The electrochemical stability of room-temperature ionic liquids (RTILs) is a critical design consideration for electrochemical applications. An electrochemical solvent, such as the electrolyte in a lithium-ion battery or supercapacitor, must support the voltage in which the device operates. In this talk, we present the insights into the electrochemical stability of RTILs obtained using a novel combination of first principles density functional theory calculations and classical molecular dynamics simulations. We show that while simple gas phase models can be used to reveal broad qualitative trends in electrochemical stability, quantitative accuracy can be achieved only by explicitly modeling all inter-ion interactions in the liquid. Additionally, detailed investigations into the six room-temperature ionic liquids (ILs) formed from a combination of two common cations, 1-butyl-3-methylimidazolium (BMIM) and N ,N -propylmethylpyrrolidinium (P13), and three common anions, PF6 , BF4 , and bis(trifl uoromethylsulfonyl)imide (TFSI) provide surprising evidence of possible cation anodic instability, particularly in BMIM-based ILs.
Insights into the electrochemical stability of ionic liquids from first principles calculations and molecular dynamics simulations
1. Insights into the
electrochemical stability of ionic
liquids from first principles
calculations and molecular
dynamics simulations
Shyue Ping Ong, Oliviero Andreussi,Yabi Wu, Nicola
Marzari, and Gerbrand Ceder
Aug 14 2014
ACS 248th National Meeting
2. Electrochemical applications of ILs
Aug 14 2014 ACS 248th National Meeting
High Thermal
Stability, Low
Volatility, Low
Flammability
Wide
Electrochemical
Window
(~5-6V)
Abundance of
Charge Carriers
Highly
Customizable
3. Outline
Optimization of
IL ions with
Isolated-atom
Quantum
Chemistry
Calculations
Accurate
Electrochemical
Windows with
Molecular
Dynamics and
DFT
High-throughputtrends
DetailedInsights
Aug 14 2014 ACS 248th National Meeting
4. ElectrochemicalWindows of ILs
Aug 14 2014 ACS 248th National Meeting
ECL
(Cathodic Limit)
EAL
(Anodic Limit)
EW = EAL – ECL
Potential (V) vs Reference
Currentdensity
Ohno, H., (2005),
Electrochemical Aspects of Ionic
Liquids,Wiley-Interscience.
Same cation, different
anion, slightly different
ECL
Different cations,
same anion, very
different ECL
Different anions,
similar cation,
very different
EAL
5. Large Space of Ion Structures
Functional Groups
Base Ions
Aug 14 2014 ACS 248th National Meeting
7. Proxy Measures forTrue Redox Stability
Hypothesis:Vred &Vox correlated
with electron affinity (EA) and
ionization energy (IE) respectively
EAs and IEs can be computed efficiently and
accurately using simple computational
methods at relatively low cost
Aug 14 2014 ACS 248th National Meeting
Koch,V. R.; Dominey, L.A.; Nanjundiah, C.; Ondrechen, M. J.
J. Electrochem. Soc.1996, 143, 798–803.
€
Iq
+ e →
−EA
Iq−1
Iq
− e→
IE
Iq+1
8. Ohno, H. (2005), Electrochemical Aspects of Ionic Liquids,Wiley-Interscience.
Relative Redox Stability of CationTypes
Aug 14 2014 ACS 248th National Meeting
S. P. Ong and G. Ceder, 2010. Investigation of the Effect of Functional Group Substitutions on the Gas-Phase
Electron Affinities and Ionization Energies of Room-Temperature Ionic Liquids Ions using Density Functional
Theory. Electrochimica Acta, 55(11), pp.3804-3811.
9. Effect ofAlkylation on Cations
Appetecchi, G. B.; Montanino, M.; Zane, D.; Carewska, M.;
Alessandrini, F. & Passerini, S. (2009), ELECTROCHIMICA ACTA
54(4), 1325-1332.
PYR1n3 -> PYR1n7 :
−3.73V -> −3.89V
Aug 14 2014 ACS 248th National Meeting
10. Effect of Fluoroalkylation onAnions
No monotonic decreasing
trend in IE with
fluoroalkylation observed
Fluorine is the most
electronegative element =>
great inductive stabilization
effect
Initial substitution do not
result in significantly
increased stabilization.
Relative oxidative stability of
common anions agrees with
recent work by Ue et al.
• PF6 > BF4 > TFSI
Aug 14 2014 ACS 248th National Meeting
0 100 200 300 400
6.2
6.4
6.6
6.8
7
7.2
7.4
7.6
7.8
8
Molecular Weight / mol gm
−1
VerticalIP/eV
Borate
Sulfonylimide
Phosphate
TFSI
BF4
PF
6
PF(CF
3
)
5
B(CF3
)3
(CF(CF3
)2
)
11. Func.Group Substitutions on
1,2,3-trimethylimidazolium
Aug 14 2014 ACS 248th National Meeting
EW
by
Ind.
