Kuongororwa kwechikonzero chekuongorora kwe lithium bhatiri simba attenuation

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Mune lithium ion bhatiri, chiyero chehuwandu chinoratidzwa sehuwandu hwehuwandu hwe electrode yakanaka kune electrode yakaipa, iyo: <000000> gamma;= m + / m- =δXC- /δYC + yekumusoro formula C inoreva theoretical coulomb kugona kwe electrode,δzvishoma,δY iri kureva kemikari metering yelithium ions yakaiswa mumagetsi asina kunaka uye electrode yakanaka. Izvo zvinogona kuoneka kubva pane iri pamusoro fomula kuti huwandu hwehuwandu hwemapango maviri huri kutsamira pahuwandu hwecoulomb hukuru uye inodzokororwa inodzokororwa lithium ions zvinoenderana nematanda maviri. Kazhinji, chiyero chiduku chehuwandu chinokonzera kushandiswa kusina kukwana kwezvinhu zvakashata zve electrode; iyo yakakura misa reshiyo inogona kuve nenjodzi yekuchengetedza nekuda kweiyo negative electrode iri overchaired.

Muchidimbu, mune yakanyanya optimized quality reshiyo, bhatiri kuita kwakaringana. Inoenderana neyakodzera Li-ION bhatiri system, munguva yayo yekutenderera, huwandu hwemukati hahuchinji, uye huwandu hwekutanga mukutenderera kwega kwega ndehumwe kukosha, asi mamiriro chaiwo akanyanya kuoma. Chero maitiro epadivi anogona kuoneka kana kushandisa lithium ions kana maerekitironi anogona kukonzera shanduko muyero yebhatiri, kana huwandu hwebhatiri hukangoitika, shanduko iyi haidzokerike, uye inogona kuunganidzwa nekutenderera kwakawanda, uye kushanda kwebhatiri kunoitika.

Serious impact. Mukuwedzera, kunze kwekuchengetwa kweoxidation ye lithium ion, kune nhamba huru yemaitiro emativi, akadai sekuongorora kwe electrolyte, kuparara kwezvinhu zvinoshandiswa, metal lithium deposition, nezvimwewo. Chekutanga: overcharge 1, graphite negative overcharge: Kana bhatiri yakanyanyisa, lithium ion inoderedzwa nyore nyore munzvimbo isina kunaka: iyo lithium yakaiswa yakafukidzwa nepamusoro-soro, ichivhara lithium embedding.

Kubudirira kwekubuda kunoderedzwa uye kurasikirwa kwemasimba, iyo yepakutanga: 1 inogona kuderedzwa ne cyclic lithium; 2 yakaisa simbi lithium uye solvent kana kutsigira electrolyte kuumba Li2CO3, LIF kana zvimwe zvigadzirwa; 3 metal lithium inowanzoumbwa pakati pe electrode yakaipa uye diaphragm, zvichida Mapores ekuvhara diaphragm anowedzera kupikisa kwemukati kwebheteri;. Kurumidza kuchaja, yakawandisa ikozvino density, yakanyanya negative polarization, lithium deposition ichave yakajeka. Iyi mamiriro ari nyore kuitika mune imwe nguva ye electrode yakaipa inoshanda.

Zvisinei, kana iri yepamusoro yekuchaja chiyero, kuiswa kwesimbi lithium kunogona kuitika kunyangwe chikamu cheiyo yakanaka uye yakaipa electrode inoshanda yakajairika. 2, iyo yakanaka chaiyo yekuita yakadzikira kana iyo yakanaka electrode inoshanda kuramba yakadzikira, uye iri nyore kuchaja. Shanduko yakanaka inoita kuti kurasikirwa kwesimba kuve nekuda kwekuitika kwe electrochemical inert zvinhu (senge CO3O4, MN2O3, nezvimwe.

), iyo inokanganisa kuenzana kwehuwandu pakati pe electrode, uye kurasikirwa kwayo kwemasimba hakugoneki. (1) liycoo2liycoo2→(1-y) / 3 [CO3O4 + O2 (G)] + Ylicoo2Y <0.4 Simultaneous positive electrode material analyzes oxygen in a sealed lithium ion battery to analyze the oxygen due to the absence of re-reactive reaction (such as the formation of H2O) and the combustible gas in the electrolyte analysis At the same time, the consequences will be unimaginable.

(2)λ-MnO2 lithium manganese reaction inoitika munzvimbo iyo lithium manganese oxide yakadzikama zvachose.:λ-Mno2→Mn2O3 + O2 (G) 3, iyo electrolyte inoiswa oxidized kana electrolyte yaiswa oxidized kana dzvinyiriro yakakwira kupfuura 4.5V, uye electrolyte (semuenzaniso.

