Chando chiri kuuya, tarisa pasi-tembiricha yekuongorora phenomenon ye lithium-ion mabhatiri

Kuita kwemabhatiri e-lithium-ion kunokanganisa zvakanyanya nemaitiro avo ekinetic. Nekuti Li+ inoda kutanga yaparadzwa kana yaiswa mukati meiyo graphite zvinhu, inoda kushandisa imwe huwandu hwesimba uye kutadzisa kupararira kweLi+ mugraphite. Pane zvinopesana, apo Li + inosunungurwa kubva kune graphite zvinhu mumhinduro, iyo solvation process ichaitika kutanga, uye solvation process haidi kushandiswa kwesimba. Li + inogona kukurumidza kubvisa graphite, izvo zvinotungamira kune yakanyanya kuderera kubhadharisa kugamuchirwa kwezvinhu zvegraphite. Mukusunungurwa kugamuchirwa .

Pakutonhora kwakadzika, maitiro ekinetic eiyo negative graphite electrode akavandudza uye anowedzera kuipa. Nokudaro, iyo electrochemical polarization ye electrode yakaipa inowedzerwa zvakanyanya panguva yekuchaja, izvo zvinogona kutungamira nyore kune kunaya kwesimbi lithium pamusoro peiyo negative electrode. Tsvakurudzo yakaitwa naChristian von Lüders weTechnical University yeMunich, Germany, yakaratidza kuti pa -2 ° C, mutengo wekutengesa unopfuura C / 2, uye chiyero chesimbi lithium precipitation inowedzera zvakanyanya. Semuenzaniso, pachiyero cheC / 2, huwandu hwe lithium plating pane inopikisana ne electrode surface inenge yese yechaji. 5.5% yehukuru asi ichasvika 9% pasi pe1C magnification. Iyo inonaya yesimbi lithium inogona kuenderera mberi uye inopedzisira yava lithium dendrites, ichibaya nepakati pe diaphragm uye ichikonzera kupfupika-kutenderera kweiyo yakanaka uye yakaipa electrodes. Naizvozvo, zvinodikanwa kuti udzivise kuchaja iyo lithium-ion bhatiri pane yakaderera tembiricha sezvinobvira. Kana ichifanira kuchaja bhatiri pane tembiricha yakaderera, zvakakosha kuti usarudze diki ikozvino kubhadharisa lithium-ion bhatiri zvakanyanya sezvinobvira uye chengetedza zvizere lithium-ion bhatiri mushure mekuchaja kuti ive nechokwadi Iyo metallic lithium inodonha kubva kune negative electrode. inogona kuita ne graphite uye yakadzikwa zvakare mune negative graphite electrode.

Veronika Zinth nevamwe veTechnical University yeMunich vakashandisa neutron diffraction nedzimwe nzira dzekudzidza maitiro e-lithium evolution ye lithium-ion mabhatiri pamhepo yakadzika -20 ° C. Neutron diffraction yanga iri nzira nyowani yekuona mumakore achangopfuura. Kuenzaniswa neXRD, neutron diffraction inonyanya kunzwisiswa nemwenje zvinhu (Li, O, N, nezvimwewo), saka yakanyatsokodzera kusakuvadza kuyedzwa kwe lithium-ion mabhatiri.

Muchiyedzo ichi, VeronikaZinth yakashandisa bhatiri reNMC111/graphite 18650 kudzidza maitiro e lithium evolution yemabhatiri e lithium-ion pane tembiricha yakaderera. Bhatiri inochajwa uye inoburitswa panguva yekuyedzwa zvinoenderana nemaitiro anoratidzwa mumufananidzo uri pazasi.

