ESM: Nrụpụta nke ultra-conformal interface nke electrolyte perfluorinated maka batrị lithium dị elu bara uru.

Ndabere Nyocha

Na batrị lithium-ion, iji nweta ebumnobi nke 350 Wh Kg-1, ihe cathode na-eji nickel-rich layered oxide (LiNixMnyCozO2, x+y+z=1, nke a na-akpọ NMCxyz). Site na mmụba nke njupụta ume, ihe egwu ndị metụtara mgbapụ ọkụ nke LIB adọtala uche ndị mmadụ. Site n'echiche ihe onwunwe, electrodes bara ụba nke nickel nwere nsogbu nchekwa dị njọ. Na mgbakwunye, oxidation/crosstalk nke akụrụngwa batrị ndị ọzọ, dị ka mmiri mmiri na-adịghị mma na electrodes na-adịghị mma, nwekwara ike ịkpalite ịgba ọsọ thermal, nke a na-ewere na ọ bụ ihe kacha akpata nsogbu nchekwa. Nhazi n'ime ebe a na-achịkwa ihe nrụnye electrode-electrolyte kwụsiri ike bụ atụmatụ bụ isi maka ọgbọ na-abịa nke batrị lithium dabere na oke ume-njupụta. Kpọmkwem, a siri ike na ok cathode-electrolyte interphase (CEI) na elu thermal kwụsie ike inorganic components nwere ike dozie nsogbu nchekwa site na igbochi ntọhapụ nke oxygen. Ka ọ dị ugbu a, enweghi nyocha gbasara ihe ndị emezigharịrị CEI cathode yana nchekwa ọkwa batrị.

Ngosipụta mmezu

N'oge na-adịbeghị anya, Feng Xuning, Wang Li, na Ouyang Minggao nke Mahadum Tsinghua bipụtara akwụkwọ nyocha nke isiokwu ya bụ "In-Built Ultraconformal Interphases Enable High-Safety Practical Lithium Battery" na Energy Nchekwa Ihe. Onye ode akwụkwọ nyochara arụmọrụ nchekwa nke batrị NMC811/Gr dị nro zuru oke yana nkwụsi ike ọkụ nke electrode ziri ezi CEI kwekọrọ. A mụọla usoro mkpochapụ ọkụ dị n'etiti ngwa na batrị mkpọ dị nro. N'iji electrolyte perfluorinated na-adịghị ere ọkụ, akwadoro ụdị batrị zuru oke nke NMC811/Gr. A kwalitere nkwụsi ike nke okpomọkụ nke NMC811 site na ebe nchekwa CEI nwere oke na LiF inorganic. CEI nke LiF nwere ike belata ntọhapụ oxygen nke mgbanwe usoro a kpatara ma gbochie mmeghachi omume exothermic n'etiti NMC811 nwere obi ụtọ na electrolyte fluorinated.

Ntuziaka eserese

Ọgụgụ 1 Ntụle nke thermal runaway characters bara uru NMC811/Gr obere akpa ụdị batrị zuru ezu site na iji perfluorinated electrolyte na omenala electrolyte. Mgbe otu okirikiri nke omenala (a) EC/EMC na (b) perfluorinated FEC/FEMC/HFE electrolyte obere akpa ụdị zuru batrị. (c) Conventional EC/EMC electrolysis na (d) perfluorinated FEC/FEMC/HFE electrolyte obere akpa ụdị batrị zuru oke mgbe 100 okirikiri gachara.

Maka batrị NMC811/Gr nwere electrolyte ọdịnala mgbe otu okirikiri gachara (Njirimara 1a), T2 nọ na 202.5°C. T2 na-eme mgbe voltaji mepere emepe dara. Otú ọ dị, T2 nke batrị na-eji perfluorinated electrolyte ruru 220.2 ° C (Figure 1b), nke na-egosi na electrolyte perfluorinated nwere ike imeziwanye nchekwa okpomọkụ nke batrị ahụ ruo n'ókè ụfọdụ n'ihi nkwụsi ike ya dị elu. Ka batrị na-akawanye nká, uru T2 nke batrị electrolyte omenala na-adaba na 195.2 °C (Figure 1c). Otú ọ dị, usoro ịka nká anaghị emetụta T2 nke batrị site na iji electrolytes perfluorinated (Figure 1d). Tụkwasị na nke ahụ, uru dT/dt kachasị nke batrị na-eji electrolyte omenala n'oge TR dị elu dị ka 113 ° C s-1, ebe batrị na-eji electrolyte perfluorinated bụ naanị 32 ° C s-1. Ọdịiche dị na T2 nke batrị ịka nká nwere ike ịpụta na nkwụsi ike dị n'ime ya nke NMC811 na-atọ ụtọ, nke a na-ebelata n'okpuru electrolytes nkịtị, mana enwere ike idobe ya nke ọma n'okpuru electrolytes perfluorinated.

