Article

pubs.acs.org/cm

Fundamental Mechanisms of Solvent Decomposition Involved in

Solid-Electrolyte Interphase Formation in Sodium Ion Batteries
Hemant Kumar,† Eric Detsi,† Daniel P. Abraham,‡ and Vivek B. Shenoy*,†
†
Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States
‡
Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
*
S Supporting Information

ABSTRACT: Prolonged decomposition of electrolytes form-

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ing a thick and unstable solid-electrolyte interphase (SEI)

continues to be a major bottleneck in designing sodium-ion
batteries (SIBs). We have carried out quantum chemistry
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simulations to investigate the fundamental mechanisms of

reduction-induced decomposition of electrolyte solvents in the
vicinity of a sodium ion. Kinetics and thermodynamics of
several reaction pathways for one- and two-electron reduction
of ethylene carbonate (EC) have been examined. Our
calculations indicate that the high reduction potential and
low barrier for the ring opening of EC is the main cause for the
continuous growth of SEI observed in SIBs. The impact of two well-known electrolyte additives, vinyl carbonate (VC) and
fluoroethylene carbonate (FEC), on SEI composition was evaluated by studying decomposition pathways of (1) VC and FEC
molecules in the bulk EC solvent and (2) an EC molecule in a supermolecular cluster comprising an EC and the additive
molecule. The additive molecules have significantly low barriers for decomposition and therefore decompose first. Additionally,
the presence of an additive molecule was also shown to increase the barrier for decomposition of EC. Another observation
suggests that the preferred reduction state of an EC molecule changes when it forms a dimer with additive molecules, and these
reduction states have different decomposition pathways which leads to formation of different SEI compounds. On the basis of
these observations, we predict that not only do the additive molecules protect solvent molecules from reductive decomposition
but also they can promote alternate pathways for the decomposition, leading to qualitatively different and potentially stable SEI
products.

1. INTRODUCTION
Solid electrolyte interphase (SEI) is a crucial determinant of
battery life.1 During the first few charging cycles of a battery,
organic solvents in the electrolyte are reduced near the anode.
The reduced solvent molecules decompose into chemically
active radicals that form new chemical entities. Mosaic structure
of these entities generates a film composed of inorganic and
organic decomposition products called the SEI.2 With the right
composition, the SEI can impart kinetic stability to the
electrolyte against further reduction in successive cycles while
allowing ionic mobility through it.3,4 The SEI acts to extend
battery life by preventing further decomposition of the solvent
molecules and by hindering solvent intercalation into the
battery anode.2 Although the SEI extends the battery life, the
formation of SEI also results in irreversible capacity loss due to
consumption of metal ions, a factor that plays an important role
in determining the cycle life of batteries.
Sodium-ion batteries (SIBs) are cost-effective alternatives to
lithium-ion batteries (LIBs) but often suffer from short cycle
lifetime,5 partly attributed to the relatively large size of the
sodium atom (Na radius 190 pm vs Li radius 167 pm), which
results in deleterious sodiation-induced volume changes,
compared to the volume changes occurring during lithiation.1
Another leading cause of the short cycle life is the formation of
unstable SEI near the anode surface.6−8 Despite the similar
ionic nature of sodium and lithium ions, the SEI in SIBs has
been shown to continuously evolve upon cycling, while it
becomes stable after the first few cycles in LIBs.9 An
experimental study comparing the SEI structure between SIB
and LIB for a given electrolyte composition has shown that the
SEI in SIBs is thicker and unstable compared to the SEI in
LIBs.6 Furthermore, recent XPS experiments suggest that the
SEI in SIBs has a higher percentage of inorganic salts, alkyl
carbonates, and CO rich compounds compared to LIBs,
which predominantly contain hydrocarbon chains
(−CH2−).7,10 In addition, it has also been shown6 that the
SEI in LIBs has a well-defined layered structure in contrast to a
relatively homogeneous structure in SIBs.
The chemical composition of the battery electrolyte
determines the resulting structure and the passivating
capabilities of the SEI. However, while the chemical
composition of the electrolytes for LIBs has been greatly
Received: August 15, 2016
Revised: November 29, 2016
Published: November 30, 2016

© 2016 American Chemical Society 8930 DOI: 10.1021/acs.chemmater.6b03403

Chem. Mater. 2016, 28, 8930−8941
Chemistry of Materials
optimized in recent years, the optimum electrolyte composition
for SIBs is still not known. Previous research has shown that
using the electrolyte compositions optimized for LIBs in SIBs
leads to the formation of unstable SEIs.11 Komaba et al. has
shown that an electrolyte containing ethylene carbonate (EC)
and diethyl carbonate (DEC) solvents retains a stable capacity
of 240 mAh g−1 after 100 cycles with hard carbon electrodes in
SIBs.12 Ponrouch et al. systematically investigated various
solvents (EC, propylene carbonate (PC), DEC, dimethyl
carbonate (DMC), tetrahydrofuran (THF), triglyme) and
sodium salts (NaClO4, NaPF6) for the optimum performance
of SIBs and concluded that a binary solvent consisting of EC
and PC with NaClO4 salt results in the best electrochemical
performance.13 Film-forming materials such as vinylene
carbonate (VC) and fluoroethylene carbonate (FEC) are
well-known additives in LIB and Li−Si batteries.14−18 Initial
studies have shown that the addition of FEC improves the cycle
life of SIBs as well.19 However, an electrolyte mixture for SIB
that can provide a cycle life comparable to LIBs is still not
known. Furthermore, the underlying reason for such character-
istically different electrolyte decomposition behaviors of these
two battery systems (in spite of the similar electronic shell
structure of their cations) is not understood. The final SEI
composition can be affected by a multitude of different factors,
such as the order of the bond breaking events, the relative
stability of resulting radical ions, and the thermodynamic
feasibility of different decomposition reactions.20 Understand-
ing the decomposition mechanism of the electrolyte
components in a reducing environment is central to the
rational design of SEI for optimum performance of the battery.
