Although high salt concentration electrolyte(HCE)can construct effective Li F-rich interphase film and solve the interphasial instability issue of graphite anode,its high cost,high viscosity and poor wettability with ...Although high salt concentration electrolyte(HCE)can construct effective Li F-rich interphase film and solve the interphasial instability issue of graphite anode,its high cost,high viscosity and poor wettability with electrode materials limit its large-scale application.Generally,localized high concentration electrolyte(LHCE)is obtained by introducing an electrochemically inert diluent into HCE to avoid the above-mentioned problems while maintaining the high interphasial stability of HCE with graphite anode.Unlike traditional inert diluents,1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluropropyl ether(TTE)with electrochemical activity is introduced into propylene carbonate(PC)-based HCE to obtain LHCE-2(1 M LiPF_(6),PC:DMC:TTE=1:1:6.1)herein.Experimental and theoretical simulation results show that TTE participates in the oxidation decomposition and film-forming reaction at the NCM622 cathode surface,conducting a cathode electrolyte interphase(CEI)rich in organic fluorides with excellent electron insulation ability,high structural stability and low interphasial impedance.Thanks to the outstanding interphasial properties induced by LHCE-2,the graphite||NMC622 pouch cell reaches a capacity retention of 80%after 500 cycles at 1 C under room temperature.While at sub-zero temperatures,the capacity released by the cell with LHCE-2 electrolyte is significantly higher than that of HCE and conventional EC-based electrolytes.Meanwhile,the LHCE-2 electrolyte inherits the advantages of TTE flame-resistant,thus improving the safety of the battery.展开更多
B-containing electrolyte additives are widely used to enhance the cycle performance at low temperature and the rate capability of lithium-ion batteries by constructing an efficient cathode electrolyte interphase(CEI)t...B-containing electrolyte additives are widely used to enhance the cycle performance at low temperature and the rate capability of lithium-ion batteries by constructing an efficient cathode electrolyte interphase(CEI)to facilitate the rapid Li+migration.Nevertheless,its wide-temperature application has been limited by the instability of B-derived CEI layer at high temperature.Herein,dual electrolyte additives,consisting of lithium tetraborate(Li_(2)TB)and 2,4-difluorobiphenyl(FBP),are proposed to boost the widetemperature performances of LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM)cathode.Theoretical calculation and electrochemical performances analyses indicate that Li_(2)TB and FBP undergo successive decomposition to form a unique dual-layer CEI.FBP acts as a synergistic filming additive to Li_(2)TB,enhancing the hightemperature performance of NCM cathode while preserving the excellent low-temperature cycle stability and the superior rate capability conferred by Li_(2)TB additive.Therefore,the capacity retention of NCM‖Li cells using optimal FBP-Li_(2)TB dual electrolyte additives increases to 100%after 200 cycles at-10℃,99%after 200 cycles at 25℃,and 83%after 100 cycles at 55℃,respectively,much superior to that of base electrolyte(63%/69%/45%).More surprisingly,galvanostatic c ha rge/discharge experiments at different temperatures reveal that NCM‖Li cells using FBP-Li_(2)TB additives can operate at temperatures ranging from-40℃to 60℃.This synergistic interphase modification utilizing dual electrolyte additives to construct a unique dual-layer CEI adaptive to a wide temperature range,provides valuable insights to the practical applications of NCM cathodes for all-climate batteries.展开更多
基金supported by the National Natural Science Foundation of China (No.21972049)the Guangdong-Hong KongMacao Greater Bay Area Exchange Programs of SCNU (2022)。
文摘Although high salt concentration electrolyte(HCE)can construct effective Li F-rich interphase film and solve the interphasial instability issue of graphite anode,its high cost,high viscosity and poor wettability with electrode materials limit its large-scale application.Generally,localized high concentration electrolyte(LHCE)is obtained by introducing an electrochemically inert diluent into HCE to avoid the above-mentioned problems while maintaining the high interphasial stability of HCE with graphite anode.Unlike traditional inert diluents,1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluropropyl ether(TTE)with electrochemical activity is introduced into propylene carbonate(PC)-based HCE to obtain LHCE-2(1 M LiPF_(6),PC:DMC:TTE=1:1:6.1)herein.Experimental and theoretical simulation results show that TTE participates in the oxidation decomposition and film-forming reaction at the NCM622 cathode surface,conducting a cathode electrolyte interphase(CEI)rich in organic fluorides with excellent electron insulation ability,high structural stability and low interphasial impedance.Thanks to the outstanding interphasial properties induced by LHCE-2,the graphite||NMC622 pouch cell reaches a capacity retention of 80%after 500 cycles at 1 C under room temperature.While at sub-zero temperatures,the capacity released by the cell with LHCE-2 electrolyte is significantly higher than that of HCE and conventional EC-based electrolytes.Meanwhile,the LHCE-2 electrolyte inherits the advantages of TTE flame-resistant,thus improving the safety of the battery.
基金supported by the National Natural Science Foundation of China(No.21972049)。
文摘B-containing electrolyte additives are widely used to enhance the cycle performance at low temperature and the rate capability of lithium-ion batteries by constructing an efficient cathode electrolyte interphase(CEI)to facilitate the rapid Li+migration.Nevertheless,its wide-temperature application has been limited by the instability of B-derived CEI layer at high temperature.Herein,dual electrolyte additives,consisting of lithium tetraborate(Li_(2)TB)and 2,4-difluorobiphenyl(FBP),are proposed to boost the widetemperature performances of LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM)cathode.Theoretical calculation and electrochemical performances analyses indicate that Li_(2)TB and FBP undergo successive decomposition to form a unique dual-layer CEI.FBP acts as a synergistic filming additive to Li_(2)TB,enhancing the hightemperature performance of NCM cathode while preserving the excellent low-temperature cycle stability and the superior rate capability conferred by Li_(2)TB additive.Therefore,the capacity retention of NCM‖Li cells using optimal FBP-Li_(2)TB dual electrolyte additives increases to 100%after 200 cycles at-10℃,99%after 200 cycles at 25℃,and 83%after 100 cycles at 55℃,respectively,much superior to that of base electrolyte(63%/69%/45%).More surprisingly,galvanostatic c ha rge/discharge experiments at different temperatures reveal that NCM‖Li cells using FBP-Li_(2)TB additives can operate at temperatures ranging from-40℃to 60℃.This synergistic interphase modification utilizing dual electrolyte additives to construct a unique dual-layer CEI adaptive to a wide temperature range,provides valuable insights to the practical applications of NCM cathodes for all-climate batteries.