有機硅電解液：安全性和高電壓性能研究進展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、SummaryOutlineSafety

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

OHighVoltageCathodeMaterialsDischargepotential(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(0<X<1,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

SolventsLiBOBLiODFBCNH

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

constant

(20-30,

55

for

SCN)Disadvantages:Poor

compatibility

with

graphitePoor

solubility

of

LiPF6

LiTFSI

(V>

4.3

V,

corrodes

collector)

LiBF4

(inferior

ability,

poor

lowtemperature

performance)J

Electrochem

Soc,

149

(2002)A920;

J

Phys

Chem

B,

115

(2011)

12120.Electrochem

Commun,

11

(2009)

1418;

11

(2009)

1073.

Sulfone-Based

Electrolytes

Advantages:

High

oxidation

potential

Low

flammable

High

melting

point;

Poor

compatibility

with

graphite;

Wetting

problem

with

separatorLi4Ti5O12/1M

LiPF6FEC/DMC/D2

3/4/3/LiNi0.5Mn1.5O4

(Data

from

ANL,

USA)

OFRf1Rf2OD2

OFEC1

C

at

55oCFluorinated

Based

ElectrolytesAdvantages:

High

oxidative

stability

High

flash

point/low

flammability

(Safe)

Compatible

with

graphite

ODisadvantages:

Bad

performance

at

elevated

temperatures

(FEC)

Harsh

synthesis

conditions/high

cost

1M

LiPF6

EC/DEC

(3/7)1M

LiPF6

EC/DMC/MFA

(3/3/4)

F

OH

C

C

O

CH3

F

MFA1M

LiPF6

MFALiCo2/

Graphite

cell

(1

Ah

cell);

Daikindata

(Japan)Fluorinated

Based

ElectrolytesEnergy

&

Environmental

Science,

6

(2013)

1806;

Electrochem

Commun,

10

(2008)

783.High

Low

flammability

High

oxidation

resistance

High

viscosity

(low

conductivity

&

ratecapability)

Poor

wettingHigh

costJ

Power

Sources,

189

(2009)

331;

225

(2013)

113;

233

(2013)