Ọgụgụ 2 Thermal nkwụsi ike nke delithiation NMC811 nti electrode na NMC811/Gr batrị ngwakọta. (A,b) Map contour nke C-NMC811 na F-NMC811 synchrotron nnukwu ike XRD na mgbanwe dị elu (003) kwekọrọ. (c) Omume ntọhapụ kpo oku na ikuku oxygen nke electrode dị mma nke C-NMC811 na F-NMC811. (d) Usoro DSC nke ngwakọta nlele nke electrode dị mma na-atọ ụtọ, electrode na-adịghị mma, na electrolyte.

Ọnụọgụ 2a na b na-egosi akụkụ HEXRD nke obi ụtọ NMC81 nwere ọkwa CEI dị iche iche na ọnụnọ nke electrolytes na-emekarị na n'oge oge site na ụlọ okpomọkụ ruo 600 ° C. Nsonaazụ na-egosi n'ụzọ doro anya na na ọnụnọ nke electrolyte, oyi akwa CEI siri ike na-eme ka nkwụsi ike nke okpomọkụ nke cathode na-etinye na lithium. Dị ka egosiri na eserese 2c, otu F-NMC811 gosipụtara ọnụ ọgụgụ kasị elu nke exothermic ji nwayọọ nwayọọ na 233.8 ° C, ebe C-NMC811 exothermic elu pụtara na 227.3 ° C. Tụkwasị na nke ahụ, ike na ọnụego nke ntọhapụ oxygen kpatara site na ntụgharị oge nke C-NMC811 dị njọ karịa nke F-NMC811, na-akwadokwa na CEI siri ike na-eme ka nkwụsi ike nke okpomọkụ nke F-NMC811 dịkwuo mma. Ọgụgụ 2d na-eme ule DSC na ngwakọta nke NMC811 nwere obi ụtọ yana ngwa batrị ndị ọzọ kwekọrọ. N'ihi na ot electrolytes, exothermic ọnụ ọgụgụ kasị elu nke samples na 1 na 100 cycles na-egosi na ịka nká nke omenala interface ga-ebelata thermal nkwụsi ike. N'ụzọ dị iche, maka electrolyte perfluorinated, ihe atụ mgbe usoro 1 na 100 gasịrị na-egosi ọnụ ọgụgụ dị elu nke exothermic sara mbara na nke dị nro, kwekọrọ na okpomọkụ TR na-akpata (T2). Nsonaazụ (Njirimara 1) na-agbanwe agbanwe, na-egosi na CEI siri ike nwere ike melite nkwụsi ike nke okpomọkụ nke ndị agadi na obi ụtọ NMC811 na ihe ndị ọzọ batrị.

Ọgụgụ 3 Njirimara nke NMC811 ezigbo electrode na-atọ ụtọ na electrolyte perfluorinated. (ab) Ihe onyonyo SEM-ngalaba nke ndị agadi F-NMC811 ezigbo electrode na eserese EDS kwekọrọ. (ch) Nkesa ihe. (ij) Onyinyo SEM-ngalaba nke agadi F-NMC811 nti electrode na mebere xy. (km) Nrụgharị nke usoro 3D FIB-SEM na nkesa oghere nke ihe F.

Iji gosi na nhazi nke fluorinated CEI nwere ike ịchịkwa, akụkụ nke akụkụ morphology na nkesa nke NMC811 dị mma electrode merelarị na batrị dị nro bụ FIB-SEM (Njirimara 3 ah). Na perfluorinated electrolyte, a edo fluorinated CEI oyi akwa na-etolite n'elu F-NMC811. N'ụzọ megidere nke ahụ, C-NMC811 na ot electrolyte enweghị F ma mepụta akwa CEI na-ezighi ezi. Ọdịnaya F nke dị na mpaghara obe nke F-NMC811 (Njirimara 3h) dị elu karịa nke C-NMC811, nke na-egosikwa na nguzobe nke mesophase inorganic fluorinated mesophase bụ isi ihe na-edobe nkwụsi ike nke NMC811 nwere obi ụtọ. . Site n'enyemaka nke FIB-SEM na maapụ EDS, dị ka egosiri na eserese 3m, ọ hụrụ ọtụtụ ihe F na ụdị 3D n'elu F-NMC811.