Iyi inotevera nhamba inoratidza shanduko yechikamu cheiyo negative electrode pasi peSoCs dzakasiyana panguva yechipiri yekuchaja kutenderera paC/30 rate yekuchaja. Zvinogona kuita sekuti pa 30.9% SoC, zvikamu zve electrode yakaipa zvakanyanya LiC12, Li1-XC18, uye zvishoma zveLiC6 Composition; mushure mekunge SoC yadarika 46%, iyo diffraction intensity yeLiC12 inoramba ichidzikira, nepo simba reLiC6 richiramba richiwedzera. Nekudaro, kunyangwe mushure mekuchaja kwekupedzisira kwapera, sezvo chete 1503mAh inochajwa pakudziya kwakadzika (iyo simba iri 1950mAh pakamuri tembiricha), LiC12 iripo mune iyo yakaipa electrode. Ngatitii kuchaja ikozvino kwakaderedzwa kusvika kuC/100. Kana zvakadaro, bhatiri rinogona kuramba richiwana huwandu hwe1950mAh pakudziya kwakaderera, izvo zvinoratidza kuti kuderera kwesimba remabhatiri e-lithium-ion pakudziya kwakaderera kunonyanya kukonzerwa nekuderera kwemamiriro ekinetic.

Mufananidzo uri pasi apa unoratidza kuchinja kwechikamu che graphite mu electrode yakaipa panguva yekuchaja maererano neC / 5 chiyero pane yakaderera tembiricha ye -20 ° C. Inogona kuona kuti shanduko yechikamu chegraphite yakasiyana zvakanyanya ichienzaniswa neC/30 rate yekuchaja. Zvinogona kuoneka kubva pamufananidzo kuti kana SoC> 40%, iyo chikamu chesimba rebhatiri LiC12 pasi peC/5 yekuchaja chiyero chinodzikira zvakanyanya zvishoma, uye kuwedzera kweLiC6 chikamu chesimba zvakare kushoma zvakanyanya kupfuura iyo yeC/30. mutengo wemari. Zvinoratidza kuti pamwero wakakwira weC/5, shoma LiC12 inoramba ichipindirana lithium uye inoshandurwa kuita LiC6.

Nhamba iri pasi apa inoenzanisa kuchinja kwechikamu cheiyo negative graphite electrode painochaja paC/30 uye C/5 rates, zvichiteerana. Iyo nhamba inoratidza kuti kune maviri akasiyana ekuchaja mareti, iyo lithium-varombo chikamu Li1-XC18 yakafanana zvakanyanya. Musiyano unonyanya kuratidzwa muzvikamu zviviri zveLiC12 uye LiC6. Zvinogona kuoneka kubva pamufananidzo kuti nhanho yekuchinja kwechikamu mune yakashata electrode iri padyo padanho rekutanga rekuchaja pasi pezviyero zviviri zvekuchaja. Yechikamu cheLiC12, kana iyo yekuchaja yasvika 950mAh (49% SoC), shanduko yekuchinja inotanga kuoneka yakasiyana. Kana zvasvika 1100mAh (56.4% SoC), iyo LiC12 chikamu pasi pemakurisa maviri anotanga kuratidza gaka rakakura. Paunenge uchibhadhara pamutengo wakaderera weC / 30, kuderera kweLiC12 danho rinokurumidza, asi kudonha kwechikamu cheLiC12 paC / 5 kunonoka; kureva kuti, iyo kinetic mamiriro ekuiswa kwe lithium mune yakaipa electrode inoderera pakudzika kwakadzika. , Kuitira kuti LiC12 iwedzere kupindirana lithium kugadzira LiC6 phase yekumhanya yakadzikira. Saizvozvo, iyo LiC6 chikamu chinowedzera nekukurumidza pachiyero chakaderera cheC/30 asi chinononoka zvakanyanya pachiyero cheC/5. Izvi zvinoratidza kuti pachiyero cheC/5, yakawedzera petite Li yakanyudzwa mukristaro chimiro chegraphite, asi chinonakidza ndechekuti bhatiri rekuchajisa (1520.5mAh) paC/5 charge rate yakakwira kupfuura iyo paC. / 30 mutengo wemari. Simba (1503.5mAh) rakakwirira. Iyo yakawedzera Li iyo isina kuisirwa mune inegative graphite electrode ingangove inonaya pamusoro pegraphite pamusoro muchimiro chesimbi lithium. Nzira yekumira mushure mekupera kwekuchaja inoratidzawo izvi kubva parutivi-zvishoma.