, Li2CO3) uye gasi rine oxidized, uye izvi insolublements inovhara ma micropores e electrode. Kutama kwe lithium ions kunokonzera kurasikirwa kwesimba panguva yekutenderera. Inokanganisa chiyero cheiyo oxidation rate: Iyo mhando uye pamusoro penzvimbo saizi ye conductive agent (carbon dema, nezvimwe.

) yakawedzerwa nechakanaka electrode material surface area size collector material (carbon black, etc.) mumushonga we electrolytic unoshandiswa parizvino, EC/DMC inoonekwa seine yakanyanya oxidation kugona. Iyo electrochemical oxidation process yemhinduro inowanzo kuratidzwa se: mhinduro→Zvigadzirwa zveoxidation (magasi, zvigadziriso uye zvinhu zvakasimba) + NE-chero solvent oxidation inogona kuwedzera kusanganiswa kwe electrolyte, kugadzikana kwe electrolyte kunodzikiswa, uye kugona kwebhatiri pakupedzisira.

Ngatitii inoshandisa chikamu chidiki che electrolyte pese painochajwa, ipapo mamwe maelectrolyte ari mubhatiri kusangana. Kune midziyo yenguva dzose, izvi zvinoreva kuti zvishoma zvishoma zvezvinhu zvinoshanda zvakatakurwa, izvo zvinozokonzera kuderera kwekutanga kukwanisa. Uyezve, kana chigadzirwa chakasimba chikaitika, firimu rekufambisa rinoumbwa pamusoro pe electrode, izvo zvichaita kuti bhatiri riwedzere kubuda kwebhatiri.

Chekutanga 2: Electrolyte (Kudzosa) I Pakuongorora kwe electrode 1 Kudzikisa huwandu hwebhatiri, kuderedzwa kwe electrolyte kunopesana nehukuru hwebhatiri uye kutenderera kwehupenyu kuchakanganisa, uye nekuda kwekuderedzwa kwegasi kuwedzera bhatiri, zvichizotungamira kune nyaya dzekuchengetedza. Iyo yakanaka electrode yekuongorora voltage kazhinji yakakura kupfuura 4.5V (inoenderana neLi / Li +), saka ivo havasi nyore kuongorora mune yakanaka.

Pane kudaro, electrolytes ari kunyanya kusiyana kuongorora. 2, electrolyte inoongororwa pane electrode yakaipa: iyo electrolyte haisi yakakwirira mu graphite uye mamwe pithonal carbon negatives, uye zviri nyore kuita kana isingadzoki. Iyo electrolytic mhinduro yekuongorora panguva yekuchaja yekutanga uye yekuburitsa ichagadzira passivation firimu pamusoro peiyo electrode, uye iyo passivation firimu inogona kudzivirira kumwe kuongorora kwe electrolyte uye kabhoni negative electrode.

Nokudaro, kugadzikana kwemaitiro e carbon negative electrode kunochengetwa. Zvakanaka, kuderedzwa kwe electrolyte kunongogumira padanho rekugadzira firimu rekupfuura, uye nzira haichaitike kana kutenderera kwagadzikana. Kuderedzwa kwekuumbwa kwemunyu we electrolyte yefirimu ye passivation inobatanidzwa mukuumbwa kwefirimu yepasi, iyo inobatsira kugadzikana kwefirimu yepasi, asi iyo yakanyungudutswa iyo yakaderedzwa kusvika kune yakanyungudutswa inokanganisa zvakashata nechigadzirwa chekuderedza kunyungudika; (2) electrolyte munyu kuderedza Kugadziriswa kwekugadzirisa kwe electrolytic kwakaderedzwa, uye pakupedzisira kwakakonzera simba rebheteri (LiPF6 kuderedza kuburitsa LIF, LiXPF5-X, PF3O uye PF3); (3) Kuumbwa kweiyo passivation firimu ndeyekushandisa lithium ions, izvo zvinogona kukonzera kuti polar kugona kusaenzana.

Bhatiri rose rakaderedzwa. (4) Kana pane kutsemuka pane passivation firimu, iyo solvent molecule inogona kutamiswa kuti iite passivation firimu yakakora, iyo isingadyi chete yakawanda lithium, asi zvinokwanisika kuvhara ma micropores pamusoro pekabhoni, zvichiita kuti lithium isakwanise kudzika uye kuburitswa Zvinokonzera kurasikirwa kwesimba kusingadzoreki. Wedzera zvimwe zvekuwedzera, senge CO2, N2O, CO, SO2, nezvimwe.