The recent surge in experimental activities related to the SEI in
SIBs has brought important insights on the formation
mechanism,21−25 but a mechanistic understanding is missing
due to a limited number of theoretical studies.
Therefore, we investigated the mechanism of reduction
induced decomposition of different alkyl carbonate molecules
and additives in the vicinity of a sodium ion using the density
functional theory (DFT) method. Thermodynamics and
kinetics of reductive decomposition of the most commonly
used solvent molecule EC and additive molecules VC and FEC
were quantified using a hybrid functional DFT scheme. Using a
molecular cluster approach, we have further studied the effect
of additive molecules (PC, VC, and FEC) on the decom-
position pathways of the EC. In this study, we elucidate the
thermodynamics of SEI formation which enables us to make
predictions to improve the performance of SEIs in SIBs.
2. COMPUTATIONAL METHODS
Structural optimization of cyclic carbonate molecules was performed
using DFT with the hybrid B3PW91 exchange-correlation function as
implemented in GAMESS.26 Gaussian basis set 6-311++G(d,p) was
employed to expand the Kohn−Sham orbitals in all the optimization
calculations as well as for the single point energy calculations. This
hybrid functional DFT has been shown to accurately reproduce the
thermochemistry data for open-shell organic molecules.27 Free energy
of the decomposition reactions was quantified at T = 298.15 K and P =
1 atm after taking into account entropy corrections obtained from
frequency analysis. Zero-point energy (ZPE) corrections were
included in all energy values unless noted otherwise. Transition states
were verified by identifying the imaginary modes along the reaction
coordinates and then performing intrinsic reaction coordinate (IRC)
simulations.
First, reduction induced decompositions of individual molecules of
EC, VC, and FEC were investigated in the vicinity of the Na+ ion
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(Figure 1). The effect of the bulk solvent was accounted for by using a
continuum solvent model (C-PCM) (eps = 89.78, rsolv = 2.476) for
Figure 1. Optimized geometries for different organic solvent and
additive molecules in the unreduced form.
EC.28,29 Both the geometry optimization and frequency calculations
were carried out using the same level of DFT in conjugation with the
continuum solvent model. This direct approach has been shown to
reproduce free energy values in solution phase comparable to the
thermodynamic cycle method.30 The role of the additives on EC
decomposition was explored by considering the decomposition of the
supermolecular clusters composed of EC and other additive molecules
in the gas phase simulations. These simple theoretical calculations may
not incorporate the complex details of SEI growth conditions in
experiments, but accurate estimates of the thermodynamics and
barriers for various decomposition reactions help to better understand
the feasibility of different reactions and infer the nature of dominant
SEI products.
3. RESULTS
3.1. Reduction Pathway for the Decomposition of EC.
The reaction pathways for the reduction induced dissociation of
the EC−Na+ complex are shown in Figure 2. The changes in
the Gibbs free energy with respect to the unreduced structure
(E0) are also shown for all stationary points along the pathway.
Two distinct reduction states with different values of reduction
free energies were found. The first reduction state corresponds
to a structure where the excess electron is completely localized
on the sodium ion. In the second reduction state, the excess
electron is shared by the carbon and oxygen atoms of the
carbonyl group of the EC molecule. These two reduction states
are subsequently designated as A and B, respectively. Our
calculations show that the free energy of reduction for the state
A (−52.65 kcal/mol) is lower than the corresponding free
energy for the state B (−51.61 kcal/mol). This indicates that
EA1 is the thermodynamically preferred reduction state. A
comparison with the corresponding free energy values in LIBs
(−45.8 kcal/mol) implies that the reduction of an EC molecule
is easier in SIBs.31 The reduction follows the homolytic
dissociation of either the CCOC bond or the CEOC bond,
opening the five-membered ring of the EC molecule. The
relative free energies of the transition states govern which of the
two possible bond dissociation reactions dominates. The
dissociation of the CEOC bond has two transition states
indicated as EA2 and EB2 in Figure 2 for both of the reduction
states A and B. The state A has a lower value of the bond
breaking barrier for reduction state A (4.50 kcal/mol (EA2)
compared to 9.31 kcal/mol in state B (EB2)), which suggests
that the CEOC bond can break easily in this reduction state.
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Chemistry of Materials
Figure 2. Reaction pathways for the reduction induced decomposition of a EC−Na+ complex studied using the continuum solvent model (PCM).
Gibbs free energies at T = 298.15 K and P = 1 atm are given with respect to the unreduced structure (E0).
