Amabhethri e-sulphur-based all-solid-state amabhethri kulindeleke ukuthi athathe indawo yamabhethri e-lithium-ion amanje ngenxa yokusebenza kwawo kokuphepha okuphezulu. Kodwa-ke, ekulungiseleleni inqubo ye-slurry yebhethri ye-solid-state, kune-polarity engahambelani phakathi kwe-solvent, i-binder ne-sulphide electrolyte, ngakho-ke ayikho indlela yokufeza ukukhiqizwa okukhulu okwamanje. Njengamanje, ucwaningo lwebhethri lesimo esiqinile kakhulu lwenziwa esikalini selabhorethri, futhi umthamo webhethri mncane kakhulu. Ukukhiqizwa kwesilinganiso esikhulu sebhethri yesimo esiqinile yonke kusabheke enqubweni yokukhiqiza ekhona, okungukuthi, into esebenzayo ilungiswa ibe udaka bese imbozwa yomiswa, okungaba nezindleko eziphansi nokusebenza kahle okuphezulu.

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Ubunzima obubhekene nabo

Ngakho-ke, kunzima ukuthola i-polymer binder efanelekile kanye ne-solvent ukusekela isisombululo soketshezi. Iningi lama-electrolyte aqinile asuselwa ku-sulphur angancibilika kuzincibilikisi ze-polar, njenge-NMP esiyisebenzisayo njengamanje. Ngakho-ke ukukhetha kwe-solvent kungahle kube nokuchema ku-polarity engeyona ye-polar noma ebuthakathaka ngokuqhathaniswa ye-solvent, okusho ukuthi ukukhethwa kwe-binder nakho kuncane ngokuhambisanayo – iningi lamaqembu asebenzayo we-polar awakwazi ukusetshenziswa!

Lena akuyona inkinga embi kakhulu. Ngokuya nge-polarity, ama-binder ahambisana ngokuqhathaniswa nezincibilikisi nama-electrolyte e-sulfide azoholela ekunciphiseni kwesibopho phakathi kwezinto ezihlanganisiwe nezinto ezisebenzayo nama-electrolyte, okungangabazeki okuzoholela ekubambeni okwedlulele kwama-electrode kanye nokubola kwamandla okusheshayo, okulimaza kakhulu ukusebenza kwebhethri.

Ukuze kuhlangatshezwane nezidingo ezingenhla, izinto ezintathu eziyinhloko (i-binder, i-solvent, i-electrolyte) zingakhethwa, kuphela izinyibilikisi ze-polar ezingezona i-polar noma ezibuthakathaka, njenge-para-(P) xylene, toluene, n-hexane, anisole, njll. ., kusetshenziswa i-polar polymer binder ebuthakathaka, Njengenjoloba ye-butadiene (BR), irabha ye-styrene butadiene (SBR), i-SEBS, i-polyvinyl chloride (PVC), irabha ye-nitrile (NBR), irabha ye-silicone ne-ethyl cellulose, ukuze kuhlangatshezwane nokusebenza okudingekayo. .

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I-in situ polar – isikimu sokuguqulwa esingeyona i-polar

Kuleli phepha, kwethulwa uhlobo olusha lwe-binder, olungashintsha i-polarity ye-electrode ngesikhathi somshini ngokusebenzisa i-chemistry yokuvikela-de-protection. Amaqembu asebenza endaweni epholile alesi sibophezelo avikelwe amaqembu asebenzayo e-tert-butyl angewona ama-polar, aqinisekisa ukuthi i-binder ingafaniswa ne-sulfide electrolyte (kulokhu i-LPSCl) ngesikhathi sokulungiswa kokunamathisela kwe-electrode. Khona-ke ngokwelashwa kokushisa, okuyinqubo yokomisa ye-electrode, iqembu elisebenzayo le-tert-butyl le-polymer binder lingaba ukuhlukaniswa okushisayo, ukufeza injongo yokuvikela, futhi ekugcineni lithole i-polar binder. Bheka Umfanekiso A.

Isithombe

I-BR (irabha ye-butadiene) ikhethwe njenge-polymer binder yebhethri ye-sulfide yesimo esiqinile ngokuqhathanisa izici zomshini ne-electrochemical ze-electrode. Ngaphezu kokuthuthukisa izakhiwo zemishini kanye ne-electrochemical yamabhethri e-solid-state yonke, lolu cwaningo luvula indlela entsha yokwakheka kwe-polymer binder, okuyindlela yokuvikela-de-ukuvikela-amakhemikhali ukugcina ama-electrode esesimweni esifanele nesifiswayo. izigaba ezahlukene zokukhiqiza ama-electrode.

