Ana sa ran tushen tushen sulfur duk-ƙaƙƙarfan baturan jihohi su maye gurbin baturan lithium-ion na yanzu saboda ingantaccen aikinsu na aminci. Koyaya, a cikin tsarin shirye-shiryen slurry mai ƙarfi-jihar, akwai polarities marasa jituwa tsakanin sauran ƙarfi, ɗaure da sulphide electrolyte, don haka babu wata hanyar da za a iya samar da manyan sikelin a halin yanzu. A halin yanzu, binciken da ake yi kan baturi mai ƙarfi ya fi yin shi akan sikelin dakin gwaje-gwaje, kuma ƙarar batirin batir kaɗan ne. Samar da babban sikelin na batir mai ƙarfi har yanzu yana kan tsarin samarwa da ake da shi, wato, ana shirya abu mai aiki a cikin slurry sannan a shafe shi kuma a bushe, wanda zai iya samun ƙarancin farashi da inganci mafi girma.

daya

Matsalolin da aka fuskanta

Sabili da haka, yana da wahala a sami mai ɗaure polymer mai dacewa da sauran ƙarfi don tallafawa maganin ruwa. Yawancin sulfur tushen sulfur electrolytes ana iya narkar da su a cikin kaushi na polar, kamar NMP da muke amfani da su a halin yanzu. Don haka zaɓin sauran ƙarfi kawai za a iya nuna son kai ga waɗanda ba iyakacin duniya ba ko in mun gwada da rauni polarity na sauran ƙarfi, wanda ke nufin cewa zaɓi na ɗaure kuma daidai kunkuntar – yawancin ƙungiyoyin aikin polar na polymer ba za a iya amfani da su ba!

Wannan ba shine mafi munin matsala ba. A cikin sharuddan polarity, masu ɗaure waɗanda suka dace da ƙauye da sulfide electrolytes za su haifar da raguwar haɗin gwiwa tsakanin aggregates da abubuwa masu aiki da electrolytes, wanda babu shakka zai haifar da matsananciyar rashin ƙarfi na lantarki da lalata ƙarfin ƙarfin aiki, wanda ke da matukar illa ga aikin baturi.

Don saduwa da buƙatun da ke sama, ana iya zaɓar manyan abubuwa guda uku (binder, solvent, electrolyte), kawai waɗanda ba iyakacin duniya ba ko rauni mai ƙarfi, kamar para- (P) xylene, toluene, n-hexane, anisole, da sauransu. ., Yin amfani da mai rauni polar polymer binder, Irin su butadiene roba (BR), styrene butadiene roba (SBR), SEBS, polyvinyl chloride (PVC), nitrile roba (NBR), silicone roba da ethyl cellulose, domin saduwa da ake bukata yi. .

biyu

A cikin situ polar – tsarin musanya mara iyaka

A cikin wannan takarda, an gabatar da wani sabon nau’in ɗaure, wanda zai iya canza polarity na electrode yayin yin injina ta hanyar sinadarai na kariya-de-kariya. Ƙungiyoyin aikin polar na wannan ɗaure suna kiyaye su ta ƙungiyoyi masu aiki marasa iyaka na tert-butyl, suna tabbatar da cewa za a iya daidaita maɗaurin tare da sulfide electrolyte (a cikin wannan yanayin LPSCl) yayin shirye-shiryen manna na lantarki. Sa’an nan kuma ta hanyar maganin zafi, wato tsarin bushewa na electrode, ƙungiyar aiki na tert-butyl na polymer binder na iya zama tsagawar thermal, don cimma manufar kariya, kuma a ƙarshe samun madaidaicin igiya. Duba Hoto A.

Hoton

BR (rubber butadiene) an zaɓi shi azaman mai ɗaure polymer don batirin sulfide duk-kauri mai ƙarfi ta hanyar kwatanta kayan inji da na lantarki na lantarki. Baya ga haɓaka kayan aikin injiniya da na lantarki na duk batura masu ƙarfi, wannan binciken yana buɗe sabon tsarin ƙirar polymer mai ɗaure, wanda shine tsarin kariya-de-kariya-sunadarai don kiyaye na’urorin lantarki a daidai da yanayin da ake so a. matakai daban-daban na masana’antar lantarki.