Since the reduction potential for the state A is higher and the
bond breaking barrier is lower compared to state B, CEOC bond
breaking is likely to occur through the reduction state A. This
behavior is in contrast to an EC−Li+ complex for which
reduction state B is the preferred state and the dissociation
barrier is ∼9.5 kcal/mol.31 After the dissociation of the CEOC
bond, both states A and B yield the same radical anion (E3)
coordinated with a sodium cation. Bond dissociation free
energies corresponding to these exothermic reactions are
−29.59 and −30.63 kcal/mol, respectively. In addition to the
CEOC bond dissociation discussed above, another probable
pathway for the ring-opening reaction involves homolytic
dissociation of a CCOC bond. However, we did not find any
stable equilibrium structures corresponding to the CCOC bond
dissociation. This suggests that the CCOC bond dissociation is
not feasible in a single electron reduction state of EC. This
behavior is similar to the EC−Li+ complex studied by Leung.32
2e Reduction of EC. The CCOC bond of an EC molecule
spontaneously dissociates when an extra electron is added to
the singly reduced state B. The anion radical (EB3) obtained
from this dissociation can further decompose in two different
ways, depending upon whether the remaining CCOC bond
(EB4) or CEOC bond (EB5) breaks. Thermodynamically,
dissociation of the CCOC bond (ΔG= −0.78 kcal/mol), which
results in the release of a CO gas molecule and formation of an
−
OCH2CH2O− anion (EB4), is favorable compared to the
dissociation of the CEOC (ΔG= 6.17 kcal/mol) bond, which
results in the release of a CO2 gas molecule and formation of an
·CH2CH2O− anion (EB5). These 2e reduction-induced
decompositions are widely accepted as the primary reaction
mechanisms to explain the release of CO and CO2 gases in
LIBs.32 In our calculations, CCOC bond dissociation is
spontaneous upon reduction and no energy barrier is observed,
while in the case of LIBs, a small barrier of ∼2.3 kcal/mol was
observed by Leung.32
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On the basis of the above observations, we concluded that an
EC molecule connected to a sodium cation is easily
decomposable compared to an EC molecule connected to a
lithium cation. This result is consistent with experimental
observations6 which show that the thickness of the SEI in SIBs
is larger compared to LIBs, indicating the prevalent
decomposition of solvent molecules near anodes. Experimental
studies have also found dissimilar proportions of organic and
inorganic compounds in these two battery systems. The SEIs in
LIBs are mainly composed of carbon rich organic compounds
while, in SIBs, the SEIs mainly contain oxygen rich inorganic
compounds.11,33 In order to determine what factors contribute
to this difference in the composition, we further examine the
termination reactions of these radicals in the following section.
3.2. SEI Components from the Decomposition of EC.
The anion radicals generated from the bond dissociation
reactions described above (E3 from CEOC bond) are highly
reactive and therefore are very likely to undergo secondary
reactions. Various reactions leading to the termination of the
anion radical (E3) are shown in Figure 3. Sodium butylene
carbonate ([CH2CH2OCO2Na]2, Na2BDC) is one of the major
components of the SEI and is generated as a result of the direct
recombination of two E3 anion radicals (Figure 3a). Barrierless
recombination of these radicals also results in a free energy gain
of −54.89 kcal/mol. Another possible pathway for radical
termination is the nucleophilic attack of anion radical E3
(Figure 3b) on the oxygen of the neighboring E3 radical. This
r e a c t io n p r o d u c e s s o d i u m et h y l e n e d i c a r b o n a t e
([CH2OCO2Na]2, Na2EDC) and ethylene (C2H4) gas.
Na2EDC is the most abundant chemical compound in a
SEI,8,25 and its formation reduces the free energy by −43.81
kcal/mol. In addition to these two direct recombination
reactions, the next pathway involves further reduction of the
anion radical E3. After reduction, the spontaneous dissociation
of the remaining CEOC bond follows (Figure 3c). This reaction
is also exothermic, and −35.46 kcal/mol of free energy is
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Chemistry of Materials
Figure 3. EC anion radical termination reactions and their Gibbs free
energy at T = 298.15 and P = 1 atm.
released. As a result, an ethylene gas molecule and NaCO−3
anion (E4) is produced. The resulting anion radical is highly
reactive due to an unpaired electron and goes through
subsequent reaction pathways. Two plausible pathways for
Figure 4. Reaction pathways for the reduction induced decomposition of VC−Na+ complex studied using a continuum solvent model (PCM). Gibbs
free energy at T = 298.15 K and P = 1 atm are given with respect to the unreduced structure (V0).
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the termination of this radical (E4) are explored here. In one
pathway, the radical E4 combines with a sodium ion (Figure
3e) to form Na2CO3, an inorganic salt experimentally observed
in SEIs. The second pathway involves a nucleophilic attack on
the oxygen of another EC−Na+ complex, which results in the
release of an ethylene gas molecule along with the formation of
a Na2EDC molecule (Figure 3f). Both of these termination
reactions are thermodynamically favorable and are equally
plausible as they produce similar free energy gains of −121.79
and −122.96 kcal/mol, respectively.
3.3. Reaction Pathway for the Decomposition of VC.
Reduction chemistry of VC in the vicinity of a sodium ion is
shown in Figure 4. Close inspection of the intermediate
reaction products shows that most of the reaction pathways
remain qualitatively similar to the case of EC. Like the EC−Na+
complex, VC−Na+ has two distinct reduction states A and B
(VA1 and VB1). However, in this case, B has a lower free
energy and is therefore the preferred reduction state. Various
decomposition pathways for this reduction state, i.e., the
dissociation of the CCOC bond (VB1−VB2−VB3) and the
dissociation of the CEOC bond (VB1−VB6−VB7), are
discussed below.
The free energy of reduction for a VC−Na+ complex
(−55.96 kcal/mol) is lower than that of an EC−Na+ complex
(−51.61 kcal/mol) in the equivalent reduction state B.