Ọgụgụ 4a) Nkesa omimi nke ihe n'elu nke mbụ na obi ụtọ NMC811 nti electrode. (ac) FIB-TOF-SIM na-agbasa nkesa nke F, O, na Li ọcha na electrode dị mma nke NMC811. (df) Ọdịdị elu elu na nkesa omimi nke F, O, na Li ọcha nke NMC811.

FIB-TOF-SEM gara n'ihu kpughee nkesa omimi nke ihe dị n'elu nke electrode dị mma nke NMC811 (Njirimara 4). E jiri ya tụnyere nke mbụ na nke C-NMC811, a hụrụ mmụba dị ukwuu na mgbaàmà F na elu elu elu nke F-NMC811 (Njirimara 4a). Tụkwasị na nke ahụ, akara ngosi O na elu Li na-adịghị ike n'elu na-egosi nhazi nke F- na Li-rich CEI layers (Figure 4b, c). Nsonaazụ ndị a niile kwadoro na F-NMC811 nwere akwa CEI nwere LiF. Tụnyere na CEI nke C-NMC811, CEI oyi akwa nke F-NMC811 nwere ihe F na Li ọcha. Na mgbakwunye, dị ka egosiri na FIGS. 4d-f, site n'echiche nke ion etching omimi, nhazi nke NMC811 mbụ siri ike karịa nke NMC811 nwere obi ụtọ. Omimi etch nke F-NMC811 merela agadi pere mpe karịa C-NMC811, nke pụtara na F-NMC811 nwere nkwụsi ike nhazi dị mma.

Ọgụgụ 5 CEI kemịkalụ kemịkalụ n'elu nke nti electrode nke NMC811. (a) XPS ụdịdị dị iche iche nke NMC811 nti electrode CEI. (bc) XPS C1s na F1s ụdịdị dị iche iche nke NMC811 ziri ezi electrode CEI mbụ na obi ụtọ. (d) Igwe microscope elektrọn na-ebufe Cryo: nkesa nke F-NMC811. (e) Onyonyo TEM jụrụ oyi nke CEI hibere na F-NMC81. (fg) onyonyo STEM-HAADF na STEM-ABF nke C-NMC811. (hi) onyonyo STEM-HAADF na STEM-ABF nke F-NMC811.

Ha jiri XPS kọwaa kemịkalụ kemịkalụ CEI na NMC811 (Njirimara 5). N'adịghị ka nke mbụ C-NMC811, CEI nke F-NMC811 nwere nnukwu F na Li mana obere C (ọgụgụ 5a). Mbelata nke ụdị C na-egosi na LiF-ọgaranya CEI nwere ike ichebe F-NMC811 site na ibelata mmeghachi omume akụkụ na-adịgide adịgide na electrolytes (Njirimara 5b). Na mgbakwunye, obere ego nke CO na C = O na-egosi na solvolysis nke F-NMC811 nwere oke. Na F1s ụdịdị dị iche iche nke XPS (Njirimara 5c), F-NMC811 gosipụtara akara ngosi LiF dị ike, na-akwado na CEI nwere nnukwu LiF sitere na ihe mgbaze fluorinated. Nkewa nke F, O, Ni, Co, na Mn ọcha na mpaghara mpaghara na akụkụ F-NMC811 na-egosi na a na-ekesa nkọwa ahụ n'otu n'otu n'ozuzu ya (Njirimara 5d). Onyonyo TEM dị ala dị na eserese 5e na-egosi na CEI nwere ike rụọ ọrụ dị ka oyi akwa mkpuchi iji kpuchie NMC811 nti electrode n'otu n'otu. N'ịkwado structural evolushọn nke interface, elu-n'akuku gbara ọchịchịrị-ubi scanning nnyefe eletrọn microscopy (HAADF-STEM na okirikiri na-egbuke egbuke-ubi scanning nnyefe eletrọn microscopy (ABF-STEM) nnwale e rụrụ maka carbonate electrolyte (C). -NMC811), N'elu nke na-ekesa nke ọma electrode enweela mgbanwe dị ukwuu na-agbanwe agbanwe, na a na-akwakọba usoro nnu nnu na-adịghị mma n'elu nke electrode dị mma (Ọnụ ọgụgụ 5f) maka electrolyte perfluorinated, elu nke F-NMC811. nti electrode na-edobe a layered Ọdịdị (Ọnụ ọgụgụ 5h), na-egosi na-emerụ Usoro na-aghọ nke ọma suppressed Na mgbakwunye, a edo CEI oyi akwa a hụrụ n'elu F-NMC811 (Ọgụgụ 5i-g) Ndị a pụta n'ihu gosi na uniformity nke CEI oyi akwa na nti electrode elu nke NMC811 na perfluorinated electrolyte.