115.Mix

with

carbonate

or

other

co-solvent

performance

Ionic

Liquid

Electrolytesthermal

stabilityVerylowrotationbarrieraroundSi-Oaxis,(ca.0.8KJ/mol)lowlinearisationenergyoftheSi-O-Siangle(~1.3kJ/mol).Organosilicon(OS)Electrolytes:HighionicconductivityNon-flammability:BiocompatibleExcellentwettingcapabilityWideliquidphaserange(-40–200oC)Lowviscosity-comparablewithalkylcarbonatesMediumwideelectrochemicalwindowVerylowglasstransitiontemperaturegoodthermalstabilityAlternative:OrganosiliconElectrolytesOOOOOR2R2R1R1=H,CH3R2=CH3,CH3CH2CarbonateelectrolytesHighlyflammable!OJ.Mater.Chem.,2008,18(31),3713-17;2010,20,8224-26.Chem.Mater.,2007,19,5734-5741.Implantneuro-stimulatormicrocell(27.53.2mm2,1g)OrganosiliconasSafeElectrolytes1.Excellentcyclability；2.Electrochemicallystable3.Nonflammable/Safe;4.EnvironmentalbenignConventionalelectrolytesOSelectrolytesMCMB/LiNi0.8Co0.15Al0.05O2,0.8MLiBOBOSelectrolytesC/5,3.0to4.0V;100%efficiencyJPowerSources,228(2013)32;196(2011)2255ElectrochemCommun,8(2006)429;ChemCommun,49(2013)1190ProgressonOrganosiliconElectrolytes(Lit.)IonicconductivityCompatibilitywithgraphiteOxidationpotential(4.2V)ChallengesofOSelectrolytes:Compoundsη/cPεoT/Cg-σ/mScm1(0)25CE/VcathodicE/VanodicEW/VSN1SN2SN3BNSTNS2.884.627.163.604.6011.612.312.815.717.3-118-111-98.4-107-1061.101.521.201.281.030.00.00.01.111.055.6015.054.494.11NCH2CH2CH2CSiOCH2CH2OCH3nCNCH2CH2Si(CH3)(3-m)(OCH2CH2OCH3)mCH3dielectricconstantoxidationpotentialIncreaseddielectricconstantIncreasedoxidationpotentialHighconductivityOrganosiliconCompoundswithNitrileGroupCH3DischargeCapacity(mAh/g)Efficiency(%)Potenial/VSpecificCapacity/mAhg-1Specificcapacity/mAhg-1Capacityretention(%)Specificcapacity/mAhg01401201008060105100959085803000.7CCCto4.4V,0.5CDCto3.0V274cycles:85.2%LCO/OSco-solvent/Graphite50100150200250Cyclenumber016014012010080604020180LCO/graphite,2.7-4.4V,0.2CBNS/0.4MLiODFB+0.6MLiPF6TNS/0.4MLiODFB+0.6MLiPF6SN1/0.4MLiODFB+0.6MLiPF640801201600525300309060120180150101520Cyclenumber0204060100800.2C2C1.5C1C0.5C0.2CMisciblewellwithcarbonateEnhancedhighrateperformance01002003004005006000.01.02.0-11MLiPF6inSN11MLiPF6inBNS/PC(4:6invol.)1MLiPF6inTNSAsEOarmincrease,Morecompatibilitywithgraphite.OrganosiliconCompoundswithNitrileGroup3.0CyclenumberJ.PowerSources,254,29-32(2014)CoulombicEfficiency/%Specificcapacity/mAhg-102040608010008040160120Cyclenumber8081971009998Retention:90.4%@100cyclesCE>99.5%LCO/graphite,3.0-4.4V0.5C,143mAhg-1ComparisonwithCommercialHigh-VoltageElectrolytesOurhigh-voltageOSelectrolyte(OSIonicLiquids)101Comp.Viscosity（mPa.s）DielectricconstantTg(℃)Conductivity-1（mS.cm）Oxidationpotential(V)FMSEOM221.799.5-108.51.464.951SM322.14.44-1120.9?EnhancedphysicalpropertiesFluorinationFluorinatedOSCompoundswithOligo(EO)1S3M2,J.Mater.Chem.,2010,20,8224;F2MSEO2Munpublisheddata..