However, there is a difference between the reductive
decomposition of the VC and EC molecules. The homolytic
dissociation of a CCOC bond has an unfavorable reaction free
energy in the single electron reduction states of an EC−Na+
complex but may occur readily for the VC−Na+ complex. The
energy barrier for this bond dissociation (VB2) is very low
(1.13 kcal/mol) implying a rapid decomposition of the VC
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Chemistry of Materials
molecule after reduction. Although this bond dissociation is an
exothermic reaction, the thermodynamic gain from this
decomposition (VB3) is quite small (ΔG = −1.53 kcal/mol)
compared to the ring opening (through CE O C bond
dissociation) in an EC−Na+ complex (ΔG = −30.63 kcal/
mol). The anion radical VB3 produced by this bond
dissociation initiates further chemical reactions. Dissociation
of the remaining CCOC bond of the VB3 radical yields an
−
OCHCHO− anion (VB4) and a CO gas molecule. This
exothermic decomposition reaction reduces the system free
energy by −38.55 kcal/mol. Another route for the decom-
position is the release of CO2 and the anion VB5 as a result of
the CEOC bond dissociation of VB3. While this decomposition
is also thermodynamically possible, the free energy gain is
comparatively small (ΔG = −12.32 kcal/mol).
The next plausible decomposition in the reduction state B
involves a CEOC bond dissociation (VB7) of the VC molecule.
The gain in Gibbs free energy as a result of this reaction is
considerable (ΔG = −15.85 kcal/mol) compared to the CCOC
bond dissociation discussed above. However, the energy barrier
for this reaction is very high (VB6, ΔGbarrier = 17.84 kcal/mol),
and therefore, the CCOC bond dissociation will kinetically
dominate over the CEOC bond dissociation in reduction state B.
Because the anion radicals generated from these dissociations
have different reaction centers, they follow different reaction
pathways and generate different decomposition products.
Hence, the relative thermodynamic viability of these bond
dissociation reactions govern SEI composition.
We also investigated the pathways originating from the
reduction state A (reduction free energy = −50.55 kcal/mol,
not shown in Figure 4). Homolytic dissociation of the CEOC
bond in the reduction state A is also exothermic and reduces
the free energy by −21.25 kcal/mol. The energy barrier for this
reaction is 8.34 kcal/mol which is much smaller than 17.84
kcal/mol in reduction state B for the same bond dissociation. A
smaller energy barrier suggests that the dissociation of the
CEOC bond is easier in the reduction state A. However, the
dissociation of the CCOC bond is not feasible in this reduction
state. We discuss this issue in Section 3.5.
2e Electron Reduction of VC. In the initial phase of SEI
formation, electron tunneling rates are high and a VC molecule
may receive two electrons. The transfer of two electrons
initiates spontaneous dissociation of the CCOC bond (VB11) of
a VC molecule. This decomposition reaction has no energy
barrier as opposed to the 1e electron reduction with an energy
barrier of 1.13 kcal/mol. The anion generated from this bond
dissociation decomposes further to produce CO and −OCH-
CHO− (VB12) and lowers free energy by −58.56 kcal/mol.
Another possibility of this anion decomposition via dissociation
of the CEOC bond produces CO2 and CHCHO− (VB13) anion.
However, this reaction is less exothermic, and the free energy is
only lowered by −41.77 kcal/mol. A similar reaction route
releasing CO was also observed by Ushirogata et al.,34 while
investigating two-electron pathways of VC decomposition in
LIBs using ab-initio molecular dynamics (AIMD) simulations.
However, they did not observe a pathway that releases CO2 as a
result of the direct decomposition of VC. This might possibly
be related to the large kinetic barrier for the dissociation of the
CEOC bond that was not overcome during the short AIMD
trajectories they studied.
Another two-electron pathway involves reduction of the
radical anion (VB7). Reduction of this radical lowers the free
energy by −86.88 kcal/mol which is much lower than the free
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energy release (−55.96 kcal/mol) due to the reduction of the
intact VC−Na+ complex. Thus, once the radical is formed, it
will get preferentially reduced. This radical remains stable after
the excess electron is reduced, as opposed to the EC radical
anion (E3) which spontaneously decomposes upon reduction
by the second electron. This metastable reduction state (VB9)
decomposes exothermically into CO32− and C2H2, and a
thermodynamic gain in free energy of −12.66 kcal/mol is
observed.
To summarize, the VC−Na+ complex decomposes readily
after reduction. For both the 1e and 2e reduction states, the
reaction mechanism involving the release of CO (VB1−VB3−
VB4, VB1−VB11−VB12) is the most feasible reaction from a
thermodynamic point of view. This leads to the formation of
the −OCHCHO− anion which is known as an oligomerization
agent due to the presence of CHCH moieties. Another
decomposition pathway results in the formation of CO32− and
C2H2 (or other organic dicarbonate, e.g., NaVDC). This
pathway has large thermodynamic gain but is kinetically
restricted due to a large free energy barrier and is therefore
less likely to contribute to SEI formation.
3.4. Reaction Pathway for the Decomposition of FEC.
The presence of a fluorine atom creates asymmetry in the five-
membered ring which in-turn leads to various possibilities for
reduction states. In addition to the reduction states A and B
discussed above, two additional states can be created by placing
the sodium and fluorine atoms opposite the ring bisector.