, inogona kukurumidza kuumbwa kwefirimu ye passivation, uye inogona kudzivisa kufananidzira uye kuongororwa kwezvinonyungudutsa, uye kuwedzerwa kwekorona ether organic additive ine maitiro akafanana, umo 12 korona 4 ether ndiyo yakanakisisa. Zvikonzero zvekurasikirwa kwesimba rekugadzira firimu: (1) Rudzi rwekabhoni; (2) electrolyte zvinhu; (3) zvinowedzera mu electrode kana electrolyte. BLYR inotenda kuti iyo ion exchange reaction inofambira mberi kubva pamusoro pechinhu chinoshanda kusvika pakati payo, iyo yakaumbwa nhanho inovigwa, uye pamusoro pezvikamu zvinoumba yakaderera ion uye erekitironi conductivity, saka spinel mushure mekuchengetedza.

More polarization pane kuchengetedza. ZHANG inoona kuenzanisa kwekuparara kweA AC impedance spectrum isati yasvika uye mushure me electrode zvinhu, nehuwandu hutsva hwekutenderera, kuramba kwepasi passivation layer kwakawedzera, uye iyo interface capacitance yakaderedzwa. Kuratidzira kukora kwepasi passivation layer inowedzerwa nehuwandu hwema cycles.

Kunyungudika kwe manganese uye kuongororwa kwe electrolyte kunoguma nekuumbwa kwefirimu yepassivation, uye mamiriro ekushisa epamusoro anowedzera kuita izvi. Izvi zvinokonzeresa kushomeka kwakanangana neanoshanda zvinhu zvimedu uye kuwedzera kweLi + migration kuramba, nekudaro kuwedzera polarization yebhatiri, uye kubhadharisa uye kubuda hakuna kukwana, uye huwandu hwakaderedzwa. II electrolytic solution reductant mechanism electrolyte inowanzo ine tsvina yakaita seokisijeni, mvura, carbon dioxide, uye oxidative reactions inoitika panguva yekuchaja bhatiri uye kubuda.

Nzira yekudzikisa ye electrolyte inosanganisira kuderedza kunyungudutsa, kuderedza electrolyte uye kuderedza kusachena zvinhu zvitatu zvinoti: 1, kuderedzwa kwePc yekuderedza solvent uye EC kunosanganisira maitiro e electron kune yechipiri electronic reaction process, yechipiri electron reaction inoumba Li2CO3: FONG, nezvimwewo, mune yekutanga Panguva yekubuda, simba re electrode riri pedyo neO.8V.

li/li +), PC / EC inogadzira electrochemical reaction pagraphite, inogadzira CH = CHCH3 (G) / CH2 = CH2 (G) uye LiCO3 (s) , Zvichikonzera kurasikirwa kwesimba kusingadzoreki pamagetsi egraphite. Aurbach et al yemhando dzakasiyana-siyana dzekudzikisa electrolyte uye zvigadzirwa zvayo pasimbi lithium electrode uye carbon-based electrode, yakawana kuti RocO2Li uye propylene zvakaitika mumagetsi maitiro ePC. Roco2li inonzwa zvakanyanya pakuronda mvura.

Chigadzirwa chakasimba ndiLi2CO3 uye propylene, asi hapana Li2CO3 mune yekuomesa kesi. Ein-Eliy akashuma kuti electrolyte yakagadzirwa nediethyl carbonate (DEC) uye diomethymethane (DMC), maitiro ekuita anoitika mubhatiri, uye methyl carbonate (EMC) inoumbwa, uye kune kumwe kurasikirwa kwekukwanisa kurasikirwa. Impact.

2, kuderedzwa kwekuita kwekudzikisa kwe electrolyte ye electrolyte kunowanzoonekwa sekubatanidzwa mukugadzirwa kwepamusoro pekabhoni electrode, uye naizvozvo, marudzi uye kusungirirwa kwayo kuchakanganisa kushanda kwekabhoni electrode. Mune zvimwe zviitiko, kuderedzwa kwe electrolyte kunobatsira kugadzikana kwekabhoni yepamusoro, uye inogona kuumba inodiwa passivation layer. Zvinowanzotendwa kuti electrolyte inotsigira iri nyore kudzikisira pane inonyungudutsa, uye chigadzirwa chekudzikisa kuiswa muiyo negative electrode yakaiswa firimu uye inokanganisa kugona kwebhatiri.