Sa’an nan, polytert-butylacrylate (TBA) da block copolymer, polytert-butylacrylate – b-poly 1, 4-butadiene (TBA-B-BR), wanda carboxylic acid aiki kungiyoyin suna kariya ta thermolyzed kungiyar T-butyl. gwajin. A zahiri, TBA shine farkon PAA, wanda galibi ana amfani dashi a cikin batirin lithium ion na yanzu, amma ba za’a iya amfani da shi a cikin batir lithium mai ƙarfi na sulfide saboda rashin daidaiton polarity. Ƙaƙƙarfan polarity na PAA na iya mayar da martani da karfi tare da sulfide electrolytes, amma tare da m carboxylic acid aiki kungiyar na T-butyl, polarity na PAA za a iya rage, kyale shi ya narkar da a cikin wadanda ba iyakacin duniya kaushi ko rauni na iyakacin duniya kaushi. Bayan maganin zafi, ƙungiyar t-butyl ester ta bazu don sakin isobutene, wanda ya haifar da samuwar acid carboxylic, kamar yadda aka nuna a cikin Hoto B. Abubuwan da aka lalata na polymer guda biyu suna wakilta ta (ba tare da kariya) TBA da (deprotected) TBA- B-BR.

Hoton

A ƙarshe, mai ɗaure mai kama da paA na iya haɗawa da kyau tare da NCM, yayin da duka tsari ke gudana a wurin. An fahimci cewa wannan shi ne karo na farko da aka yi amfani da tsarin musanya polarity a wurin a cikin batirin lithium mai ƙarfi.

Amma game da yanayin zafi na maganin zafi, ba a sami hasarar taro mai mahimmanci a 120 ℃, yayin da madaidaicin adadin butyl ɗin ya ɓace bayan 15h a 160 ℃. Wannan yana nuna cewa akwai wani yanayin zafi wanda za’a iya cire butyl (a cikin ainihin samarwa, wannan lokacin zafin jiki ya yi tsayi sosai, ko akwai yanayin da ya dace da yanayin da ya dace don inganta aikin samarwa yana buƙatar ƙarin bincike da tattaunawa). Sakamakon Ft-ir na kayan kafin da bayan deprotection ya kuma nuna cewa m electrolyte bai tsoma baki tare da tsarin kariya ba. An yi fim ɗin m tare da manne kafin da kuma bayan deprotection, kuma sakamakon ya nuna cewa adhesive bayan deprotection yana da karfi adhesion tare da mai tara ruwa. Don gwada dacewa da ɗaure da electrolyte kafin da kuma bayan deprotection, an gudanar da bincike na XRD da Raman, kuma sakamakon ya nuna cewa LPSCl m electrolyte yana da kyakkyawar dacewa tare da mai gwadawa.

Na gaba, yi baturi mai ƙarfi duka kuma duba yadda yake aiki. Yin amfani da NCM711 74.5%/ LPSCL21.5% / SP2%/ ɗaure 2%, ƙarfin tsiri sandar sandar ya nuna cewa ƙarfin tsiri shine mafi girma lokacin da ake amfani da ɗaure tBA-B-BR (kamar yadda aka nuna a Hoto 1). A halin yanzu, lokacin cirewa kuma yana da tasiri akan ƙarfin tsiri. Takaddun lantarki na TBA da aka kayyade yana da karye kuma yana da sauƙin karye, don haka TBA-B-BR tare da sassauci mai kyau da ƙarfin kwasfa an zaɓi babban ɗaure don gwada aikin baturi.

Hoto 1. Ƙarfin kwasfa tare da ɗaure daban-daban

Mai ɗaure da kanta shine insulating na ionic. Don yin nazarin tasirin ƙari na binder akan haɗin gwiwar ionic, an gudanar da ƙungiyoyi biyu na gwaje-gwaje, rukuni ɗaya wanda ke dauke da 97.5% electrolyte + 2.5% binder da sauran rukuni wanda ba shi da ɗaure. An gano cewa ionic conductivity ba tare da ɗaure shi ne 4.8×10-3 SCM-1, da kuma conductivity tare da ɗaure shi ne kuma 10-3 tsari na girma. An tabbatar da kwanciyar hankali na electrochemical na TBA-B-BR ta gwajin CV.