Furthermore, Na and F can be placed either on the same or on
the opposite sides of the ring plane. Six distinct stable reduction
structures arising from such permutations are shown in Figure
5. The relative free energy values with respect to the unreduced
Figure 5. Different reduction states of the FEC−Na+ complex along
with the reduction free energy (in kcal/mol) at T = 298.15 K and P =
1 atm obtained using the PCM method.
structure are also shown in Figure 5. The free energies of
reduction for four out of six FEC−Na+ structures are lower
than that of an EC−Na+ complex. All structures corresponding
to the reduction state B have lower free energies compared to
those of reduction state A, irrespective of the placement of the
fluorine atom. However, for a given reduction state (A or B),
structures with sodium and fluorine placed on the same side of
the ring bisector (e.g., Figure 5d,e) have a free energy lower
than those structures where sodium and fluorine are placed
opposite the bisector by ∼1.5 kcal/mol. Among all the
structures, Figure 5d has the lowest reduction in free energy
and is therefore the most probable reduction state.
Decomposition pathways of FEC−Na+ in the 1e reduction
states are shown in Figure 6. Unlike an EC−Na+ complex, the
CCOC bond of a FEC can easily break, even in the singly
reduced state with a small free energy barrier of 0.96 kcal/mol.
The radical anion generated from this bond dissociation
undergoes further decomposition, and two subsequent bond
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Figure 6. Reaction pathways for the reduction induced decomposition of FEC−Na+ complex studied using continuum solvent model (PCM). Gibbs
free energy at T = 298.15 K and P = 1 atm is given with respect to the unreduced structure (F0). Numbers in blue correspond to the reduction state,
Figure 5f.
dissociation reactions are possible: a CEOC bond can break that
releases a CO2 gas molecule and generates CHCHO− anion
(FB4) or a CCOC bond can break that releases a CO gas
molecule and generates a CH2CHO2− (FB5) anion. Thermo-
dynamically, the reaction involving CO2 is more favorable (ΔG
= −43.99 kcal/mol) than the reaction in which CO is released
(ΔG = −29.76 kcal/mol). Dissociation of the second CCOC
bond in the FEC molecule is accompanied by simultaneous
breaking of the C−F bond leading to the release of the fluorine
atom. This sequential dissociation of multiple bonds as a result
of the single electron reduction of FEC was experimentally
observed15 for LIBs as well. The fluorine atom generally
combines with a nearby sodium ion, creating NaF, a commonly
observed inorganic salt when FEC is introduced as an additive.
The presence of LiF in LIBs was recently shown to act as a link
between multiple decomposition products which in-turn
promotes a network structure in SEI.35
In addition to these two dissociation reactions, there is a
third possibility when fluorine and sodium do not form NaF
after dissociation of CCOC and CEOC bonds. In this case, both
H and F atoms are released simultaneously and can combine to
form a HF molecule. The vinyl anion (FB6) generated as a
result of this reaction is the same as the previous reaction
involving the release of CO. However, this reaction is less
exothermic (ΔG = −24.36 kcal/mol) compared to the other
two reactions discussed above. It should be noted that this
decomposition mechanism of FEC releasing HF was also
proposed for LIBs.36 However, Leung et al. did not observe this
reaction for LIB in their AIMD simulations.14 We believe the
different outcomes stem from the different sequences of bond
breaking considered in the two studies. As we observed here,
sequential bond decompositions (of CCOC and CEOC bonds)
do not lead to the release of HF, but simultaneous dissociation
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leads to the formation of HF. It should also be noted that, for
an EC molecule, these secondary reactions are thermodynami-
cally feasible only in the 2e reduction state and do not occur in
the 1e reduction states.
Like VC molecule decomposition, the alternative ring-
opening reaction through dissociation of a CEOC bond is
kinetically unfavorable. However, while this bond dissociation
has a high free energy barrier (FB7) of 16.83 kcal/mol, making
it kinetically unfavorable, free energy gain is favorable compared
to the CCOC bond dissociation (−78.16 vs −65.20 kcal/mol).
The radical anion (FB8) generated from this reaction
decomposes further, thereby releasing the CH2CHF and
NaCO3− anion (FB9). It is important to note that, in a single
electron reduction state, this reaction is thermodynamically
uphill (ΔG = 3.14 kcal/mol) and thus unlikely to happen. On
the other hand, subsequent attack of another electron on the
radical makes this decomposition thermodynamically favorable
and the free energy of reaction would be −106.65 kcal/mol
(FB10).
2e Electron Reduction of FEC. Like EC and VC, the CCOC
bond spontaneously dissociates after 2e reduction of FEC
(FB11). Subsequent reactions generate CO or CO2 gases along
with anions (FB12 and FB13) similar to the case of the 1e
reduction described above. Two significant differences were
observed between 1e and 2e decomposition pathways. Free
energy gain for these reactions is very large for 2e reduction
(ΔGFB12 = −98.8 kcal/mol, ΔGFB13 = −69.52 kcal/mol)
compared to 1e reduction (ΔGFB4 = −43.99 kcal/mol, ΔGFB5 =
−29.76 kcal/mol). Additionally, the fluorine atom drifts away as
fluorine ion instead of combining with the sodium atom as in
the case of 1e reduction.
3.5. CEOC Bond Dissociation Is Preferred in the
Reduction State A while CCOC Bond Dissociation Is
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Preferred in the Reduction State B. For all the solvent
molecules studied above, energy barriers for the CEOC bond
dissociations are higher in reduction state B than reduction
state A. On the other hand, transition states corresponding to
the CCOC bond dissociation exist only for reduction state B. All
attempts to find a transition state for the CCOC bond
dissociation in state A led to a transition state for reduction
state B, suggesting that the CCOC bond dissociation can be
initiated only in the reduction state B. Surprisingly, the CCOC
bond dissociation reactions in LIBs systems have been
discussed only in reduction state B without any reference to
state A.32 Observations made here suggest that the two distinct
reduction states, A and B, have a preference over which bond is
likely to dissociate after reduction, and hence, qualitatively
different SEI products might be observed depending on the
preferred reduction state of the decomposing molecule. The
CEOC bond dissociation is preferred in reduction state A, which
eventually leads to the formation of the carbonate salts (e.g.,
Na2CO3, Na2EDC, Na2BDC) and hydrocarbon gas molecules.