Bese, i-polytert-butylacrylate (TBA) kanye ne-block copolymer yayo, i-polytert-butylacrylate – b-poly 1, 4-butadiene (TBA-B-BR), amaqembu ayo asebenzayo e-carboxylic acid avikelwe yiqembu le-T-butyl elishisayo, akhethwa ku- ukuhlola. Eqinisweni, i-TBA iyisandulela se-PAA, evame ukusetshenziswa kumabhethri e-lithium ion amanje, kodwa ayikwazi ukusetshenziswa kumabhethri e-lithium asekelwe ku-sulfide ngenxa yokungafani kwayo kwe-polarity. I-polarity eqinile ye-PAA ingasabela ngobudlova ngama-electrolyte e-sulfide, kodwa ngeqembu elisebenzayo le-carboxylic acid elivikelayo le-T-butyl, i-polarity ye-PAA ingancishiswa, ivumele ukuthi incibilike kuma-non-polar noma ku-polar solvents ebuthaka. Ngemuva kokwelashwa kokushisa, iqembu le-t-butyl ester liyachithwa ukuze likhulule i-isobutene, okuholela ekwakhekeni kwe-carboxylic acid, njengoba kuboniswe kuMfanekiso B. Imikhiqizo ye-polymer evinjiwe emibili imelelwa (ivinjiwe) i-TBA kanye (evikelekile) i-TBA- B-BR.

Isithombe

Ekugcineni, i-paA-like binder ingahlangana kahle ne-NCM, kuyilapho yonke inqubo yenzeka endaweni. Kuyaqondakala ukuthi kungokokuqala ngqa ukuthi isikimu sokuguqula i-in situ polarity sisetshenziswe kubhethri le-lithium elinombuso oqinile.

Ngokuqondene nezinga lokushisa lokwelashwa kokushisa, akukho ukulahleka kwesisindo okusobala okubonwe ku-120℃, kuyilapho isisindo esihambisanayo seqembu le-butyl salahleka ngemva kwamahora angu-15 ku-160℃. Lokhu kubonisa ukuthi kukhona izinga lokushisa elithile lapho i-butyl ingasuswa khona (ekukhiqizeni kwangempela, lesi sikhathi sokushisa side kakhulu, kungakhathaliseki ukuthi kukhona izinga lokushisa elifanele kakhulu noma isimo sokuthuthukisa ukusebenza kahle kokukhiqiza sidinga ucwaningo olwengeziwe kanye nengxoxo). Imiphumela ye-Ft-ir yezinto ngaphambi nangemva kokuvinjelwa iphinde yabonisa ukuthi i-electrolyte eqinile ayizange iphazamise inqubo yokuvikela. Ifilimu yokunamathisela yenziwe nge-adhesive ngaphambi nangemva kokuvinjelwa, futhi umphumela wabonisa ukuthi i-adhesive ngemva kokuvinjelwa yayinokunamathela okuqinile nomqoqi we-fluid. Ukuze kuhlolwe ukuhambisana kwe-binder ne-electrolyte ngaphambi nangemva kokuvinjelwa, ukuhlaziya kwe-XRD ne-Raman kwenziwa, futhi imiphumela yabonisa ukuthi i-electrolyte eqinile ye-LPSCl yayinokuhambisana okuhle nesibophezelo esihloliwe.

Okulandelayo, yenza ibhethri lesimo esiqinile futhi ubone ukuthi lisebenza kanjani. Kusetshenziswa i-NCM711 74.5%/ LPSCL21.5% /SP2%/ i-binder 2%, amandla okukhumula eshidi lesigxobo abonisa ukuthi amandla okukhumula makhulu uma kusetshenziswa i-binder tBA-B-BR (njengoba kuboniswe kuMfanekiso 1). Phakathi naleso sikhathi, isikhathi sokukhumula siphinde sibe nomthelela emandleni okukhumula. Ishidi le-electrode ye-TBA elivinjiwe liyaphuka futhi kulula ukuphuka, ngakho-ke i-TBA-B-BR evumelana nezimo ezinhle namandla acwebile aphezulu ikhethwa njengesibophezelo esikhulu sokuhlola ukusebenza kwebhethri.

Umfanekiso 1. Amandla e-peel ngezibophezelo ezihlukene

I-binder ngokwayo i-ionic insulating. Ukuze kufundwe umphumela wokwengezwa kwe-binder ekuqhubeni kwe-ionic, amaqembu amabili okuhlola aqhutshwa, iqembu elilodwa liqukethe i-97.5% ye-electrolyte +2.5% i-binder kanye nelinye iqembu elingenayo i-binder. Kwatholakala ukuthi i-ionic conductivity ngaphandle kwe-binder yayingu-4.8 × 10-3 SCM-1, kanti ukuqhutshwa kwe-binder kwakubuye kube yi-oda ye-10-3 yobukhulu. Ukuzinza kwe-electrochemical kwe-TBA-B-BR kwafakazelwa ukuhlolwa kwe-CV.

