Sulfur-based all-solid-state mabhatiri anotarisirwa kutsiva ikozvino lithium-ion mabhatiri nekuda kwekuita kwavo kwekuchengetedza kwepamusoro. Zvisinei, mukugadzirira kwese-solid-state bhatiri slurry, pane zvisingaenderani polarities pakati pe solvent, binder uye sulphide electrolyte, saka hapana nzira yekuwana kugadzirwa kwakakura panguva ino. Parizvino, tsvagiridzo yezvese-yakasimba-nyika bhatiri inonyanya kuitwa pachiyero cherabhoritari, uye huwandu hwebhatiri hushoma. Iyo yakakura-yakakura kugadzirwa kwese-yakasimba-nyika bhatiri ichiri yakanangana neiyo iripo yekugadzira maitiro, ndiko kuti, chinhu chinoshanda chinogadzirirwa kuita slurry uye chobva chaputirwa nekuomeswa, icho chinogona kuve nemutengo wakaderera uye kugona kwakanyanya.

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Matambudziko akatarisana nawo

Naizvozvo, zvakaoma kuwana yakakodzera polymer binder uye solvent kutsigira mvura mhinduro. Mazhinji sulfur-based solid electrolytes anogona kunyungudutswa mu polar solvents, senge NMP yatinoshandisa parizvino. Saka sarudzo yekunyungudutsa inogona kungove yakarerekera kune isiri-polar kana kuti isina kusimba polarity yeanonyungudutsa, izvo zvinoreva kuti kusarudzwa kwebinder kwakafananawo kwakamanikana – mazhinji emapoka epolar anoshanda epolymer haagone kushandiswa!

Iri harisi dambudziko rakaipisisa. Panyaya ye polarity, mabhainda ayo anowirirana nezvinonyungudutsa uye sulfide electrolytes anozotungamira mukuderedzwa kwechisungo pakati peaggregates uye inoshanda zvinhu uye electrolytes, izvo pasina mubvunzo zvinotungamira kune yakanyanyisa electrode impedance uye kukurumidza kupera simba, izvo zvinonyanya kukanganisa kushanda kwebhatiri.

Kuti zvizadzise zvinodiwa pamusoro apa, zvinhu zvitatu zvikuru (binder, solvent, electrolyte) zvinogona kusarudzwa, chete zvisiri-polar kana zvisina simba zvinonyungudutsa polar, zvakadai separa-(P) xylene, toluene, n-hexane, anisole, nezvimwe zvakadaro. ., uchishandisa isina simba polar polymer binder, Senge butadiene rubber (BR), styrene butadiene rubber (SBR), SEBS, polyvinyl chloride (PVC), nitrile rubber (NBR), silicone rubber uye ethyl cellulose, kuitira kuti isangane nekushanda kunodiwa. .

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In situ polar – isiri-polar shanduko chirongwa

Mupepa iri, rudzi rutsva rwebhainda runotangwa, runogona kushandura polarity ye electrode panguva yekugadzira kuburikidza nekudzivirira-de-protection chemistry. Mapoka anoshanda epolar eiyi binder anodzivirirwa neasiri-polar tert-butyl anoshanda mapoka, kuve nechokwadi kuti binder inogona kuenderana ne sulfide electrolyte (munyaya iyi LPSCl) panguva yekugadzirira kwe electrode paste. Zvino kuburikidza nekupisa kwekupisa, kureva kuomesa kwe electrode, iyo tert-butyl inoshanda boka repolymer binder rinogona kutsemurwa kupisa, kuzadzisa chinangwa chekudzivirira, uye pakupedzisira kuwana polar binder. Ona Mufananidzo A.

Mufananidzo

BR (butadiene rubber) yakasarudzwa sepolymer binder ye sulfide yose-yakasimba-nyika bhatiri nekuenzanisa ma mechanical uye electrochemical properties ye electrode. Pamusoro pekusimudzira ma mechanical and electrochemical properties of all-solid-state mabhatiri, tsvagiridzo iyi inovhura nzira itsva yekugadzirwa kwepolymer binder, inova nzira yekudzivirira-de-protection-chemical yekuchengeta maelectrodes ari munzvimbo yakakodzera uye yainodiwa. matanho akasiyana ekugadzira electrode.

