固态电解质理论配方设计与实验

Adesignermaterialsapproach

forsolidbatterymaterials:theoryvs.experiments

Dr/ProfGuoshengShao

StateCentreforInternationalCooperationonDesignerLow-carbon&

EnvironmentalMaterials(CDLCEM)低碳环保材料智能设计国际联合实验室

ZhengzhouUniversity郑州大学

ZhengzhouMaterialsGenomeInstitute(ZMGI)

--KeyInnovationOrganizationofHenanProvince

Safetyisagreatconcernformetalionbatteries

•Everincreasingdemandsofmetalionbatteriestosustainalow-carbonworld

•Fireaccidentsinvolvingnumerouslargescalebatterysystemsandelectricalvehicles

•HigherenergybatterieswithhigherVOCandenergydensitiesareevenlesssafe

•Solidelectrolytesarerecognizedtobefundamentallypromising

Necessarytobeabletoformulatenewmaterialsmoreefficientlyatloweredcosts:sustainableresources,greenandcheapmatter.

MSUP-adesignerapproach

•configurations(shape,size,interface/surface)

Need

•properties(mechanical,physical,chemical)

•functionalities(electronic,photonic,magnetic,biological,catalytic…)

系统试验-》可靠表征--》理论演绎

Tosee

Tom

Theory

MSUP

ake

Tounderstand

Data

Experiment

Materialsscience

•compositions

•microstructures

Topredict

•properties/functionalities

理论先行-》实验验证--》工艺优化

DFTbasisfordesigningbatterymaterials

ApproximationsforDFTonlyhiddeninXCfunctionals

Localfunctionals(LDA,GGA)largelydependabletostructure-energypropertiesatthegroundstate(zerokelvin,crystallinephases),e.g.PBEdescriptionofGGA

Entropy(vibrational)fordynamicallystablephasesdeterminedbygroundstatebinding

Electrochemicalpropertiesdictatedbycohesiveenergy(bindingenergyfromfreeatomsinlargevacuum).Thermalcontributionforbatterymaterialsrathertrivial

(energyformeltingonlyaround10%ofthecohesiveenergy)

A→B=一1/z.{EtotalLix+ΔxΠ一EtotalLixΠ/Δx一EtotalLi}

ReasonablyacceptablehybridXCavailableforbandstructures,e.g.HSE06,albeitbeingawareofnoubiquitousnon-localformalism(Asanextremecase,noneof

anyoneofthenon-localsiscapabletocopewithcopperoxidesCuO,Cu2O!)

IntegratedDFTMaterialsGenomeApproach

forsolidbatterymaterials

1.Cubicargyroditehali-chalcogenidesLi6PA5I

Globalsearchforstablestructures:energeticanddynamicalstabilities

(a)Li6PS5I,(b)Li6PSe5I,(c)Li6PTe5I,(d)Li6PSO4I,(e)Li6PSeS4I,and(f)Li6PTeS4I

(a)Li6PS5I,(b)Li6PSe5I,(c)Li6PTe5I,(d)Li6PSO4I,(e)Li6PSeS4I,(f)Li6PTeS4I,(g)Li6PS5Cl,(h)Li6PTeS4Cl,and(i)Li6PTe5Cl.

TuningAlloyingforsuperbionicconductivity:

TeforS,ClforI,excessLi@charge-neutrality

Li6PS5ClLi6PTe5Cl

Li6PS4TeCl

J.Mater.Chem.A,2017,5,21846-21857

Experimentalrealization

σ=D=D0exp(−)=exp(−

J.Mater.Chem.A,2018,6,19231-19240

Latticesoftening–superbionicconductivity

--“Grainboundaryresistance”conceptquestionable

Gradedelectrolytebufferstoavoidinterfacialreactions

xnLi6PS5-xOxCl

Li6PO5Cl|Li0.25MnO2interfacialstructures(a)beforeand(b)afterAIMD

calculation.(c)Li+diffusionpathacrosstheLi6PO5Cl|Li0.25MnO2interface(90psat400K).

JMaterChemA2019,7,5239-5247

StableLCO@LiNbO3|Li6.25PS5.25Cl0.75|Licell

JEnergyChemistry53(2021)147–154

PartialOforS:morestableSSE

EEM2022Onestonefortwobirds:goodSSEwithoutneedofcoatingforLCO!Remarkable

electrochemicaladvantageoverLGPS.GreatcommercialinterestinpracticalexploitationacrossChina-Japan.

2.Anti-perovskitetodouble-anti-perovskite

!!

Electricinsulating,superblyionicconducting

(a)Li+vacancydiffusivepathway

(b)interstitialchannelinadumbbellpathway

AIMD:Ea=0.18eV,Li+conductivity(300K)=12.5mS/cm

Thematerialshavebeenmade

J.Mater.Chem.A,2018,6,73-83ACSAppl.EnergyMater.2019,2,6288-6294

3.Na6SOI2doubleanti-perovskite

Na+conductivity(mS/cm):10.36(300K),1.79(223K)

Activation0.16eV

J.Mater.Chem.A,2018,6,19843-19852

4.Whatifseparatedinto2Dlayers?