EW
by
Res.
EW
by
Ind.
ED
by
Res.
ED
by
Ind.
EW
by
Ind.
ED
by
Res.
12. Effect of substitution position
ED
Resonance
Effect
Dominates
Over EW
Inductive
Effect
EW
Inductive
Effect
Dominates
Over ED
Resonance
Effect
Aug 14 2014 ACS 248th National Meeting
14. Designing ILs for electrochemical applications
Electron-donating functional groups stabilize cations
and electro-withdrawing groups stabilize anions
• Unfortunately, scope for increase in anodic limits appear to be limited
given that current anions seems to be near optimal.
Effect due to combination of inductive and resonance
effects, relative strength of which depends on
substitution position
Efficient computational methods can be used to
quickly screen candidate IL structures to maximize
electrochemical windows
Aug 14 2014 ACS 248th National Meeting
15. Outline
Optimization of
IL ions with
Isolated-atom
Quantum
Chemistry
Calculations
Accurate
Electrochemical
Windows with
Molecular
Dynamics and
DFT
High-throughputtrends
DetailedInsights
Aug 14 2014 ACS 248th National Meeting
16. ElectrochemicalWindows of ILs
Aug 14 2014 ACS 248th National Meeting
ECL
(Cathodic Limit)
EAL
(Anodic Limit)
EW = EAL – ECL
Potential (V) vs Reference
Currentdensity
Ohno, H., (2005),
Electrochemical Aspects of Ionic
Liquids,Wiley-Interscience.
Same cation, different
anion, slightly different
ECL
Different cations,
same anion, very
different ECL
Different anions,
similar cation,
very different
EAL
Same EMI cation,
different anions,
similar EAL!
17. Electrochemistry ofTFSI at negative potentials
TFSI anion
decomposes at less
negative potentials
than P13 cation.
Polarizable Continuum
Model (PCM)
calculations showed
similar qualitative
results, but unable to
provide quantitative
accuracy.
P. Howlett, E. Izgorodina, M. Forsyth, D. Macfarlane. Zeitschrift fur
Physikalische Chemie, 2006, 220, 1483-1498. doi:10.1524/zpch.
2006.220.10.1483
Aug 14 2014 ACS 248th National Meeting
18. Investigated six ILs formed from two cations and
three anions
N N
H3C C4H9 B
F
F
F
F
N
H3C C3H7
P
FF
F
FF
F
N
SS
O
O
O
O
CF3F3C
TFSI
PF6 BF4
P13
BMIM
Cations Anions
Aug 14 2014 ACS 248th National Meeting
19. SimplerApproximations – Isolated molecules and
PCM
Treat ions as isolated
molecules in vacuo
or in a polarizable
continuum model
(PCM).1
Calculate electron
affinity (EA) and
ionization energy (IE)
of each ion.
1J.Tomasi, B. Mennucci, B., R. Cammi. Chemical Reviews, 2005, 105, 2999-3093.
ε= 12
Aug 14 2014 ACS 248th National Meeting
20. −5 0 5 10 15
P13
BMIM
PF6
BF4
TFSI
Potential (V)
Cathodic
Limit
Anodic
Limit
Predicted electrochemical windows from isolated
molecule approximation
Predicts that cathodic
limits are always set by
the cation, and anodic
limits are always set by
the anion.
Reasonable
electrochemical
windows of ~3-5V are
predicted.
S. P. Ong G. Ceder, G. Electrochimica Acta, 2010, 55(11), 3804-3811.
Aug 14 2014 ACS 248th National Meeting
21. 0 5 10
P13
BMIM
PF6
BF4
TFSI
Potential (V)
Cathodic
Limit
Anodic
Limit
Predicted electrochemical windows from PCM
approximation
Predicts that both
cathodic and anodic limits
are always set by the
cation, except P13TFSI.
Severely overestimates
the electrochemical
windows; EWs of 6.5V
are predicted.
Dielectric medium
overstabilizes highly-
charged ions.
