Uhlalutyo lwe-CATL phosphate itshaja ibhetri ye-lithium yobushushu obuphezulu bokugcina ubushushu besizathu

作者：Iflowpower – Kaasaskantava elektrijaama tarnija

ICatlcatl isebenzisa ibhetri ye-ion ye-lithium ye-iron phosphate ion ukuphonononga izizathu zayo zokuphulukana nomthamo wokugcina kwindawo yombane, i-60 ° C. Indlela yokuthomalalisa umthamo webhetri ukusuka kwisistim yebhetri kunye nenqanaba lepali ngokubonakaliswa komzimba kunye novavanyo lwentsebenzo ye-electrochemical. I.

Imifuniselo yenkqubo yovavanyo kusetyenziswa imveliso yeCATL yesikwere se-phosphate ion ibhetri ene-86AH. Ibhetri yinto efanelekileyo ye-electrode kwi-LifePO4, i-graphite yinto engafanelekanga ye-electrode, isebenzisa i-polyethylene separator kunye ne-electrolyte ye-LiPF6. Khetha iibhetri ezingama-20 kufutshane nebhetshi efanayo kunye nokusebenza kombane ukugcina, vavanya ukusebenza kombane webhetri.

I-100% ye-SOC ibhetri ye-60 ° C igcinwe kumshicileli phakathi kwe-2.50 ukuya kwi-3.65V, ukukhutshwa kwe-0.

Ukwandiswa kwe-5C - umjikelo wokutshaja. Emva koko ibhetri egcwalisekayo ngokupheleleyo igcinwa kwi-60 ° C. Oku kuphindaphindiweyo, ukurekhoda inkqubo yokunciphisa umthamo webhetri.

Ngexesha lokuvavanywa komthamo ngamnye, ukuxhathisa kwangaphakathi kwe-DC (DCR) kwebhetri 5C / 30S kuvavanywa. Thatha ibhetri kumaxesha ahlukeneyo ogcino kwaye ikwimeko yokukhutshwa ngokupheleleyo, idityaniswe kwibhokisi yeglavu yegesi ye-AR. Sebenzisa imakroskopu ye-electron ephumayo ukujonga i-polar morphology, sebenzisa uhlalutyi lomphezulu oluthile ukuvavanya indawo ethile yomphezulu.

Kwibhokisi yeglavu, isiqwenga se-electrode sitywinwe ngeteyiphu ebonakalayo, kwaye izinto ze-electrode zihlalutywa kusetyenziswa i-X-ray diffractometer. Isiqwenga se-polar emva kokuchithwa kwebhetri yi-electrode esebenzayo, i-lithium sheet yi-counter electrode, kwaye ifakwe kwi-CR2032 ibhetri ye-buckle, kunye neempawu ze-electrochemical ze-yin kunye ne-plate ephantsi. I-electrochemical impedance spectrum yebhetri ye-buckle ene-electrochemical workstation.

Uhlalutyo lwesiqulatho se-elementi yephepha le-electrode usebenzisa i-spectrometer yokukhutshwa kwe-plasma inductive coupling. Okwesibini, iziphumo zaxoxa nge-1. Uhlalutyo lwentsebenzo yebhetri Umzobo 1 kukunciphisa umthamo webhetri kunye nokutshaja kunye nokukhupha ukusebenza.

Ngokwandiswa kwexesha lokugcina, umthamo webhetri uwohloka ngokuthe ngcembe. Xa ixesha lokugcina lifikelela kwi-575d, ukuthotywa kwamandla ebhetri yi-85.8% yomthamo wokuqala.

Ibhetri ihlawuliswa kwaye ikhutshwe kwi-0.02 C, kwaye i-curve ye-voltage yebhethri ephakathi iqulethe i-lithium ion efakwe kwi-platformity eninzi ebangelwa yi-graphite, ebonisa ukuba ukukhulisa i-0.02c kunikezelwe kwisakhiwo se-graphite kwisakhiwo se-graphite ngexesha lenkqubo ye-lithium ion.

Kwanele. , Ukuphelisa ngokufanelekileyo imiphumo ye-polarization kwimijikelezo. Umzobo 1 Ukunciphisa umthamo webhetri kunye nokusebenza kwentlawulo kunye nokukhupha kuthelekiswa ne-0.

Ukwandiswa kwe-5, umlinganiselo wentlawulo kunye nokukhutshwa kuncitshiswe kwi-0.02c, enokunyusa kuphela umlinganiselo wokugcinwa kwamandla okugcina i-181 kunye ne-575d iibhetri kwi-0.8% kunye ne-1.