Zvadaro, polytert-butylacrylate (TBA) uye yayo block copolymer, polytert-butylacrylate – b-poly 1, 4-butadiene (TBA-B-BR), ane carboxylic acid anoshanda mapoka anodzivirirwa ne thermolyzed T-butyl boka, vakasarudzwa mukati kuedza. Kutaura zvazviri, TBA ndiyo inotangira PAA, iyo inowanzoshandiswa mumabhatiri e-lithium ion, asi haigoni kushandiswa mu-sulfide-based all-solid lithium mabhatiri nekuda kwekukanganiswa kwayo kwe polarity. Iyo yakasimba polarity yePAA inogona kuita zvechisimba ne sulfide electrolytes, asi nekudzivirira carboxylic acid inoshanda boka reT-butyl, iyo polarity yePAA inogona kuderedzwa, ichibvumira kuti iparadze mune zvisiri-polar kana zvisina simba polar solvents. Mushure mekupisa kwekupisa, boka re-t-butyl ester rakaora kuti risunungure isobutene, zvichiita kuti pave nekugadzirwa kwecarboxylic acid, sezvinoratidzwa mumufananidzo B. Zvigadzirwa zvepolymer mbiri dzakadzivirirwa zvinomiririrwa ne (deprotected) TBA uye (yakadzivirirwa) TBA- B-BR.

Mufananidzo

Pakupedzisira, iyo paA-yakafanana binder inogona kubatana zvakanaka neNCM, nepo maitiro ese achiitika mune situ. Zvinonzwisisika kuti ino ndiyo nguva yekutanga in situ polarity conversion scheme yakashandiswa mune yose-yakasimba-state lithium battery.

Kana iri tembiricha yekurapa kwekupisa, hapana kurasika kwakawanda kwakaonekwa pa120 ℃, nepo huwandu hunoenderana hweboka rebutyl hwakarasika mushure me15h pa160 ℃. Izvi zvinoratidza kuti pane imwe tembiricha iyo butyl inogona kubviswa (mukugadzirwa chaiko, iyi tembiricha nguva yakarebesa, ingave paine tembiricha yakakodzera kana mamiriro ekuvandudza kugona kwekugadzira kunoda kumwe kutsvagisa nekukurukurirana). Ft-ir mhedzisiro yezvinhu zvisati zvaitika uye mushure mekudzivirira zvakare zvakaratidza kuti yakasimba electrolyte haina kukanganisa maitiro ekudzivirira. Iyo inonamira firimu yakagadzirwa neinonamira isati yasvika uye mushure mekudzivirira, uye mhedzisiro yakaratidza kuti chinonamira mushure mekudzivirirwa chaive chakasimba chekunamatira nemuunganidzi wemvura. Kuti kuyedze kugarisana kwebhainda uye electrolyte isati yadzivirirwa uye mushure mekudzivirira, XRD neRaman ongororo yakaitwa, uye mhedzisiro yakaratidza kuti LPSCl yakasimba electrolyte yaive yakanaka kuenderana neyakaedzwa binder.

Tevere, gadzira-yakasimba-nyika bhatiri uye ona kuti rinoita sei. Uchishandisa NCM711 74.5%/ LPSCL21.5% /SP2%/ binder 2%, simba rekubvisa pepa redanda rinoratidza kuti simba rekubvisa ndiro guru kana binder tBA-B-BR inoshandiswa (sezvinoratidzwa mumufananidzo 1). Zvichakadaro, nguva yekubvisa inewo simba rekubvisa simba. Pepa reTBA rakadzivirirwa elekitirodhi harina kutsemuka uye riri nyore kutsemuka, saka TBA-B-BR ine kuchinjika kwakanaka uye kusimba kweganda repamusoro inosarudzwa semusungiro mukuru wekuyedza kuita kwebhatiri.

Mufananidzo 1. Peel simba nemabhaidhi akasiyana

Iyo binder pachayo ionic insulating. Kuti uongorore kushanda kwekuwedzerwa kwebinder pane ionic conductivity, mapoka maviri ekuedza akaitwa, boka rimwe rine 97.5% electrolyte + 2.5% binder uye rimwe boka risina binder. Zvakaonekwa kuti ionic conductivity isina binder yaiva 4.8 × 10-3 SCM-1, uye conductivity ine binder yaivawo 10-3 kurongeka kwehukuru. Iyo electrochemical kugadzikana kweTBA-B-BR kwakaratidzwa neCV bvunzo.

