductivity, amaqela amabini ovavanyo aqhutywe, elinye iqela eliqukethe i-97.5% ye-electrolyte + i-2.5% ye-binder kunye nelinye iqela elingenayo i-binder. Kwafunyaniswa ukuba i-ionic conductivity ngaphandle kwe-binder yayingu-4.8 × 10-3 SCM-1, kunye ne-conductivity kunye ne-binder nayo yayiyi-10-3 umyalelo wobukhulu. Ukuzinza kwe-electrochemical ye-TBA-B-BR kwangqinwa ngovavanyo lwe-CV.

Ntathu

Isiqingatha sebhetri kunye nokusebenza ngokupheleleyo kwebhetri

Iimvavanyo ezininzi zokuthelekisa zibonisa ukuba i-binder ekhutshiweyo inokubambelela okungcono kwaye ayinayo impembelelo ekufudukeni kwe-lithium ion. Ukusebenzisa i-binder eyahlukeneyo eyenziwe isiqingatha seseli ukuvavanya iimpawu ze-electrochemical, iiseli zovavanyo ezahlukeneyo zesiqingatha ngokulandelelana ngokuxutywa kunye ne-binder ye-positive, akukho binder ye-electrolyte eqinileyo kunye ne-Li – Kwi-electrode yovavanyo lwento enye, engaxutywanga ne-binder Kwi-electrolyte eqinileyo, ukubonisa ukuba impembelelo eyahlukileyo kwi-anode binder. Iziphumo zayo ze-electrochemical performance ziboniswe kumzobo ongezantsi:

Umfanekiso

Kulo mfanekiso ungasentla: a. yintsebenzo yomjikelo wesiqingatha seseli yee-binders ezahlukeneyo xa ubuninzi bendawo echanekileyo yi-8mg / cm2, kwaye i-B yinkqubo ye-half-cell cycle ye-binders ezahlukeneyo xa ubuninzi bendawo elungileyo yi-16mg / cm2. Inokubonwa kwezi ziphumo zingentla ukuba (ekhuselweyo) i-TBA-B-BR inomsebenzi ongcono kakhulu womjikelo webhetri kunezinye izibophelelo, kwaye umzobo womjikelo uthelekiswa nomzobo wamandla amaxolo, obonisa ukuba iipropati zomatshini zezibonda zidlala indima ebalulekileyo ekusebenzeni komjikelo wokusebenza.

Umfanekiso

Umfanekiso osekhohlo ubonisa i-EIS ye-NCM711 / Li-IN yesiqingatha seseli ngaphambi komjikelezo, kwaye umzobo ochanekileyo ubonisa i-EIS yesiqingatha seseli ngaphandle komjikelezo we-0.1c kwiiveki ze-50. I-EIS yesiqingatha seseli kusetyenziswa (ekhutshiweyo) TBA-B-BR kunye ne-BR binder ngokulandelelanayo. Inokuqukunjelwa kumzobo we-EIS ngolu hlobo lulandelayo:

1. Kungakhathaliseki ukuba mingaphi imijikelo, i-electrolyte layer ye-RSE yebhetri nganye ijikeleze i-10 ω cm2, emele ukuxhathisa umthamo wendalo we-electrolyte LPSCl 2. I-impedance transfer transfer (RCT) yanda ngexesha lomjikelo, kodwa UKUNYUKA kwe-RCT isebenzisa. Isibophelelo se-BR sasiphezulu kakhulu kunokusebenzisa isibophelelo se-tBA-B-BR. Ingabonwa ukuba ukudibanisa phakathi kwezinto ezisebenzayo usebenzisa i-BR binder yayingenamandla kakhulu, kwaye kwakukho ukukhulula kumjikelezo.

Umfanekiso

I-SEM yayisetyenziselwa ukujonga i-cross-section of pole slices kumazwe ahlukeneyo, kwaye iziphumo ziboniswa kumzobo ongentla: a. I-Tba-b-br ngaphambi kokujikeleza (ukukhusela); B. phambi kokusasazwa kwe-BR; C. TBA-B-BR emva kweeveki ezingama-25 (ukukhuselwa); D. emva kweeveki ezingama-25 BR;

Umjikelo phambi kokuba zonke i-electrodes zibonwe ngokusondeleyo uqhagamshelwano phakathi kwamaqhekeza asebenzayo, unokubona kuphela imingxuma emincinci, kodwa emva kweeveki ezingama-25, unokubona utshintsho olucacileyo, olusetyenziswe kwi-c (ukukhupha) amaqabane – b – umsebenzi omhle we-BR uninzi lwamaqhekeza. okanye akukho ziqhekeko, kunye nokusebenzisa umsebenzi we-electrode we-BR binder particles kukho ezininzi iintanda phakathi, Njengoko kubonisiwe kwindawo ephuzi ye-D, ukongeza, i-electrolyte kunye ne-NCM particles zihluke kakhulu, ezizizathu ezibalulekileyo zebhetri. ukuthomalalisa ukusebenza.

Umfanekiso

Ekugqibeleni, ukusebenza kwayo yonke ibhetri kuqinisekisiwe. I-electrode enhle ye-NCM711 / i-electrode engalungile yegraphite inokufikelela kwi-153mAh / g kumjikelezo wokuqala kwaye igcine i-85.5% emva kwemijikelezo ye-45.

Ne

Isishwankathelo esifutshane

Ukuqukumbela, kuzo zonke iibhetri ze-lithium eziqinileyo, uqhagamshelwano oluqinileyo phakathi kwezinto ezisebenzayo, iimpawu eziphezulu zemishini kunye nokuzinza kwe-interface zibaluleke kakhulu ukufumana ukusebenza okuphezulu kwe-electrochemical.