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安全性和高电压性能研究进展
1、Background? Safety issues related with Li-ion Batteries? Safe electrolytes for high-voltage batteries2、Organosilicon based electrolytes? High-voltage OS-based electrolytes? OS-based electrolytes for Si anodes4、SummaryOutline
Safety issues of LIBs:High flammability ofcarbonate electrolytes!LiFePO4 batteryNot safe enough!Safety of Lithium-Ion Batteries Safety (abuse tolerance): ? When overcharged, thermal runaway leads to fires etc. ? Runaway reaction caused by release of oxygen from cathode materials (e.g., LiCoO2).The development of newSafe electrolyte materials!OOORRDMC: R=CH3DEC: R=CH2CH3OOEC O
HighVoltageCathodeMaterialsDischargepotential(V)RedoxcoupleTheoreticalCapacity(mAh/g)PotentialRange(V)LiCoPo44.82+/3+Co1673.0–5.1LiNiPo4~5.12+/3+Ni1673.0–5.5Li3V2(PO4)3LiMPO43.83+/4+/5+V1973.0–4.8Li2CoP2O74.92+/3+Cob1092.0–5.5Li2MnP2O74.452+/3+Mnb1102.0–4.7Li2NiPO4F~5.12+/3+Nib1433.0–5.5LiNiSO4FC5.2–5.42+/3+Ni149—Li2NiSiO4LiNiMnC4.8O42+/3+Nib163—1.5LiNi0.5Mn1.5O44.72+/3+/4+Ni1473.5–5.0LiFe0.5Mn1.5O44.53+/4+3+/4+Fe,Mn1483.0–5.3xLi2MnO3·(1-x)LiMeO2(0X1,Me=Ni,Co,Mn)3.52+/3+/4+3+/4Ni,Co3+/4+Mnd~3142.0–4.8Es= Qcapacity * Vvoltage1. Safety!2. High-voltage Stability!J. Power Sources, 237 (2013) 229.High-voltage cathodes require compatible electrolytes Electrolyte Challenges:
NSAdditivesDinitrilesIonic liquidsSulfoneFluorinated solventInorganic compoundsSulfonateesters CarboxylanhydridesPhosphidesCCNNnO FC OOO OO CF3 FFCF3R4N+R2 O CF R1 OF R1 N+ R2 O - CF F F R1N+ R2 R3 O S FOO SSOOOOS OOOOSOOOO SOOSOCF3CF3F3CF3CF3CCF3O POO OO O BOOO OOLiBOOOOFFLiElectrolyte solvents and additives for high-voltage SolventsLiBOBLiODFB
CNH H Cn C N LiNi0.5Mn1.5O4/Li, 3.5-4.9V, 1/12 CJ Electrochem Soc, 156 (2009)A60.; 159 (2012)A370;160 (2013)A838. J Power Sources, 189 (2009) 576.Aprotic aliphatic dinitrile solvents n=3ADN, n=5 PMN n=6 SUN, n=8 SEN Advantages: Electrochemical window (7-8V) Flash point (110 ℃, 163 ℃ forADN) Dielectric constan
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