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Uhhafu webhethri nokusebenza okugcwele kwebhethri

Ukuhlola okuningi okuqhathanisayo kubonisa ukuthi isibopho esivinjiwe sinokunamathela okungcono futhi asinawo umthelela ekufudukeni kwe-lithium ion. Kusetshenziswa i-binder ehlukile eyenziwe uhhafu weseli ukuze kuhlolwe izici ze-electrochemical, isigamu seseli sokuhlola esihlukahlukene ngokulandelana ngokuxutshwa nesibophezelo esiphozithivu, alikho isibopho se-electrolyte eqinile kanye no-Li – Ku-electrode yokuhlolwa kwesici esisodwa, esingaxutshwe ne-binder Ku-electrolyte eqinile, ukufakazela ukuthi ithonya elihlukile ku-anode binder. Imiphumela yayo yokusebenza kwe-electrochemical iboniswa esithombeni esingezansi:

Isithombe

Emfanekisweni ongenhla: a. ukusebenza komjikelezo wengxenye yeseli yezibophezelo ezihlukene lapho ukuminyana kwendawo eqondile kungu-8mg/cm2, futhi B ukusebenza komjikelezo wengxenye yeseli yezibophezelo ezihlukene lapho ukuminyana kwendawo eqondile kungu-16mg/cm2. Kungabonakala emiphumeleni engenhla ukuthi (ivinjiwe) i-TBA-B-BR inokusebenza okungcono kakhulu komjikelezo webhethri kunezinye izibophezelo, futhi umdwebo womjikelezo uqhathaniswa nomdwebo wamandla wekhasi, obonisa ukuthi izakhiwo zemishini yezigxobo zidlala indima ebalulekile ekusebenzeni komjikelezo.

Isithombe

Isibalo esingakwesokunxele sibonisa i-EIS ye-NCM711/ Li-IN uhhafu weseli ngaphambi komjikelezo, futhi isibalo esingakwesokudla sibonisa i-EIS yesigamu seseli ngaphandle komjikelezo ongu-0.1c amaviki angu-50. I-EIS yeseli elinguhhafu lisebenzisa (elivinjiwe) i-TBA-B-BR ne-BR binder ngokulandelanayo. Kungaphethwa ngomdwebo we-EIS kanje:

1. Kungakhathaliseki ukuthi mingaki imijikelezo, isendlalelo se-electrolyte i-RSE yebhethri ngayinye icishe ibe ngu-10 ω cm2, emele ukumelana nevolumu engokwemvelo ye-electrolyte LPSCl 2. I-Impedans yokudlulisa ukushaja (RCT) yenyukile phakathi nomjikelezo, kodwa UKWANDA kwe-RCT kusetshenziswa. I-BR binder ibiphezulu kakhulu kunaleyo esebenzisa i-tBA-B-BR. Kuyabonakala ukuthi ukuhlangana phakathi kwezinto ezisebenzayo kusetshenziswa i-BR binder bekungenamandla kakhulu, futhi bekunokuxega emjikelezweni.

Isithombe

I-SEM yasetshenziswa ukuze kubhekwe ukuhlukaniswa kwezingcezu zezigxobo ezifundeni ezihlukene, futhi imiphumela ikhonjiswe emfanekisweni ongenhla: a. I-Tba-b-br ngaphambi kokujikeleza (ukuvikela); B. ngaphambi kokusabalalisa BR; C. TBA-B-BR ngemva kwamasonto angu-25 (ukuvinjelwa); D. ngemva kwamasonto angama-25 BR;

Umjikelezo ngaphambi kokuthi wonke ama-electrode angabonwa ngokuseduze ukuxhumana phakathi kwezinhlayiya ezisebenzayo, angabona kuphela izimbobo ezincane, kodwa ngemva komjikelezo wamaviki angu-25, angabona ushintsho olucacile, olusetshenziswe ku-c (ukusuka) abalingani – b – umsebenzi omuhle wezinhlayiya eziningi ze-BR noma kungabikho ukuqhekeka, futhi usebenzisa umsebenzi we-electrode wezinhlayiya ze-BR binder kukhona ukuqhekeka okuningi phakathi, Njengoba kuboniswe endaweni ephuzi ye-D, ngaphezu kwalokho, izinhlayiya ze-electrolyte kanye ne-NCM zihlukaniswe kakhulu, okuyizizathu ezibalulekile zebhethri. ukuncishiswa kokusebenza.

Isithombe

Ekugcineni, ukusebenza kwebhethri lonke kuqinisekiswa. I-electrode ephozithivu ye-NCM711/ i-electrode graphite engalungile ingafinyelela ku-153mAh/g kumjikelezo wokuqala futhi igcine u-85.5% ngemva kwemijikelezo engu-45.

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Isifinyezo esifushane

Sengiphetha, kuwo wonke amabhethri e-lithium aqinile, ukuthintana okuqinile phakathi kwezinto ezisebenzayo, izakhiwo eziphakeme zemishini kanye nokuzinza kwesixhumi esibonakalayo kubaluleke kakhulu ukuthola ukusebenza okuphezulu kwe-electrochemical.