Mufananidzo unotevera unoratidza chimiro chechikamu cheiyo negative graphite electrode mushure mekuchaja uye mushure mekusiiwa kwemaawa makumi maviri. Pakupera kwekuchaja, chikamu cheiyo negative graphite electrode chakasiyana kwazvo pasi pematanho maviri ekuchaja. PaC/20, chiyero cheLiC5 mu graphite anode chakakwira, uye chikamu cheLiC12 chakaderera, asi mushure mekumira kwemaawa makumi maviri, mutsauko pakati pezviviri wave mudiki.

Mufananidzo uri pasi apa unoratidza shanduko yechikamu cheiyo negative graphite electrode panguva ye20h kuchengetedza maitiro. Inogona kuona kubva pamufananidzo kuti kunyange zvazvo zvikamu zvema electrode maviri anopesana zvichiri zvakasiyana zvikuru pakutanga, sezvo nguva yekuchengetedza inowedzera, iyo miviri yemhando yekuchaja Chikamu chegirafu anode pasi pekukura chakashanduka pedyo zvikuru. LiC12 inogona kuramba ichishandurwa kuita LiC6 panguva yekusherufu, zvichiratidza kuti Li icharamba yakamisikidzwa mugirafu panguva yekuvharirwa. Ichi chikamu cheLi chinogona kunge chiri simbi lithium inonaya pamusoro peiyo negative graphite electrode pakudziya kwakaderera. Kumwe kuongorora kwakaratidza kuti pakupera kwekuchaja pachiyero cheC/30, dhigirii rethium intercalation yeiyo negative graphite electrode yaive 68%. Zvakadaro, dhigirii re lithium intercalation yakawedzera kusvika 71% mushure mekugara, kuwedzera kwe3%. Pakupera kwekuchaja pachiyero cheC / 5, iyo lithium yekuisa dhigirii yeiyo negative graphite electrode yaive 58%, asi mushure mekusiiwa kwemaawa makumi maviri, yakawedzera kusvika 20%, kuwedzera kwe70%.

Tsvagiridzo iri pamusoro inoratidza kuti kana uchichaja pane tembiricha yakaderera, huwandu hwebhatiri hunodzikira nekuda kwekuipa kwemamiriro ekinetic. Ichawedzerawo simbi yelithium pamusoro peiyo negative electrode nekuda kwekuderera kweiyo graphite lithium yekuisa rate. Zvisinei, mushure menguva yekuchengetedza, Ichi chikamu chesimbi lithium chinogona kuiswa mugraphite zvakare; mukushandiswa chaiko, nguva yesherufu kazhinji ipfupi, uye hapana vimbiso yekuti simbi yese yelithium inogona kuiswa mugirafu zvakare, saka inogona kuita kuti imwe simbi lithium irambe iripo mune yakaipa electrode. Iyo lithium-ion bhatiri yepamusoro inokanganisa simba re lithium-ion bhatiri uye inogona kugadzira lithium dendrites inoisa panjodzi kuchengetedzeka kwerithium-ion bhatiri. Naizvozvo, edza kudzivirira kuchaja iyo lithium-ion bhatiri pane yakaderera tembiricha. Yakaderera ikozvino, uye mushure mekugadzirisa, chengetedza nguva yakakwana yesherufu yekubvisa simbi lithium mune yakaipa graphite electrode.

Ichi chinyorwa chinonyanya kureva zvinyorwa zvinotevera. Chirevo ichi chinongoshandiswa kusuma nekuongorora ane chekuita nesainzi mabasa, kudzidzisa mukirasi, uye tsvagiridzo yesainzi. Kwete kushandiswa kwekutengesa. Kana uine nyaya dzekodzero, ndapota inzwa wakasununguka kutibata nesu.

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2.Lithium plating mumabhatiri e-lithium-ion akaongororwa nekuzorodza kwemagetsi uye in situ neutron diffraction,Journal of Power Sources 342(2017)17-23, Christian von Lüders, Veronika Zinth, Simon V.Erhard, Patrick J.Osswald, Michael Hofman , Ralph Gilles, Andreas Jossen

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