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Hafu yebhatiri uye yakazara bhatiri kuita

Miedzo yakawanda yekuenzanisa inoratidza kuti bhainda rakadzivirirwa rine kunamatira kuri nani uye harina mhedzisiro pakufamba kwe lithium ions. Kushandisa bhainda rakasiyana rakaita hafu sero kuyedza maitiro e electrochemical, akasiyana-siyana ekuyedza hafu sero zvichiteerana nekusanganiswa nebhainda iyo yakanaka, isina binder yeiyo yakasimba electrolyte uye Li – Mu electrode ye single factor miedzo, isina kusanganiswa nebinder Muiyo yakasimba electrolyte, kuratidza kuti akasiyana pesvedzero pane anode binder. Yayo electrochemical performance mhedzisiro inoratidzwa mumufananidzo uri pazasi:

Mufananidzo

Mumufananidzo uri pamusoro: a. ndiyo hafu-sero cycle yekushanda kwezvisungo zvakasiyana-siyana apo kuwanda kwehutano hwakanaka huri 8mg / cm2, uye B ndiyo hafu-cell cycle yekushanda kwezvibatanidza zvakasiyana-siyana apo kuwanda kwenzvimbo yakanaka ndeye 16mg / cm2. Zvinogona kuonekwa kubva pane zvawanikwa pamusoro apa kuti (yakadzivirirwa) TBA-B-BR ine zvirinani kuita kwebhatiri kutenderera kupfuura mamwe mabhandi, uye dhizaini inofananidzwa neiyo peel simba dhizaini, iyo inoratidza kuti michina zvimiro zvemapango zvinotamba. basa rakakosha mukuita kwekuita kutenderera.

Mufananidzo

Mufananidzo wekuruboshwe unoratidza EIS yeNCM711 / Li-IN hafu sero isati yatenderera, uye nhamba yekurudyi inoratidza EIS yehafu yesero pasina kutenderera kwe0.1c kwemavhiki makumi mashanu. Iyo EIS yehafu yesero uchishandisa (yakadzivirirwa) TBA-B-BR uye BR binder zvichiteerana. Inogona kupedzwa kubva pamufananidzo weEIS sezvinotevera:

1. Hazvina mhosva kuti mapeji mangani, iyo electrolyte layer RSE yebhatiri rimwe nerimwe inosvika 10 ω cm2, iyo inomiririra inherent volume resistance ye electrolyte LPSCl 2. The charge transfer impedance (RCT) yakawedzera panguva yekutenderera, asi INCREASE yeRCT uchishandisa. BR binder yaive yakakwira zvakanyanya kupfuura iyo inoshandisa tBA-B-BR binder. Zvinogona kuonekwa kuti kusungirirwa pakati pezvinhu zvinoshanda uchishandisa BR binder kwakanga kusina kusimba zvakanyanya, uye kwaiva nekusunungura mumhepo.

Mufananidzo

SEM yakashandiswa kuona kuchinjika-chikamu chemapole zvimedu munzvimbo dzakasiyana, uye mhedzisiro inoratidzwa mumufananidzo uri pamusoro: a. Tba-b-br isati yatenderera (deprotection); B. isati yatenderera BR; C. TBA-B-BR mushure memavhiki e25 (kudzivirirwa); D. mushure memavhiki makumi maviri nemashanu BR;

Cycle pamberi pemagetsi ese anogona kucherechedzwa zvakanyanya kusangana pakati pezvimedu zvinoshanda, anogona kungoona maburi madiki, asi mushure memavhiki makumi maviri nemashanu kutenderera, anogona kuona shanduko iri pachena, inoshandiswa muc (bvisa) shamwari – b – basa rakanaka reBR zvidimbu zvakawanda. kana pasina kuputika, uye kushandisa electrode basa reBR binder particles kune zvakawanda zvakaputika pakati, Sezvinoratidzwa munzvimbo yero yeD, kuwedzera, electrolyte uye NCM zvimedu zvakaparadzana zvakanyanya, izvo zvikonzero zvakakosha zvebhatiri. performance attenuation.

Mufananidzo

Pakupedzisira, kushanda kwebhatiri rose kunosimbiswa. Iyo yakanaka electrode NCM711 / negative electrode graphite inogona kusvika 153mAh/g mukutanga kutenderera uye kuchengetedza 85.5% mushure me45 cycles.

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Pfupiso pfupi

Mukupedzisa, mune zvese-yakasimba-state mabhatiri e-lithium, kubatana kwakasimba pakati pezvinhu zvinoshanda, yakakwira mechanical zvivakwa uye kugadzikana kwechimiro ndiyo inonyanya kukosha kuwana yakakwira electrochemical performance.