On the other hand, the CCOC bond dissociation is favored in
reduction state B, which leads to the formation of oxygen rich
SEI products (e.g., aloxide, glycol group) along with CO and
CO2 gas molecules.37 These differing outcomes of the two
reduction states are likely to be valid for LIBs as well but, to the
best of our knowledge, have not been identified yet. A clear
distinction between the two reduction states has important
implications for controlling the SEI composition. As we will
show later in this paper, preference for reduction states A or B
can be adjusted by introducing suitable additive molecules in
the electrolyte.
3.6. Solvation Behavior of Different Solvent Mole-
cules: Structure of a Sodium Ion Solvation Shell. Before
investigating the effects of additives on reductive decom-
position, it is important to understand the solvation behavior of
commonly used molecules in the electrolyte. The structure of
an ion solvation shell plays a major role in battery operation. A
large solvation shell not only limits ion-mobility during the
charge/discharge cycle but also changes ion-transfer kinetics
near the electrodes.38 From the point of view of SEI formation,
the structure of an ion solvation shell can have significant
effects as well.39,40 Preferential solvation of an additive molecule
over the solvation of the solvent molecules changes the
electronic environment of the decomposing molecules and, as a
result, changes the reduction chemistry.40 We examine the
solvation characteristics of a sodium ion in the EC solvent and
investigate potential consequences of additive molecules (PC,
VC, and FEC) on solvation thermodynamics (Figure 7).
Formation free energy of ECn−Na+ (n = 1···4) clusters
suggest that a maximum of three EC molecules can stay in the
Figure 7. Solvation shell structure of a sodium ion in the EC solvent
(a) before reduction and (b) after reduction. Structures were
optimized in the gas phase simulation using B3PW91/6-311++G(d,p)
DFT simulations.
8936
Article
sodium ion solvation shell (Table 1). The addition of the fourth
EC molecule to an EC3−Na+ cluster leads to a positive
Table 1. Formation Free Energy with an Increasing Number
of EC Molecules in the Solvation Shell of a Sodium Iona
formation free reduction free
cluster energy energy
EC + (EC)Na+ → (EC)2Na+ −18.70 −64.06
EC + (EC)2Na+ → (EC)3Na+ −8.22 −56.75
EC + (EC)3Na+ → (EC)4Na+ 10.23 −54.12
a
Reduction free energy is also given for different cluster sizes. All
energy values are in kcal/mol.
formation free energy (ΔG = GEC4−Na+ − GEC3−Na+ − GEC) of
10.23 kcal/mol. The inability of the sodium ions to solvate four
EC molecules in an electrolyte is in sharp contrast to the case of
LIBs which are known to form a stable tetrahedral structure
with four EC molecules.31,41 Due to the smaller size of a lithium
ion, the charge density at the surface of the ion is higher than a
sodium ion, and therefore, a lithium ion can solvate more
molecules than a sodium ion, accounting for the larger
solvation shell of lithium ions. The smaller solvation shell of
the sodium ion is beneficial for battery operation because a
small cluster of molecules can be transported easily in the
electrolyte solution resulting in faster charge/discharge rates.
Reduction free energies of the EC with increasing number of
molecules in the solvation shell are also given in Table 1. With
increasing cluster size, free energy of reduction increases and
approaches the value obtained from the continuum solvent
model. This gives us confidence that the PCM model employed
above can accurately reproduce the reduction characteristics of
explicit solvent molecules.
Next, we studied the effects of additive molecules on the
structure of the solvation shell. Inclusion of an additive
molecule (PC, VC, FEC) in an EC3−Na+ cluster has a positive
formation free energy, illustrating that the three-coordinated
solvation shell is still the most stable configuration even in the
presence of additives. To investigate the possibility of additive
molecules replacing an EC from the three-coordinated
solvation shell, we computed the formation free energies of
clusters where an EC molecule is replaced by an additive
molecule. For each of the additive molecules, we considered the
free energy of formation of the EC2−X−Na+ complex (X = EC,
PC, VC, FEC) defined as ΔGformation= ΔGEC2−X − ΔGEC2 −
ΔGX. Values of the free energies of formation for all the
additive molecules have been shown in Table 2. For all the
trimers studied, EC3−Na+ is the most stable state, and
substituting an EC molecule with any other molecule results
in a less stable solvation shell. The formation energies of Na+−
Table 2. Formation Free Energy of Adding Different
Molecules to EC-Dimer Completing the Solvation Shell of a
Sodium Iona
formation free reduction free
cluster energy energy
PC + (EC)2Na+ → (EC)2Na+PC −8.08 −55.76
VC + (EC)2Na+ → (EC)2Na+VC −5.13 −58.88
FEC + (EC)2Na+ → (EC)2Na+FEC −5.15 −59.86
a
Reduction free energies of the EC molecule in these solvation shells
are also given for all clusters. All energy values are in kcal/mol.
DOI: 10.1021/acs.chemmater.6b03403
Chem. Mater. 2016, 28, 8930−8941
Chemistry of Materials Article

Figure 8. (a) Three distinct reduction states for a heterodimer (EC−VC, EC−PC, or EC−FEC), optimized using B3PW91/6-311++G(d,p) DFT
simulations. (b) Change in the reduction free energy for both reduction states of EC in the vicinity of different additive molecules.