Maitirwo akati wandei anotsigira maelectrolyte anogona kuitika seizvi: 3, iyo yemvura iri mukuderedzwa kweKusachena (1) Mvura iri mu electrolyte inoburitsa LiOH (S) uye Li2O deposition layers, izvo zvisingaite kuti lithium ion embedding, zvichikonzera kurasikirwa kwesimba kusingadzoreki: H2O + E.→OH- + 1 / 2H2OH- + Li +→LiOH (s) LiOH + Li ++ E-→Li2O (S) + 1 / 2H2 inogadzira LiOH (S) kuti iise pamusoro pe electrode, kuumba firimu guru repamusoro rine kupikisa kukuru, kutadzisa Li + embedded graphite electrodes, zvichikonzera kurasikirwa kwesimba kusingadzoreki. Mvura yepakati mune solvent (100-300×10-6) Iko hakuna mhedzisiro pakuita kwegraphite electrode. (2) CO2 mu solvent inogona kuderedzwa pa electrode yakaipa kuti iite CO uye LiCO3 (S): 2CO2 + 2E- + 2LI +→Li2CO3 + COCO ichawedzera bhatiri mubhatiri, nepo Li2CO3 (S) inowedzera bhatiri kuramba inowedzera kushanda kwebhatiri.

(3) Kuvapo kweokisijeni mumushonga kunoumbawo Li2O nokuti mutsauko unokwanisa pakati pesimbi lithium uye kabhoni ye zvachose parallel lithium iduku, uye kuderedzwa kwe electrolyte pa carbon kwakafanana nekuderedzwa kwe lithium. Pakutanga 3: Kuzvibvisa wega-kuzviburitsa zvinoreva kuti bhatiri rinongorasika risingashandiswe. Lithium-ion battery self-discharge inoguma mumatambudziko maviri: imwe inodzoserwa kurasikirwa kwemasimba; yechipiri kurasikirwa kwesimba risingadzoreki.

Iko kudzoreredzwa kwesimba kurasikirwa kunoreva kuti kugona kwekurasikirwa kunogona kudzoserwa panguva yekuchaja, uye iyo isingadzoserwe kurasikirwa kwesimba inodzoserwa kumashure, uye yakanaka uye yakaipa electrode inogona kushandiswa mu micro-sero kushandiswa ne electrolyte munzvimbo yekuchaja, uye lithium ion yakadzikwa uye yakasiiwa, yakanaka uye isina kunaka embedding uye kudzima. Iyo lithium ions yakavharidzirwa inongobatana chete neiyo lithium ions ye electrolyte, uye iyo yakanaka uye yakaipa electrode simba naizvozvo haina kuenzana. Ichi chikamu chekurasikirwa kwesimba hachigone kudzoserwa kana uchichaja.

Zvakadai se: Lithium manganese oxide yakanaka electrode uye solvent inogona kuburitsa yega-discharge inokonzerwa nekuzviburitsa: mamorekuru anonyungudutsa (semuenzaniso, PC) anoiswa oxidized senge microbial masero pamusoro pezvinhu conductive kabhoni dema kana yazvino fluid: zvakafanana, negative electrode active substance Inogona kuzvibuditsa kubva kune electrolytic solution kune electrolyte , electrolyte PF uye yakaderedzwa electrolyte (zvakadai seLiPF6).

Iyo lithium ion inobviswa kubva kune yakaipa electrode ye microcontroller seyakashata electrode yehurumende yekuchaja: self-discharge Factors: Kugadzira maitiro ezvakanaka zve electrode zvinhu, kugadzirwa kwebhatiri, electrolyte properties, tembiricha, nguva. Iyo yekuzviburitsa inodzorwa zvakasimba ne solvent oxidation rate, saka kugadzikana kweiyo solvent kunokanganisa hupenyu hwekuchengetedza bhatiri. Iyo oxidation yezvinonyungudutsa inoitika pamusoro pekabhoni nhema, uye iyo kabhoni dema pamusoro penzvimbo inokwanisa kudzora chiyero chekuzviburitsa, asi kune iyo LIMN2O4 yakanaka electrode zvinhu, kuderedza nzvimbo yechinhu chinoshanda zvakare yakasimba, uye ikozvino muunganidzi anotarisana nekushandiswa kwesolvent oxidation haigone kufuratirwa.

Ikozvino yakaburitswa nebhatiri diaphragm inogonawo kukonzera kuzviburitsa mubhatiri re lithium ion, asi maitiro acho anoganhurirwa neiyo diaphragm kuramba, pamwero wakaderera, uye hauna chekuita nekupisa. Tichifunga kuti chiyero chekuzvibvisa chebhatiri chiri kuvimba zvakasimba pane tembiricha, iyi nzira haisi nzira yakakosha mukuzviburitsa. Kana iyo yakaipa electrode iri mumamiriro emagetsi akakwana, zviri mukati mebhatiri zvinoparadzwa, izvo zvichaita kuti kusingaperi kurasikirwa kwemasimba.