4%. Ke ngoko, ukucutha umthamo webhetri okubangelwa kukugcinwa kobushushu obuphezulu bexesha elide kukuthomalalisa umthamo ongenakuguqulwa. Ukongeza, kuboniswa ukuba i-amplitude yebhetri ye-DC yangaphakathi yokuxhathisa inyuka kwaye ayibalulekanga, nto leyo ebonisa ukuba i-polarization yangaphakathi yebhetri ayiyona sizathu esibalulekileyo sokugcina ikhalenda umthamo webhetri ukungaguquki.

2. Ukuhlalutya iNdlela yokuHlalutya iNdlela yokuHlalutya imvelaphi yebhetri, ibhetri ihlawuliswa kwi-100% SOC okanye ikhutshwe kwi-100% ye-DOD emva kokukhulisa i-1C. Uhlalutyo lwesibonda esichithwayo ukuvavanya imiphumo yokugcina ukushisa okuphezulu kwisakhiwo, ukubunjwa kwe-elemental kunye neempawu ze-electrochemical ze-yin kunye nezinto ezingaphantsi ezisebenzayo.

Uhlalutyo lokuntywiliselwa kwi-slides ye-100% ye-DOD ye-DOD ye-XRD eyahlukileyo ngexesha lokugcinwa kwebhetri. Xa kuthelekiswa nomgangatho we-XRD we-spectrum ye-LifePO4 kunye ne-FEPO4, zonke iincopho ze-diffraction zesilayidi se-polar zihambelana, akukho sigaba esixubileyo. Umzobo we-2 XRD i-spectrum ye-cathode yebhetri yamaxesha ahlukeneyo okugcinwa kweqondo lokushisa eliphezulu Imemori yangemuva ye-electrode sheet iipropathi ze-electrochemical zinciphisa amaxesha ahlukeneyo okugcina kwi-100% ye-SOC, apho i-electrode isetyenziswa njenge-electrode esebenzayo Ibhetri, ukuhlawulisa kunye novavanyo lokukhupha nge-0.

Ukwandiswa kwe-1C. Umlinganiselo wokuqala wokukhutshwa kwe-cathode esebenzayo yezinto ezahlukeneyo zokugcina ixesha leebhetri liphezulu kune-155 mah / g, kunye nomthamo othile we-cathode esebenzayo ngaphandle kwebhetri yokugcina isondele kugcino lwesakhiwo se-LIFEPO4 ngaphandle komonakalo ocacileyo. Intlawulo yombane engaguqukiyo yebhetri yebhanti kuMfanekiso 3 (c) yongezwa kancinane, kodwa isixa esipheleleyo sokutshaja sisasondele kumthamo othile wecathode esebenzayo yento ngaphandle kwebhetri yokugcina.

I-polarization ye-cathode yebhetri emva kwe-575D inyukile, kodwa amandla okugcina i-lithium yezinto ze-cathode ayichaphazeleki, kwaye i-electrolyte decomposition product deposition in the storage process can be related. Ikhiwane. I-3 ibhetri ye-buckle apho intlawulo kunye nokukhupha ijika yebhetri ye-buckle ihlanganiswe yi-electrode yangaphakathi yebhetri engasonjululwanga ivela kwi-181 kunye ne-575d, ngokulandelanayo, kunye ne-335.

6 kunye ne-327.1 mAh / g, ngokulandelanayo, ngokulandelanayo. Ibhetri ye-buckle ye-anode yebhetri egciniweyo iguqulwe ibe yi-0.

I-8% kunye ne-3.0%, ebonisa ukuba ukugcinwa kokushisa okuphezulu kwe-lithium graphite nayo incinci kakhulu. Ngombono wokhuseleko lwebhetri, inani elipheleleyo le-anode kwibhetri yonke lidla ngokudlula i-10% yomthamo opheleleyo we-cathode, ngoko ke ukuthotywa kwe-anode engenakuguquleka okubangelwa kukugcinwa kobushushu obuphezulu akuchaphazeli umthamo webhetri yonke.

Ukugcinwa kwe-181 kunye ne-575D I-anode yi-anode yokuqala yokulinganisa umthamo wexabiso elingenakunqandwa le-90.4% kunye ne-84.5% yentlawulo yokuqala ye-anode, ngokulandelanayo, kunye nesantya sokugcinwa kwamandla ebhetri yangempela isondele.

Ke ngoko, isizathu esibalulekileyo sokunciphisa umthamo webhetri kukulahleka kwee-ion ze-lithium ezisebenzayo kuzo zonke iibhetri. Isishwankathelo, ukugcinwa kweqondo lokushisa eliphezulu akuyi kuchaphazela kakhulu i-deintercalation ye-LIFEPO4 kunye ne-graphite electrodes. I-100% ye-DOD ibhetri yokugcina iqondo lokushisa eliphezulu I-cathode ye-pell kubukho, imbangela yesixa se-lithium ion ekwazi ukufumana i-anode ayikho utshintsho olubalulekileyo ekukwazini ukuguqula ngokukhawuleza izinto ezisebenzayo ze-electrode, kodwa ngenxa yebhetri ebhetri.