Figure 9. Reaction pathways for the reduction induced decomposition of dimer complexes studied in the gas phase. Gibbs free energies at T =
298.15 K and P = 1 atm are given with respect to an unreduced structure. Molecules marked with A represent additive molecules (A = EC, PC, VC,
FEC). The upper half of the figure represents pathways involving the ring opening of the EC while the lower half represents pathways involving
decomposition of the additive molecules.

EC3 and Na+−EC2−PC are almost identical (ΔGformation =
−8.21 kcal/mol vs ΔGformation = −8.08 kcal/mol), while
solvation shells incorporating a VC (ΔGformation = −5.13 kcal/
mol) or a FEC (ΔGformation = −5.15 kcal/mol) molecule are
comparatively less stable. These results suggest that the most
stable solvation shell is formed with EC molecules, and additive
molecules are less likely to replace an EC molecule from the
solvation shell, although a solvation shell with an additive
molecule is thermodynamically stable.
3.7. Role of Additive Molecules on the Decomposition
of EC. In LIB electrolytes, the addition of VC and FEC has
8937
been proven to extend battery life by improving the SEI
composition.29,42,43 Additive molecules generally have higher
reduction potentials compared to solvent molecules and are
therefore preferentially reduced at the anode. This sacrificial
reduction is considered to be the main protection mechanism
for the additives. However, it was recently shown that the
sacrificial reduction of additives can only be partially accounted
for in the enhancement of the battery life.34 Ushirogata et al.
showed that a VC molecule preferentially reacts with an EC
anion radical.34 This suppresses the two-electron reduction of
EC molecules and thus enhances the SEI composition.
DOI: 10.1021/acs.chemmater.6b03403
Chem. Mater. 2016, 28, 8930−8941
Chemistry of Materials
Figure 10. Change in (a) the free energy barrier and (b) the free energy released after dissociation of the CEOC bond of EC and additive molecule in
the reduction state A of different dimers.
Additionally, reaction pathways for decomposition of the
solvent molecules are also altered when additive molecules
are present in the vicinity.35,42 In order to investigate the role of
additives on EC decomposition, we simulated decomposition
pathways for four dimers, namely, EC−EC, EC−PC, EC−VC,
and EC−FEC. VC and FEC are commonly used additives; PC
is often used as a cosolvent of EC, and the EC−EC cluster
representing the pure EC solvent is considered as a reference
structure. In the case of a heterodimer, any of the two
molecules can get reduced in the A or B reduction states. Since
the reduction state A involves localization of the excess electron
on the sodium ion, this state is identical for the reduction of
both molecules, leaving three distinct reduction states for a
heterodimer as shown in Figure 8a.
Variation in the reduction free energy of an EC molecule in
conjugation with other molecules is depicted in Figure 8b for A
and B reduction states. The reduction free energy of the
homodimer molecule in the presence of another EC molecule
is −64.0 kcal/mol, which is marginally lower than the reduction
free energy (−52.65 kcal/mol) in the continuum EC solvent
discussed in Section 3.1. To quantify the impact of different
additive molecules on the decomposition pathways, we
consider the EC−Na+−EC complex as a reference and
systematically replace the nonreducing EC molecule with
additive molecules.
When the EC molecule is replaced with a PC molecule,
reduction of EC becomes favorable by −1.2 kcal/mol. Similarly,
replacing the EC molecule with a VC or FEC molecule also
lowers reduction free energy of the EC molecule (Figure 8b).
However, the addition of these two additive molecules changes
reduction free energy more significantly (∼4 kcal/mol) for
both of the reduction states. This demonstrates that the
reduction of an EC molecule forms a more stable structure in
the presence of an intact additive molecule compared to the
pure EC solvent. EC decomposition pathways that follow these
reductions are shown in Figure 9. As elucidated in the previous
section, because the decomposition of an EC molecule after 1e
reduction is most likely to occur through the reduction state A
followed by the dissociation of a CEOC bond, we consider only
those pathways that initiate from reduction state A.The energy
barrier for the dissociation of a CEOC bond in conjugation with
a PC molecule is 4.94 kcal/mol which is slightly higher
compared to the EC dimer. The same trend of a higher energy
barrier holds for the other two molecules as well (Figures 9 and
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10). In the presence of a VC molecule, the value of the energy
barrier is 4.58 kcal/mol, and in the presence of a FEC molecule,
it is 4.78 kcal/mol. These results suggest that, even though the
reduction of the EC molecule becomes thermodynamically
favorable in the presence of additive molecules, the ring
opening as a result of CEOC bond dissociation becomes
kinetically unfavorable.
The heat of bond dissociation, defined as the change in the
dimer free energy due to bond dissociation, also varies in the
presence of another molecule in the dimer. While homolytic
dissociation of the CEOC bond remains thermodynamically
favorable in the presence of all molecules studied here, the heat
of bond dissociation varies with the additive molecule (see
Figures 9 and 10). The presence of VC or FEC not only
increases the energy barrier but also lowers the free energy (by
∼2.5 kcal/mol) released upon bond dissociation, making this
bond dissociation thermodynamically even more unfavorable.
On the other hand, in the presence of a PC molecule, the heat
of the bond dissociation increases by ∼1 kcal/mol making the
bond dissociation slightly more favorable.