S. P. Ong, O.Andreussi,Y.Wu, N. Marzari, G. Ceder, G. Chemistry of Materials, 2011,
23(11), 2979-2986. doi:10.1021/cm200679y
Aug 14 2014 ACS 248th National Meeting
22. Explicit modeling of entire liquid structure
Molecular dynamics
simulations of IL
−8 −6 −4 −2
0
20
40
60
80
100
120
Energy (eV)
DensityofStates
Gap
= 3.82 eV
BMIM
BF
4
DFT Calculations of the Density
of States (DOS)
S. P. Ong, O.Andreussi,Y.Wu, N. Marzari, G. Ceder, G. Chemistry of Materials, 2011,
23(11), 2979-2986. doi:10.1021/cm200679y
Aug 14 2014 ACS 248th National Meeting
23. Calculated electrochemical windows
1 2 3 4 5 6 7 8 9
BMIM PF6
BMIM BF4
BMIM TFSI
P13 PF6
P13 BF4
P13 TFSI
− EFermi
Li
Cathodic
Limit
Anodic
Limit
Potential (V)
Clear difference in
CL for P13 vs BMIM
Same AL for all BMIM-
based ILs, despite different
anions!
Expected behavior for
P13-based ILs.
PF6 BF4 TFSI
S. P. Ong, O.Andreussi,Y.Wu, N. Marzari, G. Ceder, G. Chemistry of Materials, 2011,
23(11), 2979-2986. doi:10.1021/cm200679y
Aug 14 2014 ACS 248th National Meeting
24. Are the cathodic and anodic limits set by the
cation or anion?
−8 −6 −4 −2
0
20
40
60
80
100
120
Energy (eV)
DensityofStates
GGA Gap
= 3.82 eV
BMIM
BF4
−8 −6 −4 −2
0
50
100
HSE06 Gap
= 5.08 eVHOMO –
Determines
anodic limit
LUMO –
Determines
cathodic limit
Aug 14 2014 ACS 248th National Meeting
25. −8 −6 −4 −2
0
20
40
60
80
100
120
Energy (eV)
DensityofStates
Gap
= 3.82 eV
BMIM
BF4
−8 −6 −4 −2
0
20
40
60
80
100
120
Energy (eV)
DensityofStates
Gap
= 3.74 eV
BMIM
PF
6
−8 −6 −4 −2
0
20
40
60
80
100
120
Energy (eV)
DensityofStates
Gap
= 3.87 eV
BMIM
TFSI
Cathodic limit is always set by BMIM
cation
Anodic limit also almost always
set by BMIM cation
BMIM-based ILs
Aug 14 2014 ACS 248th National Meeting
26. −8 −6 −4 −2 0
0
20
40
60
80
100
120
Energy (eV)
DensityofStates
Gap
= 5.36 eV
P13
BF
4
−8 −6 −4 −2
0
20
40
60
80
100
120
Energy (eV)
DensityofStates
Gap
= 5.38 eV
P13
PF
6
−8 −6 −4 −2 0
0
20
40
60
80
100
120
Energy (eV)
DensityofStates
Gap
= 4.46 eV
P13
TFSI
Possible cathodic instability in P13
PF6 and P13 TFSI
Anodic limit generally set by anion,
except for P13PF6.
P13-based ILs
Aug 14 2014 ACS 248th National Meeting
27. Further refinements to MD + DFT method
Aug 14 2014 ACS 248th National Meeting
DFT HOMO/LUMO
AIMD relaxation and
quenching
Classical MD
Zhang,Y.; Shi, C.; Brennecke, J. F.; Maginn, E. J. Refined Method for Predicting Electrochemical Windows of Ionic
Liquids and ExperimentalValidation Studies., J. Phys. Chem. B, 2014, doi:10.1021/jp5034257.
28. Conclusions
−8 −6 −4 −2
0
20
40
60
80
100
120
Energy (eV)
DensityofStates
GGA Gap
= 3.82 eV
BMIM
BF4
−8 −6 −4 −2
0
50
100
HSE06 Gap
= 5.08 eV
MD + DFT
Explicitly modeled
entire IL structure
Achieved semi-
quantitative accuracy
in EW prediction
Surprising prediction
of BMIM instability,
consistent with exp.
evidence
Cathodic limits are not always set by
cations and anodic limits are not always
set by anions
Aug 14 2014 ACS 248th National Meeting
29. Acknowledgements and Publications
Funding from E. I. du Pont de Nemours Co. via the DuPont-
MIT Alliance program.
William L. Holstein and Steve R. Lustig from DuPont for useful
insights and assistance.
TeraGrid resources provided by the Pittsburgh
Supercomputing Center.
Aug 14 2014 ACS 248th National Meeting
S. P. Ong, O.Andreussi,Y. Wu, N. Marzari, G. Ceder. Electrochemical Windows
of Room-Temperature Ionic Liquids from Molecular Dynamics and
Density FunctionalTheory Calculations. Chemistry of Materials, 2011, 23(11),
2979-2986.
S. P. Ong G. Ceder, Investigation of the Effect of Functional Group
Substitutions on the Gas-Phase Electron Affinities and Ionization Energies
of Room-Temperature Ionic Liquids Ions using Density FunctionalTheory.
Electrochimica Acta, 2010, 55(11), 3804-3811.