Inani leeyoni liba lincinci. I-lithium ion esebenzayo kwibhetri idliwe yi-electrode / electrolyte interface ye-electrode / electrolyte interface, kwaye ingcambu ye-lithium ion ilahleko esebenzayo inceda ukujulisa ulwazi lwendlela yokulahlekelwa kwamandla okugcina. Uhlalutyo lwe-polar micropatological ye-LifePO4 particles in the cathode in the cathode, ubukhulu be-particle bu malunga ne-200 nm; emva kokugcinwa kwe-181D, ubungakanani be-void phakathi kweengqungquthela ze-LIFEPO4 abutshintshi kakhulu; emva kokugcinwa kwe-575D, i-gap phakathi kwamaqhekeza iyancipha kakhulu.

Kwi-anode yegraphite, njengoko ixesha lokugcina liye landa, inani lemveliso yecala elisebenzayo liyatshintshwa [Umfanekiso. 4 (d), (e), (f)]. Imveliso ye-sub-reactive kwinkqubo yokugcinwa kweqondo lokushisa eliphezulu ifakwe kwisibonda, kwaye i-morphology yesibonda iyatshintshwa.

Ukuze ubonise impembelelo ye-sub-reaction kwi-lithium ion ilahleko ekhankanywe ngasentla, umxholo we-Li kwi-yin kunye ne-element yendoda ihlaziywa ngakumbi ukuze ufunde ingcambu ye-lithium ion loss esebenzayo. Umfanekiso we-4 I-Battery pole morphology table 1 yisiphumo sovavanyo lwe-ICP-OES ye-100% ye-SOC yebhetri yin anode. Utshintsho kumxholo weLi kwi-cathode ayibonakali.

Umxholo we-LI we-anode nawo ugcinwe kwinqanaba elifanayo, ngoko ke inani lilonke lokuqina kwe-yin kunye ne-polite endala ye-LI kwiibhetri zexesha lokugcinwa kwezinto ezahlukeneyo azitshintshi kakhulu. Itheyibhile 1 Iibhetri zexesha elihlukeneyo lokugcinwa (i-100% SOC) umxholo we-polar element Ekubeni i-100% ye-SOC ibhetri ye-cathode sheet iqulethe ephantsi kakhulu, ukulahlekelwa kwe-lithium ion esebenzayo kubalulekile ukufaka kwi-anode. Kwi-100% ye-SOC yokugcina ubushushu obuphezulu, i-anode ikwimeko apho ipotium ikwimo apho amandla aphantsi kakhulu, kwaye i-electrolyte isabela ngokulula kumphezulu wayo, kwaye i-ion ze-lithium zidliwe, kunye ne-lithium-equlathe imveliso esebenzayo yecala.

Ukuze unqume ukubunjwa kwendawo ye-lithium e-soluble ye-anode, ukuchithwa kwebhetri ye-DOD ye-100% i-titrated, kwaye iziphumo ziboniswe kwiThebhile 2. Itheyibhile ye-2100% ibhetri ye-DOD i-Anode i-lithium e-soluble ihlanganisa i-anode surface kwi-carbonate morphology, eyonyuswa njengoko ixesha lokugcina lilongeziwe (jonga i-Table 2), ebonisa ukuba inkqubo yokugcina ibhetri ivelisa inani elikhulu lezinto zetyuwa ze-lithium ezingaphili. Ityuwa ye-inorganic iyimveliso ebalulekileyo ye-reaction yokunciphisa i-solvent, ebangelwa inani elikhulu lokubola kwe-electrolyte ngexesha lokugcinwa kwebhetri.

I-Electrode Reaction Dynamics I-Electrochemical Exhaust Spectroscopy (jonga uMzobo 5), nangona i-cathode RCT iyanda ngexesha lokugcina ukushisa okukhulu [Umfanekiso. I-5 (a)], kodwa i-cathode RCT incinci, ukuchasana kwangaphakathi kwebhetri kuncinci. Anode EIS [Fig.

I-5 (b)] I-RSEi ayibonakali kunye nexesha lokugcina, kodwa i-RCT ithatha ixesha elide kunye nexesha lokugcina. Ngenxa yokubekwa kwemveliso ye-electrolyte sub-reaction ngexesha logcino lobushushu obuphezulu, indawo yomphezulu we-anode iyancipha ngexesha lokugcina, kwaye indawo ethile ye-anode ye-0, 181 kunye ne-575d yebhetri yi-3.42, 2.