-1dQ/dVCap.mAh/gSpecificcapacity/mAhgCoulombicefficiency/%Potential(Vvs.Li+/Li)F2MSEO2M/1MLiPF6+0.2MLiODFB0204060804016012080200240Cyclenumber4.4VLCO/Li,0.2C8010095908510090.8%95.8%4.5V0.00.40.5Graphite/Li,0.01-3.0V1MLiPF6PC:DMC:DEC:F2MSEO2M(28:35:35:2vol.)UnpublisheddataFluorinatedOSCompoundswithOligo(EO)Goodcompatibilitywith1020Cycle#3040320280graphite!400360Highvoltageperformances:LCO/Ccell,94cycles4.4V:96%capacityretention4.5V:90%capacityretentionSpecificcapacity(mAh/g)Current()Efficiency(%)Potential(Vvs.Li/Li)0204060801006080120100180160140200Cyclenumber040208060100LCO/TMOSC3GC/graphite2.7-4.4V,C/10HighlypolargroupDielectricconstantConcentrationofLi+-1012345+TMOSC3GCTEOSC3GCDSC3GCOOOOSiOOSiOSiOOOOWangJL,etal.,2013,tobesubmittedCarbonateFunctionalizedTrialkoxysilanes(RO)3Si(CH2)nOOOOR=CH3O,CH3CH2O;n=0,2,3ODielectricconstantashighas37.8!220Current/A3.03.54.04.55.05.56.0320240160800Voltage/Vvs.Li/Li+commericalcarbonateelectrolytecommericalcarbonateelectrolyte+30%SN1W.E.platinumC.E.lithiumR.E.lithiumScanrate:10mv/s(a)OSbasedelectrolytesfor4.4VLCO/graphitecellcommercialcarbonateelectrolyte:GT303(LB303)commercialcarbonateelectrolyte+30%SN1:GT303+30%SN1-1Specificcapacity/mAhg030609012015012010080commercialcarbonateelectrolytecommercialcarbonateelectrolyte+30%SN1LCO/graphite,3.0-4.4V@0.5CCyclenumbercommercialcarbonateelectrolyte:GT303+2%wt.VC+2%wt.PScommercialcarbonateelectrolyte+30%SN1:70%TC4.35+30%SN1,0.1MLiODFB+1MLiPF6,2%wt.VC+2%wt.PSOSbasedelectrolytesfor4.4VLCO/graphitecell(b)160140-1Specificcapacity/mAhg01020304050601000.2C0.5C0.7C1C1.5Ccommericalcarbonateelectrolytecommericalcarbonateelectrolyte+30%SN10.2C(c)160140120Cyclenumbercommercialcarbonateelectrolyte:GT303+2%wt.VC+2%wt.PScommercialcarbonateelectrolyte+30%SN1:70%TC4.35+30%SN1,0.1MLiODFB+1MLiPF6,2%wt.VC+2%wt.PSOSbasedelectrolytesfor4.4VLCO/graphitecellElectrochemicalwindowsImidazoliumILs:ca.4VTertraalkylammoniumILs:ca.6VR=(CH3)3SiCH2,(CH3)3CCH2A=N(CF3SO2)2,BF4J.Phys.Chem.B,109,21576(2005);111,4819(2007);111,4885(2007);Talanta,71,68(2007).N+NR-A+SiNNC4H9-PF6TertraalkylPhosphoniumILs:excellentthermalstabilityElectrochim.Acta,51,5567(2006)OrganosiliconBasedIonicLiquidsAdvantagesOverCarbonAnaloguesWeakeIntermolecularinteractionsLowerviscosityLowglasstransitiontemperatureHydrophobicX=N,P;n=1,3;R1=CH3,CH3CH2;R2=Alkyl,alkoxyA=BF4,PF6,TFSI,BOB,NCN2R2R2SiR2(CH2)nXR1(OCH2CH3)2-AOOOOOOOF3CSNSCF3OOTFSIBOOBOBAnionstructures:US2010029970A1;WO2009045609A1;CHNPat:CN201010265833.2OrganosiliconBasedIonicLiquidsMassRetaintion(%)