Mashandisiro ekushandisa AC impedance data kuona iyo diffusion coefficient ye lithium yemagetsi zvinhu?

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I-lithium-ion bhatiri ndiyo kutama uye kupararira kweLi + pakati pemapango akanaka uye asina kunaka, uye mutsauko wehutano weLi unosimbiswa pakati pemagetsi akanaka uye asina kunaka, nokudaro kuchengetedza simba remagetsi. Nokudaro, kupararira pakati peLi + pakati pemapango akanaka uye asina kunaka kunokanganisa kushanda kwe lithium ion battery performance. Kana isu takarongwa mumhando dzakasiyana-siyana kubva kumhanyisa-kusvika-inononoka kumhanya kweLi +, hapana mubvunzo kuti kupararira kweLi + mu electrolyte ndiko kwakanyanya.

Kurumidza, inoteverwa nechaji chekuchinjana cheLi + munzvimbo yakanaka uye isina kunaka, kumhanya kweichi chiitiko kunonoka, zviri nyore kudzikamisa kudzikisira kudzoreredzwa, uye Li + ndiyo inononoka mune yakanaka uye yakaipa zvinhu, ichi chinongedzo chinowanzoita kiyi yekudzora magnification kuita kwe lithium ion bhatiri. Seyakakosha parameter solid phase diffusion coefficient ye reactive substance in the active substance, solid phase diffusion coefficient ndiyo kiyi yehuwandu hwezvinhu, asi maparamendi ezvishandiso haasi nyore. Kazhinji, iyo nzira yekuverenga iyo yakasimba chikamu diffusion coefficient yechinhu chinoshanda chine yakakosha inogona kutaurwa, inogara iripo titration, uye AC impedance data.

Nguva pfupi yadarika, Tienquangnguyen (Masevhisi Ekutanga) naCorneliabreitkopf (Munyori Anowirirana) wekuGermany Dresden University of Technology vakaronga nzira itsva yekuwana diffusion coefficients kuburikidza neAC impedance data. Iyo diffusion coefficient yekuwana zvinhu uchishandisa EIS data haisi pfungwa nyowani. Pakave nemhando dzakawanda dzakashandisa diffusion impedance value muAC impedance kuverengera diffusion coefficient ye electrode kana zvinhu, asi mamodheru aya anowanzo kufanira kusanganiswa nekupararira.

Kuverengera kwezviyero zvakaita sehurefu, uye kukosha uku kunowanzo kuverengerwa nehukobvu hwe electrode kana chidimbu cheradius. Nzira iyo Tienquangnguyen yaakakurudzira chete kushandisa AC impedance data kuti uwane ese ma paramita anodiwa kuverenga iyo diffusion coefficient. Zvinoenderana nechirevo cheiyo diffusion coefficient, tinogona kuwana diffusion coefficient nereshiyo pakati peiyo ID kureba uye yekuparadzira nguva taud (sezvinoratidzwa mune inotevera fomula).

Inogona kuonekwa kubva pane fomula iri pamusoro. Kuti tiwane diffusion coefficient tinofanirwa kuwana ma parameter ari pamusoro nekuyedza data kana theoretical model data. Mune electrochemical system, kufamba kweion kunogona kuverengerwa zvichienderana nenguva yekuzorora tau2 muukobvu hwemaviri-magetsi layer lambDAD uye polarization.

Kuti tiwane iwo akakosha maparamendi eiyo diffusion coefficient, isu tinofanirwa kutanga tawana iyo data yeiyo diffusion layer gobvu. Iyo inodaidzwa kunzi diffusion layer inoreva huwandu hwehuwandu hwehuwandu hwehuwandu mukupararira, uye Bandaraampmellanderandcoelho et al. Et al.

Model kuverengera ukobvu hweiyo diffusion layer. Mufananidzo uri pazasi unoratidza kusagadzikana kweiyo electrochemical system yekaviri inovharira electrode uye yekurasikirwa kona yakajairika kukosha. Iyo inoshanda dielectric constant inogona kuverengerwa neinotevera fomula 3, apo j inhengo yekufungidzira, Delta ndiyo reshiyo pakati pehafu yehupamhi hwesample uye ukobvu hweiyo diffusion layer, kazhinji isu tinotenda kukosha uku kwakakura kupfuura gumi.

Iyo kona yekurasikirwa ndiyo reshiyo pakati pekurasikirwa kwedielectric uye iyo chaiyo dielectric inongogara (inoratidzwa muFormula 4). Kubva pamufananidzo B, zvinokwanisika kuona kuti kurasikirwa kwekona node ine kukosha kwepamusoro panguva inogara TAU2, uye hukama huri pakati pekurasikirwa kwekona yakakosha kukosha neDelta inoratidzwa muFormula 5, saka iyo diffusion layer thickened inogona kuverengerwa neformula inotevera 6. Mune iyo data yeEIS, iyo yakaganhurirwa Warburg diffusion impedance ine maparamendi akadai sekupararira kureba, diffusion coefficient, uye diffusion velocity, kazhinji isu tinogona kushandisa yakaenzana dunhu kuti ikwane EIS yekuona mhedzisiro neZVIEW uye mamwe maturusi kuwana diffusion nguva paramita.

