Rationally designing electrolyte additives for highly improving cyclability of LiNi_(0.5)Mn_(1.5)O_(4)/Graphite cells

High voltage is necessary for high energy lithium-ion batteries but difficult to achieve because of the highly deteriorated cyclability of the batteries.A novel strategy is developed to extend cyclability of a high voltage lithium-ion battery,LiNi_(0.5)Mn_(1.5)O_(4)/Graphite(LNMO/Graphite)cell,which emphasizes a rational design of an electrolyte additive that can effectively construct protective interphases on anode and cathode and highly eliminate the effect of hydrogen fluoride(HF).5-Trifluoromethylpyridine-trime thyl lithium borate(LTFMP-TMB),is synthesized,featuring with multi-functionalities.Its anion TFMPTMB-tends to be enriched on cathode and can be preferentially oxidized yielding TMB and radical TFMP-.Both TMB and radical TFMP can combine HF and thus eliminate the detrimental effect of HF on cathode,while the TMB dragged on cathode thus takes a preferential oxidation and constructs a protective cathode interphase.On the other hand,LTFMP-TMB is preferentially reduced on anode and constructs a protective anode interphase.Consequently,a small amount of LTFMP-TMB(0.2%)in 1.0 M LiPF6in EC/DEC/EMC(3/2/5,wt%)results in a highly improved cyclability of LNMO/Graphite cell,with the capacity retention enhanced from 52%to 80%after 150 cycles at 0.5 C between 3.5 and 4.8 V.The as-developed strategy provides a model of designing electrolyte additives for improving cyclability of high voltage batteries.

Synergistic interphase modification with dual electrolyte additives to boost cycle stability of high nickel cathode for all-climate battery

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.