Current()OSIonicLiquidSN1IL-TFSIAN1IL-TFSICETMA-TFSIσmS/cm1.354.291.10cp125.436.0-TdecoC362325329EanodicV0.000.651.30EcathodicV5.395.305.78NovelOrganosiliconBasedIonicLiquids0125634Potential(V)SN1IL-TFSIAN1IL-TFSICEN1IL-TFSI0100500600120100806040200SN1IL-TFSIAN1IL-TFSICEETMAIL-TFSI200300400oTemperature(C)Capacity(mAh/g)Capacity(mAh/g)Efficiency(%)Efficiency(%)003015012090601800102030405060708090Cycle2080604010005253003015012090601800.2C2C1.5C1C0.5C101520Cyclenumber0.2C020806040100120CellPerformancesforNovelOSIonicLiquidsLCO/Graphite,2.7-4.4V,0.2CSN1IL-TFSI:DMC=1:1byvol.210Capacity(mAh/g)Efficiency(%)Capacity(mAh/g)Efficiency(%)0102030405060708090100220200180160140120100806040200CycleNumber100806040200NMC-LIcell;CapacityRetention:96%(100cycle)SN1IL-TFSI-EMC-1-1024622020018016014012010080604020081012141618202224262830CycleNumber100806040200NMC/graphite(2.7-4.6V)SN1IL-TFSI-EMC-1-1CellPerformancesforNovelOSIonicLiquidsCoulombicefficiency/%Specificcapacity/mAhg-1051015202530350804020016012004020Cyclenumber28Graphite/NMC,2.7-4.5V,0.2C2%PS0.2MLiODFB0.8MLiPF6BNSBNSfor4.5Vgraphite/NMCcellProvidedbyYTQ1008060Specificcapacity/mAhg-1Efficiency(%)05101520250Cyclenumber(a)210180150120906030010080604020SN1IL-TFSIfor4.5and4.6Vgraphite/NMC2.7-4.6V2.7-4.5VGraphite/NMC@0.2CSN1IL-TFSI/EMC(1:1byvol.)Capacity/mAh140001200010000800060004000200000100200300400500600700E12A084-1668Cycle；83.53%EST:811Cycle；80%10AAE7365270PM3HSE)---11500mAhCommercializationofOSElectrolytesNMC/OSElectrolyte/CBattery(10Ah)NumberofCycleCharge:CC10Ato4.2V;CV4.2Vto3.5hror200mAcut-offatRTDischarge:10Ato2.75VatRT采測一1s采采集集一一個數數據據兩種種電電解解液液的的電電池池在在穿穿刺刺測測試試過過程程中溫溫升升趨趨勢勢和和最最高高溫溫度度均均沒沒有有明明顯顯差差異異，，即電電池池內內部部的的放放熱熱反反應應方方式式和和程程度度沒沒有有變化化，，但但有有機機硅硅電電解解液液能能有有效效抑抑制制易易燃燃成分分的的燃燃燒燒。。有機機硅硅電電解解液液與與商商業業電電解解液液三三元元動動力力電電池池（（10Ah)針刺刺安安全全性性對對比比有機機硅硅電電解解液液電電池池煙煙霧霧噴噴射射力力度度較較小小，，地地上上的的黑黑色色物物質質少少商業業電電解解液液電電池池煙煙霧霧噴噴射射力力度度較較大大，，地地上上的的黑黑色色物物質質多多，，部部分分電電池池會著著火火爆爆炸炸OSelectrolytebatteryPack(10.8V，100Ah)DemonstrationofOSBatteryPackApplication:SolarEnergyNavigationlightCollaboration：GDMaritimeSafetyAdministration(廣州州航航標標局局））Si@CcompositeCompatabilityofOSElectrolytewithSiAnodeDischargecapacity(mAh/g)Capacityretention(%)Columbicefficiency(%)ElectrolyteLB303LB303+FECLB303+BNSElectrode1stCE1streversiblecap.100thCE100threversiblecap.CapacityretentionSi77.1%270698.8%1365.0%Si@C79.7%105498.4%49546.9%Si86.4%308998.7%128841.7%Si@C84.2%107596.0%84178.2%Si86.1%334899.4%203560.8%Si@C82.0%113996.9%100388.1%Currentdensity:400mA/g02080100010008000700060005000400030002000Sianode(LB303)Sianode(LB303+FEC)Sianode(LB303+BNS)Si@Canode(LB303)Si@Canode(LB303+FEC)Si@Canode(LB303+BNS)4060Cyclenumber1008060020406080100100806