97 kunye ne-1.84cm2 / g. Ummandla we-anode umphezulu we-anode unciphisa umsebenzi wokusabela kwe-electrochemical okwenzeka kumphezulu we-anode, okukhokelela ekwandeni kokumelana nokudluliselwa kwe-RCT kumphezulu we-anode / electrolyte.

Ikhiwane. I-5 ichazwe kwi-electrochemical impedance spectrum yebhetri ye-buckle. Ngexesha lokugcinwa kweqondo lokushisa eliphezulu, i-lithium state anode ikwimeko ephantsi, kwaye ukusabela kokunciphisa i-electrolyte kudla i-lithium ion esebenzayo, kwaye ekugqibeleni ivelise ityuwa ye-lithium ye-inorganic; ubushushu obuphezulu bongeze i-electrolysis Ireyithi yokusabela yokunciphisa ulwelo, eyenza isixa esikhulu se-lithium ion (Umfanekiso 6).

Ngapha koko, idiphozithi yemveliso ye-anode esebenzayo, ifilimu ye-SEI iyajiya, ibangele ukuwohloka kokusebenza kwekinetic ye-electrode. Umzobo 6, umatshini wokunciphisa umthamo wokugcina ubonisiwe. 3.

Ukusebenza kwebhetri ubushushu obuphezulu bokugcinwa kwebhetri Kuphuculwe ngenxa yokulahleka kwamandla kwibhetri ubushushu obuphezulu benkqubo yokugcina i-lithium ion ilahleko ebangelwa ziimpendulo ezisecaleni ukusuka kumphezulu we-anode, Ukusukela ngokongeza ifilimu ye-SEI i-thermal stabilizing additives (ASR) inokuphucula ukuzinza kobushushu obuphezulu befilimu ye-SEI, ukunciphisa i-reactivity yecala kumphezulu we-anode, ukunciphisa ilahleko ye-lithium ion esebenzayo. Umzobo 7 Iigophe ezahlukeneyo zokugcina ibhetri ye-electrolyte kunye ne-SEI membrane thermostability infrastructure yongeza i-1% ye-ASR inokuphucula ngokufanelekileyo ubomi bokugcina ukushisa kwebhetri. Emva kokongeza i-1% ye-ASR, i-575D yokugcinwa kwamandla inyuke ukusuka kwi-85.

8% ukuya kuma-87.5% [Umfanekiso 7 (a)]. I-DCR Rolling Rate iphantsi kakhulu kunesiseko se-electrolyte, kwaye umxholo we-anode e-soluble lithium-containing compound nawo uye wehla (Itheyibhile 3).

Uhlalutyo lwe-DSC lwenziwa kwi-100% ye-SOC yebhetri anode [Amakhiwane. 7 (b)], ukufunxa ubushushu kufikelela kwincopho engaphantsi kwe-100 ° C kwisinyibilikisi esishiyekileyo. Itheyibhile 3 Ngaphambi kokuba i-lithium e-soluble ye-100% ye-DOD ibhetri, i-lithium ene-anode yongezwa, kwaye i-anode 90 ° C iqala ukukhupha, echithwa kwi-anode surface SEI; Emva kokongeza i-ASR, iqondo lokushisa lokubola liyenyuka ukuya kwi-101 ° C.

Emva kokongeza i-ASR, ukuzinza kwe-thermal ye-SEI kuphuculwe kakhulu, kwaye ilahleko ye-lithium ion esebenzayo ingancitshiswa ngokufanelekileyo, kwaye ubomi bokugcina ibhetri bunokuphuculwa. Okwesithathu, isiphelo sokugqibela sihlalutya iipropati ze-electrochemical, i-polar physics kunye ne-electrochemical properties of commercialized phosphate ion ibhetri yokugcinwa kobushushu obuphezulu, kwaye yafumanisa ukuba ukulahleka kwamandla ebhetri kwindawo yokugcina ukushisa kubalulekile kwi-anode yokunciphisa i-electrolyte kwi-low potential. , Okubangela ukulahleka kwe-ion lithium esebenzayo.

Imveliso ye-sub-reactive ye-electrolyte yokunciphisa i-anode ifakwe kwi-anode, kwaye i-inorganic component kwi-deposit ithintela ukusabalalisa kwe-lithium ion, ukwenzela ukuba i-anode reaction kinetics iyancipha. Ngokongeza i-SEI membrane thermostability kwi-electrolyte ukuphucula ngokufanelekileyo ukuzinza kwe-thermal yefilimu ye-SEI, ukunciphisa ukusabela kokunciphisa i-electrolyte, ukunciphisa ukusetyenziswa kwe-lithium ion esebenzayo, kunye nokuphucula ubomi bokugcina ukushisa okuphezulu.