DiscoveryofRuddlesden-Poppertypeanti-perovskite(ARP)

Identifiedfirststablehali-chalcogenideNa4OSI2

basedalloys

withrespecttostableconstituentphases

Na+/Li+DualIonalloyingeffect

Na4-x)LixS0.5O0.5I2(0≤x≤1)

Na3LiS0.5O0.5I265correspondingtominimalenergy!

BestandstableNa+conductorsidentified

6.3(300K)1.31(223K)mS/cm

Na31S4O4I16vs.Na23Li8S4O4I16

OnesystemforbothcathodeandSE:Lowlattice

mismatch&widevoltagerange

Fullcellwithcompatiblephasesinthesamesystem

StablematerialssystemMechanicallycompatible

Theoreticalenergydensitylimitover900Wh/kg

Reversibleenergydensity320Wh/kg

J.Mater.Chem.A,2019,7,10483-10493

5.Na3AO4X(A=S/Se,X=F/Cl)ascompletelystableSE

•Anti-perovskiteNa3SO4Clmetastable

Doubleanti-perovskite

Na3SeO4F0.5Cl0.5:

Na6Xoctahedrons

(S,Se)O4atbody-centres

•Doubleanti-perovskitewithalternatingNa6ClandNa6Funits

completestability

Insensitivetowateroroxygen

Na+conductivityinNa3SeO4F0.5Cl0.5,:8.167mS/cmat300Kand1.31mS/cmat223K;

activationbarrieronly0.137eV

O2-

H+

AIMDsimulationtorevealinteractionofoxygenandwater,showingtrajectoriesofO2-andH+nextto(a,d)

Na3SO4F0.5Cl0.5,(b,e)Na3SO4Cland(c,f)Na3SeO4F0.5Cl0.5overasimulationtimeof180psat300K.

J.Mater.Chem.A,2019,7,21985-21996

6.Li+encagedsystems:Voc>4V;compatablewithLi-anode

J.Mater.Chem.A,2021,9,14969-14976.

Optimal

IonConductivity(mS/cm)

Ea(eV)

Li2.125Y0.625Cl4

6.11

0.247

Li2.5Y0.5Cl4

8.42

0.244

Li3AlCl6

with1/80Li/Clvac

8.98

0.242

LiZnCl3

7.524

0.237

Li3AlCl6

LiZnCl3

(a)Li6MX8(M=Co,Cu,Fe,Mg,Mn),Li6NiCl8;(b)Li6TiX8;(c)Li4MX6(M=Fe,Mn,Ti);(d)Li3AlCl6,Li3FeX6;(e)Li2TiX4,Li2MnBr4,Li2CoCl4,Li2MgBr4;(f)Li2CuX4,(g)Li2CoBr4;(h)Li2MgCl4,Li2MnCl4,Li2FeX4;(i)LiFeX4;(j)LiNiX3;(k)LiCuX3;(l)LiTiCl3;(m)LiZnCl3

J.Mater.Chem.A,2021,9,25585-25594.

7.Anode-cathodeforSIBs

•IntercalationofNa+continuouslytoMXeneTi2CO(upto10

layers)

•Cathodeandanodebasedonsamesystem：highcapacity,wideVwindow,flexible

J.Mater.Chem.A2020,8,11177-11187

8.ProtectivecoatingtoLianode

•Li-halides:highoxidation

potentialbutveryinsulatingtoLi+

•Li-nitrides:goodLi+conductor,butverylowoxidationpotentialabout0.5V

•IdentifiedLi6NCl3asstable

compound,withbothhigh

oxidationpotentialandhighionicconductivity

Phys.Chem.Chem.Phys.,2020,22,12918-12928

Relatedexperimentalproofinprinciple:Wangetal.AdvMater2020,200274.(LiF-Li3N)

Publications

1.ZhuoWangandG.Shao,J.Mater.Chem.A,2017,5,21846-21857.

2.Z.Wang,HongjieXu,M.XuanandG.Shao,J.Mater.Chem.A,2018,6,73-83.

3.Z.WangandG.Shao,J.Mater.Chem.A,2018,6,6830-6839.

4.MinjieXuan,WeidongXiao,H.Xu,Y.Shen,ZhenzhenLi,ShijieZhang,Z.WangandG.Shao,J.Mater.Chem.A,2018,6,19231-19240.

5.YuranYu,Z.WangandG.Shao,JMater.Chem.A,2018,6,19843-19852.

6.H.Xu,Y.Yu,Z.WangandG.Shao,J.Mater.Chem.A,2019,7,5239-5247.

7.H.Xu,Y.Yu,Z.WangandG.Shao,EnergyEnviron.Mater.,2019,2,234-250.

8.Y.Yu,Z.WangandG.Shao,J.Mater.Chem.A,2019,7,21985-21996.

9.Y.Yu,Z.WangandG.Shao,J.Mater.Chem.A,2019,7,104