040200120Sianode(LB303+BNS)Si@Canode(LB303)Si@Canode(LB303+FEC)Si@Canode(LB303+BNS)CyclenumberSianode(LB303)Sianode(LB303+FEC)Dischargecapacity(mAh/g)Dischargecapacity(mAh/g)Columbicefficiency(%)Columbicefficiency(%)Currentdensity:400mA/g68%capacityretention05010015020010000200040003000Si@C(LB303)Si@C(LB303+FEC)Si@C(LB303+BNS)200406010080LB303+BNSSi85.9%262199.7%1696CyclenumberCurrentdensity:600mA/gElectrolyteElectrode1stCE1streversiblecapacity200thCE200threversiblecapacity0502001000020003000400060005000Sianode(LB303+BNS)100150CyclenumberCurrentdensity:600mA/g6050708010090Si@CSi納米硅硅顆粒粒負極極材料料極片片在商商業電電解液液和使使用了了FEC添添加劑劑時，，極片片在首首次嵌嵌脫鋰后電電極出出現明明顯的的脫落落，在在使用用了有有機硅硅電解解質（（BNS））為添添加劑劑時，，極片片脫落現象象明顯顯改善善。與與裸硅硅負極極材料料相比比，經經過碳碳包覆覆后制制備出出的碳碳硅復復合材材料極極片在使使用商商業電電解液液時，，經過過嵌脫脫鋰后后有部部分剝剝落，，但情情況比比裸硅硅電極極已有有改善善。當使用用了FEC和BNS為添添加劑劑時有有明顯顯的改改善，，極片片并為為出現現類似似的剝剝落現現象。。Intensity(a.u.)Intensity(a.u.)Intensity(a.u.)Ramanshift(cm)Ramanshift(cm)Ramanshift(cm)RamandataRef:[1]Adv.Mater.2013,25,4498––4503[2]J.Non-Cryst.Solids2006,352,4101.1、BNS作為為添加加劑易易于在在Si表面面形成成含有有Si-O-Si的的SEI膜膜2、與與傳統統的SEI膜膜不同同，形形成的的這種種SEI膜膜可能有有一定定的脫脫嵌鋰鋰活性性(Li2Si2O5)3、在在脫鋰鋰后，，BNS作作為添添加劑劑時產產生的的SEI膜較其其它兩兩種電電解液液相比比能穩穩定存存在50010001500SiLB303LB303+FECLB303+BNS-1Delithiationat1.5V500100015002000Sibeforcycle50010001500Si-SistretchingLB303LB303+FECLB303+BNS-1Si-O-SibendinginLi2Si2O5-1Lithiationat0.01VSi-OstretchingvibrationSiIntensity(a.u.)Intensity(a.u.)Intensity(a.u.)Ramanshift(cm)Ramanshift(cm)Ramanshift(cm)500100015002000Si@CLB303LB303+FECLB303+BNSSi-O-SibendingLithiationat0.01VSi-OstretchingvibrationinLi2Si2O5-1500100015002000Si@CDelithiationat1.5VLB303LB303+FECLB303+BNSGbandDband-11、BNS作為為添加劑劑在Si@C表表面形成含有有Si-O-Si的SEI膜膜2、由于于有包覆覆碳層的的存在，，以FEC和和BNS作為添添加劑時時產生的的SEI膜膜都較穩穩Ref:[1]Adv.Mater.2013,25,4498–4503[2]J.Non-Cryst.Solids2006,352,4101.500100015002000Si@Canodebeforecycle-1AnodeSiSi@CElectrolyteLithiationDelithiationLithiationDelithiationLB3033.6%46.4%1.8%2.4%LB303+FEC5.5%26.8%4.8%6.3%LB303+BNS14.2%8.6%6.8%9.5%Intensity(a.u.)Intensity(a.u.)1.52.02.5LB303+BNS(Lithiation)LB303+BNS(Delithiation)LB303(Delithiation)KevOCLB303(Lithiation)FSiSianode0.51.02.02.5LB303+BNS(Delithiation)LB303+BNS(Lithiation)LB303(Delithiation)LB303(Lithiation)Si@CanodeSiFOC1.5Kev0.51.0Si元素含量量分析1、LB303和LB303+FEC:Si電極極在循環環后表面面硅含量量猛增，，SEI膜的破破壞硅的的裸露2、BNS作作為添加加劑時產產生的SEI膜膜中Si含量高高于LB303形成的的，證明明Si成成分參與與成膜3、在Si@C中碳層層的存在在對三種種電解液液來說都都有利形形成更加加穩定的的SEI膜Transmission(a.u.)Transmission(a.u.)Transmission(a.u.)5002500Delithiation100015002000Wavenumber(cm-1)LithiationLB303+FECSianode5002500DelithiationLithiationLB303Sianode100015002000Wavenumber(cm-1)*1、(LB303)870：：LiPF6峰的相對對強度明明顯減小小，說明明經過脫鋰鋰后SEI的分分解（Ref:J.Phy.Chem.C2011,28,965-976）2、(LB303