Nekudaro, mune zvimwe zviitiko zveimwe impedance, iyo yakakodzera mhedzisiro inowanzova isina kunaka, uye dambudziko iri rinogona kugadzirwa kuti rikwane rakawanda data nekukodzera nzvimbo yekuchinja muAC impedance data. Iyo yakaganhurirwa kureba kweWarburg diffusion impedance inogona kuratidzwa mune formula 7, uko RW iri shoma yekuparadzira impedance, uye nguva yekuparadzira inogona kuverengerwa nepamusoro fomula 1. Hukama hweparameta mufomula iri pamusoro inoratidzwa mune maformula 9, 10, uye iyo yakasimba uye yekufungidzira chikamu cheinogumira diffusion impedance inogona kurerutswa muchimiro cheiyo inotevera formula 13 neinotevera fomula 11 uye 12.

13 tinogona kuona kuti RW inogona kureva kutsetseka kwehukama pakati peZ neOmega1 / 2. Mufananidzo uri pamusoro unoratidza yakajairwa AC impedance mepu, iyo inogona kuona kutsetseka kweiyo impedance curve munzvimbo yekuchinja ye45 madhigirii kubva pamufananidzo, izvo zvinoreva kuti kukosha kweiyo chaiyo uye yekufungidzira chikamu cheiyo impedance munharaunda ino yakaenzana. Nezve kupararira maitiro eiyo interface, isu tinokwanisa kukwana iyo Randles yakaenzana sedunhu inoratidzwa pazasi.

Sezvo iyo WARBURG element uye frequency square midzi uye chikamu chekona zvakabatana zvisina kunaka, iyo peni yakananga kuora ine yakaenzana dunhu reWarburg element ichiri Basa rakaoma kwazvo, saka isu tinogona kuitsiva seyakafanana RW neCW, saka iyo impedance yese yeyakaenzana dunhu inoratidzwa pazasi inoratidzwa muFormula 15, uye iyo yakazara pakati peiyo impedance chaiyo inoratidzwa chikamu cheiyo Fig. 16, chikamu chaicho uye chikamu chekufungidzira chinogona kuchinjwa kuva capacitance kukosha kwezvikamu zviviri zvemagetsi epamusoro pechiso che electrode muchimiro che electrode surface muchimiro chechipiri chechipiri 17, iyo iduku zvikuru. Kazhinji, mu 1-10uf / cm2, iyo impedance yeiyo impedance yakazara mumufananidzo unotevera wedunhu inogona kutorwa seyakaenzana nechikamu chekufungidzira cheWarburg impedance, kureva z = omGAZ, uye iyo inonyanya kukosha yekupararira ID yeiyo diffusion coefficient inogona kuve yemagetsi The diffusion coefficient uye diffusion nguva inoverengerwa iyo inotevera mubhadharo, senge inoratidzwa mubhadharo. iyo diffusion coefficient yema electrons inogona kutsiviwa neion mobility, uye nguva yekupararira inogona kushandiswa Nguva inogara ichienderana nearc panzvimbo yakakwirira mufrequency curve inoratidzwa muFIG.

Naizvozvo, iyo fomula iri pamusoro inogona kushandurwa kuita iyo fomati inoratidzwa mufomula. Zvinoenderana neataurwa pamusoro apa modhi vanyori vanoodza data kubva muzvinyorwa, inogona kuona masampula mashanu akasarudzwa kubva pamufananidzo unotevera ane musiyano wakasiyana muyekuro yekupararira kweiyo yakaderera frequency nzvimbo, uye akati wandei masampuli anoumbwa semi-denderedzwa dunhu. Ipapo kune kushomeka kwekupararira kunokanganisa kweanenge madhigirii makumi mana neshanu kuruboshwe uye kurudyi muhuwandu hwehushoma hwema frequency, uye nekudaro, zvinoenderana nemuenzaniso wepamusoro, nguva yekuparadzira nguva yemhando dzakati wandei dzeWSC = 2, 4, 5, 6 uye 15 ndeye 4, zvichiteerana.

16, 25, 36, uye 225 (inoratidzwa muTebhurari 1 pazasi). Kuti aenzanise migumisiro yemuenzaniso wepamusoro, munyori anotora nzira yekushambadza kwemamorekuru emvura ari pamusoro pe sulphate zirconium sulphate, kutanga achishandisa Randles yakaenzana yedunhu kuti ienderane nemigumisiro yekuongorora miedzo, uye inogona kuona chikamu chaicho chekudzivirira kubva pamufananidzo uri pasi apa. Iko kukanganisa pakati peyedzo kukosha uye kukosha kwakakodzera kwakasvika 25%, uye kuziviswa kwedunhu rakakodzera mhedzisiro ine Warburg impedance haina kunaka mune iyo yakakwira impedance kana ruzha rwakanyanya.

Naizvozvo, iwo manhamba akakodzera anogona chete Reference. Mumufananidzo uri pasi apa, munyori anofananidza kukodzera kweiyo nzira yemuenzaniso inotsanangurwa neyakafanana yakaenzana yedunhu nzira uye munyori. Kubva pamufananidzo wezasi wekuruboshwe, zvinodikanwa kuti uone iyo yakakodzera mhedzisiro inowanikwa neiyo nyowani modhi nzira.

Zviri nani pane zvechinyakare zvakaenzana dunhu. Iyo diffusion coefficient yakawanikwa kubva kune inotevera Tafura 3 inogona kuona mhedzisiro yekufambiswa kweion net uye mhute yemvura uye mhedzisiro yekuonekwa kwevamwe vanhu. Iyo nzira yakatsanangurwa naTienquangnguyen inoenderana nekukodzera iyo inopera diffusion kureba chikamu mu AC impedance, peni yakatwasuka uye kureba kwekupararira kureba, nekudaro kuona nekukurumidza uye kwakaringana kutsunga kwekutsanya uye kwakaringana data uchishandisa AC impedance data.