uku

Rabin baturi da cikakken aikin baturi

Yawancin gwaje-gwajen kwatankwacin sun nuna cewa abin da aka lalata yana da mafi kyawun mannewa kuma ba shi da wani tasiri akan ƙaura na ion lithium. Amfani daban-daban daure sanya rabin cell don gwada electrochemical Properties, daban-daban gwaji rabin cell bi da bi da gauraye da m, babu mai ɗaure da m electrolyte da Li – A cikin lantarki na guda factor gwaje-gwaje, ba gauraye da mai ɗaure A cikin m electrolyte, don tabbatar da cewa tasirin daban-daban akan mai ɗaure anode. Ana nuna sakamakon aikin electrochemical a cikin hoton da ke ƙasa:

Hoton

A cikin hoton da ke sama: a. shine aikin sake zagayowar rabin tantanin halitta na masu ɗaure daban-daban lokacin da ƙimar fage mai kyau shine 8mg/cm2, kuma B shine aikin sake zagayowar rabin tantanin halitta na nau’ikan ɗaure daban-daban lokacin da ƙimar tabbataccen saman shine 16mg/cm2. Ana iya gani daga sakamakon da ke sama cewa (ba a kare) TBA-B-BR yana da mafi kyawun aikin sake zagayowar baturi fiye da sauran masu ɗaure, kuma ana kwatanta zanen sake zagayowar tare da zane mai ƙarfin kwasfa, wanda ke nuna cewa kayan aikin injinan sanduna suna taka rawa. muhimmiyar rawa wajen aiwatar da aikin sake zagayowar.

Hoton

Hoton hagu yana nuna EIS na rabin tantanin halitta NCM711/ Li-IN kafin zagayowar, kuma adadi na dama yana nuna EIS na rabin tantanin halitta ba tare da sake zagayowar 0.1c na makonni 50 ba. EIS na rabin tantanin halitta ta amfani da (tsararre) TBA-B-BR da BR daure bi da bi. Ana iya kammala shi daga zane na EIS kamar haka:

1. Komai yawan hawan keke, RSE na electrolyte Layer na kowane baturi yana kusa da 10 ω cm2, wanda ke wakiltar juriya na ƙarfin lantarki na LPSCl 2. Ƙaƙƙarfan cajin cajin (RCT) ya karu a lokacin sake zagayowar, amma ƘARUWA na RCT ta amfani da shi. BR mai ɗaure yana da girma fiye da wancan ta amfani da ɗaurin tBA-B-BR. Ana iya ganin cewa haɗin kai tsakanin abubuwa masu aiki ta amfani da BR mai ɗaure ba su da ƙarfi sosai, kuma akwai sassautawa a cikin sake zagayowar.

Hoton

An yi amfani da SEM don lura da ɓangaren giciye na igiya a cikin jihohi daban-daban, kuma an nuna sakamakon a cikin adadi a sama: a. Tba-b-br kafin wurare dabam dabam (kariya); B. kafin zagayawa BR; C. TBA-B-BR bayan makonni 25 (kariya); D. bayan makonni 25 BR;

Zagaye kafin duk na’urorin lantarki za a iya lura a hankali lamba tsakanin aiki barbashi, iya kawai ganin kananan ramuka, amma bayan 25 makonni sake zagayowar, iya ganin bayyananne canji, amfani a c (dauka) abokan – b – m aiki na BR mafi barbashi. ko babu fasa, da kuma yin amfani da electrode aiki na BR binder barbashi akwai mai yawa fasa a tsakiya, Kamar yadda aka nuna a cikin rawaya yankin na D, bugu da žari, electrolyte da NCM barbashi sun fi tsanani rabu, wadanda suke da muhimmanci dalilai na baturi. attenuation aiki.

Hoton

A ƙarshe, ana tabbatar da aikin gabaɗayan baturi. Ingantacciyar na’urar lantarki NCM711/ graphite mara kyau na iya kaiwa 153mAh/g a zagayowar farko kuma ta kula da 85.5% bayan zagayowar 45.

hudu

Takaitaccen bayani

A ƙarshe, a cikin batir lithium mai ƙarfi-mai ƙarfi, ƙaƙƙarfan lamba tsakanin abubuwa masu aiki, manyan kaddarorin inji da kwanciyar hankali sune mafi mahimmanci don samun babban aikin electrochemical.