Ọnụọgụ 6a) TOF-SIM ụdịdị dị iche iche nke oge interphase n'elu NMC811 nti electrode. (ac) Nyocha miri emi nke iberibe ion nke abụọ akọwapụtara na electrode dị mma nke NMC811. (df) TOF-SIMS ụdịdị kemịkalụ kemịkalụ nke abụọ ion iberibe mgbe 180 sekọnd nke sputtering na mbụ, C-NMC811 na F-NMC811.

A na-ewerekarị iberibe C2F dị ka ihe ndị dị ndụ nke CEI, na akụkụ LiF2 na PO2 na-ewerekarị dị ka ụdị inorganic. E nwetara akara ngosi LiF2- na PO2 nke ọma na nnwale ahụ (Njirimara 6a, b), na-egosi na oyi akwa CEI nke F-NMC811 nwere ọnụ ọgụgụ buru ibu nke ụdị inorganic. N'ụzọ megidere nke ahụ, C2F-signal nke F-NMC811 adịghị ike karịa nke C-NMC811 (Ọgụgụ 6c), nke pụtara na CEI oyi akwa nke F-NMC811 nwere obere emebi emebi organic ụdị. Nchoputa ndi ozo choputara (Nyocha 6d-f) na enwere otutu umu anumanu na CEI nke F-NMC811, ebe enwere umu inorganic di nta na C-NMC811. Nsonaazụ ndị a niile na-egosi nguzobe oyi akwa CEI bara ụba nke inorganic na electrolyte perfluorinated. E jiri ya tụnyere batrị NMC811/Gr soft-pack na-eji electrolyte ọdịnala, nkwalite nchekwa nke batrị dị nro site na iji electrolyte perfluorinated nwere ike ịsị na: Nke mbụ, nhazi n'ime ọnọdụ nke oyi akwa CEI bara ụba na LiF inorganic bara uru. Nkwụsi ike dị n'ime ya nke NMC811 ziri ezi electrode na-ebelata ntọhapụ nke oxygen lattice kpatara site na mgbanwe oge; Nke abuo, ihe siri ike inorganic CEI nchebe oyi akwa n'ihu na-egbochi ukwuu reactive delithiation NMC811 site na ịkpọtụrụ electrolyte, ibelata exothermic akụkụ mmeghachi omume; atọ, The perfluorinated electrolyte nwere elu thermal kwụsie ike na elu okpomọkụ.

Mmechi na Outlook

Ọrụ a kọrọ na mmepe nke ụdị akpa akpa Gr/NMC811 zuru oke na-eji electrolyte perfluorinated, nke mere ka arụmọrụ nchekwa ya dịkwuo mma. Nkwụsi ike ikuku dị n'ime. Ọmụmụ ihe omimi nke usoro mgbochi TR na njikọ dị n'etiti ihe na ọkwa batrị. Usoro ịka nká anaghị emetụta okpomọkụ TR na-akpalite (T2) nke batrị electrolyte perfluorinated n'oge oke ifufe ahụ dum, nke nwere uru doro anya karịa batrị ịka nká site na iji electrolyte omenala. Na mgbakwunye, ọnụ ọgụgụ dị elu nke exothermic kwekọrọ na nsonaazụ TR, na-egosi na CEI siri ike na-akwado nkwụsi ike nke okpomọkụ nke electrode dị mma na-enweghị lithium na ihe ndị ọzọ batrị. Nsonaazụ ndị a na-egosi na njikwa n'ime ọnọdụ nke oyi akwa CEI kwụsiri ike nwere mkpa nduzi dị mkpa maka ngwa bara uru nke batrị lithium dị elu dị nchebe.

Ozi akwụkwọ

Interphases Ultraconformal arụnyere arụnyere na-eme ka batrị lithium bara uru dị elu, ngwa nchekwa ike, 2021.