+FEC)870：：LiPF61640,1450,1090,1810:為FEC分解產產物（Ref:Langmuir2011,28,965-976）5001000150020002500*SianodeLB303+BNSDelithiationLithiationWavenumber(cm-1)3、(LB303+BNS)870：：LiPF6峰的相對對強度減減小不明明顯，說說明經過生成的的SEI較為為穩定，對比比三種電解液液，1060處的Si-O-Si鍵明顯增強，，證實了SEI膜中的Si-O-Si成分，脫脫鋰后任然能夠穩穩定存在Transmission(a.u.)Transmission(a.u.)Transmission(a.u.)Si@Canode5002500LB303+FECLithiationDelithiationSi@Canode100015002000Wavenumber(cm-1)5001000150020002500DelithiationLithiationWavenumber(cm-1)5001000150020002500Si@CanodeLB303DelithiationLithiationWavenumber(cm-1)LB303+BNS1、SEI結構分析參考考Sianode2、與Si電極不同，由由于C的存在，形成成的SEI膜更加穩定(870：LiPF6峰的相對強度在脫鋰后后變化沒有Si電極那么么明顯）Sianode(Electrolyte:LB303)發生膨脹Lithiationat0.01V發生收縮開裂裂Delithiationat1.5V生成的SEI膜生成的SEI膜碎裂Sianode(Electrolyte:LB303+10%BNS)較小膨脹Lithiationat0.01V并未發生收縮縮開裂Delithiationat1.5V生成的SEI膜生成的SEI膜穩定存在Si@Canode(Electrolyte:LB303)發生一定的膨膨脹Lithiationat0.01V發生收縮Delithiationat1.5V生成的SEI膜生成的SEI膜有些消失但但是跟裸硅電極相比還還是更加穩定定的，由于有碳層的存存在Si@Canode(Electrolyte:LB303+10%BNS)較小的膨脹Lithiationat0.01V發生一定的收收縮Delithiationat1.5V生成的SEI膜生成的穩定定的SEI膜-Z''()-Z''()-Z''()050100150200250300300250200150100500Z'()02004006008001000120014002001000300400600500LB303Sianode(berforecycle)Sianode(afterLithiation)Sianode(afterDelithiation)Z'()LB303+BNSSianode(berforecycle)Sianode(afterDelithiation)Sianode(afterLithiation)01002003004005006001000200300500400LB303+FECSianode(berforecycle)Sianode(afterLithiation)Sianode(afterDelithiation)Z'()對Si電極極用三種不不同的電解解液時嵌脫脫鋰及形成SEI膜的過過程研究，，與上面的的其他表征結果果一致，使使用LB303+BNS時在嵌脫鋰前前后形成的的SEM在在脫鋰過程程后依然穩定存存在，且這這種這種穩穩定的Si-O-SiSEI膜有有利于Li的脫嵌，，表現在EIS圖中中就是具有有較小的阻阻抗（與上上面其它的表征征結果相一一致）。-Z''()-Z''()-Z''()0306090120150180LB303+BNSafterDelithiationafterLithiationberforecycleZ'()02040100120140afterLithiationafterDelithiationberforecycleLB303+FECSi@Canode6080Z'()0100Si@Canode5000200100400300500afterDelithiationberforecycleafterLithiationLB303Si@Canode200300400Z'()與硅負極分分析類似Organosiliconbasedelectrolytesarestableelectrochemically,lessflammablethanorganiccarbonates,andshowexcellentelectrochemicalperformanceassafeelectrolytesforhigh-voltageLi-ionbatteries(4.4V-4.6V).OrganosiliconbasedelectrolytesexhibitsuperiorperformanceswithSi-basedanodes,eitherasadditives(betterthanFEC)orasco-solvents.SummaryAcknowledgement&Collaboration:HundredTalentsProgram(CAS)NationalNaturalScienceFoundationofChinaAmperexTechnologyLimited(ATL)GuangzhouLithiumForceCo.GrinnellCollege(IA,USA)UniversityofWisconsin-Madison(WI,USA)9、靜靜夜夜四四無無鄰鄰，，荒荒居居舊舊業業貧貧。。。。12月月-2212月月-22Wednesday,December28,202210、雨中黃葉樹樹，燈下白頭頭人。。20:50:1920:50:1920:5012/28/20228:50:19PM11、以以我我獨獨沈沈久久，，愧愧君君相相見見頻頻。。。。12月月-2220:50:1920:50Dec-2228-Dec-2212、故故人人江江海海別別，，幾幾度度隔隔山山川川。。。。20:50:1920:50:1920:50Wednesday,December