Reaction pathways discussed above lead to the formation of
anion radicals which undergo secondary termination reactions
similar to the monomer reactions discussed in the previous
section. Among many different reaction possibilities, the attack
of an excess electron on an anion radical to generate a
carbonate anion and to release an ethylene molecule is the most
prominent one. Thermodynamic data corresponding to this
reaction in the presence of the additive molecules are also
shown in Figure 9. These data suggest that the dissociation of
the second CEOC bond of an EC anion radical is mostly
exothermic in the presence of a PC molecule, followed by EC,
VC, and finally FEC.
3.8. Preferential Decomposition of the Additive
Molecules. In addition to the decomposition of EC discussed
above, reductive decompositions of other molecules (i.e.,
additive) in a dimer are also plausible. In fact, the
decomposition of additive molecules is considered to be the
primary mechanism of solvent protection by the additives.18
When a dimer is reduced, an excess electron is more likely to
localize on the molecule with a higher reduction potential, and
by this virtue, the additive molecules, instead of the solvent EC
molecule in the dimer, undergo reduction-induced decom-
position. The thermochemistry of such decomposition
reactions is also shown in Figure 9. From the single molecule
DOI: 10.1021/acs.chemmater.6b03403
Chem. Mater. 2016, 28, 8930−8941
Chemistry of Materials
decomposition studies, it is evident that the homolytic
dissociations of both CEOC and CCOC bonds are thermody-
namically feasible in the 1e reduction state of VC and FEC but
not of EC. We have also shown that CEOC bond dissociation is
likely to occur in reduction state A, while CCOC bond
dissociation is favored in reduction state B. Keeping this in
mind, we have investigated both bond dissociations starting
from their preferred reduction states.
For the EC−VC dimer reduction, localization of the excess
electron over the carbonyl group of the VC (as seen in the
reduction of VC in state B) gives the most stable structure
(shown in [iii] of Figure 8a) compared to the other two
possibilities ([i] and [ii] in Figure 8a). The free energy barrier
for the CCOC bond dissociation of VC in this reduction state is
0.97 kcal/mol, indicating that bond dissociation will be almost
spontaneous after reduction. However, thermodynamic gain as
a result of this bond dissociation is much smaller (−2.82 kcal/
mol). In the reduction state A, dissociation of a CEOC bond is
preferred compared to the CCOC bond. However, this reaction
has a free energy barrier of ∼9.04 kcal/mol. For the same
reduction state, the free energy barrier for CEOC bond
dissociation of EC is 4.58 kcal/mol. The thermodynamic gain
as a result of the CEOC bond dissociation is −17.46 and −32.91
kcal/mol for VC and EC, respectively.
On the basis of these free energy values, it is evident that the
EC−VC dimer is most likely reduced in the reduction state B of
VC. In this reduction state, dissociation of the CCOC bond of a
VC molecule will occur almost spontaneously and the EC
molecule will remain undecomposed. This sacrificial decom-
position of the VC molecules to protect the EC molecules is in
contrast to the findings from Wang et al.17 which showed that
the VC molecules are more likely to remain intact due to the
large free energy barrier for their decomposition. Due to this
higher free energy barrier, if the dimer is reduced in the
reduction state A, the CEOC bond dissociation of EC is
kinetically preferred. We suggest this discrepancy is because
Wang et al. only considered the dissociation of the CEOC
bond.17 Our calculations also show that C E O C bond
dissociation has a higher free energy barrier but an alternative
decomposition pathway (dissociation of CCOC bond) is more
likely to occur due to the smaller barrier.
Like the EC−VC dimer, reduction of a EC−FEC dimer gives
the most stable structure ([iii] in Figure 8a) if localization of
the excess electron occurs over the carbonyl group of FEC (as
seen in the reduction of FEC in state B). Due to the small free
energy barrier for CCOC bond dissociation in this reduction
state, spontaneous dissociation of the CCOC bond occurs in
FEC if the excess electron is localized to form reduction state B.
In comparison, the free energy barrier for CEOC bond
dissociation of FEC is 7.76 kcal/mol, while it is 4.78 kcal/
mol for the CEOC bond dissociation of EC in the reduction
state A of this EC−FEC dimer. This suggests that, in the
reduction state A, EC can also undergo bond dissociation,
further evidence opposing the conventional belief that only
additive molecules decompose first. However, since the
reduction potential of reduction state A is lower compared to
reduction state B, dissociation of the FEC remains the more
thermodynamically favorable pathway of dimer decomposition.
4. DISCUSSION AND CONCLUSIONS
We have characterized the reductive decomposition of EC, VC,
and FEC by computing the reduction potentials, the free
energy barriers for decomposition, and heats of bond
8939
Article
dissociation. Several experiments have demonstrated reduction
potentials of EC-based electrolytes in the range of 0.4 to 0.7 eV
for different anode materials.19,44,45 Komaba et al. observed
electrochemical decompositions at 0.7 eV vs Na+/Na (2.41 eV
physical scale) for the PC−FEC-based electrolyte.44 The
reduction potential of an EC molecule (52.65 kcal/mol or
2.28 eV), computed in our calculations, is in good agreement
with these experiments. Using DFT calculations with the same
exchange functional, the reduction potential of EC in LIBs was
calculated to be 45.8 kcal/mol. In addition to a higher tendency
for reduction, the barrier for the ring opening is smaller in both
the 1e and 2e reduction states of EC in SIBs as opposed to
LIBs. In the 2e reduction state, EC decomposes without any
barriers in SIB while there is a small barrier of ∼2.0 kcal/mol in
LIBs. Similarly, the decomposition barrier in the preferred 1e
reduction state of EC−Na+ is smaller (4.50 kcal/mol) than for
the preferred reduction state of EC−Li+ (9.5 kcal/mol). These
results suggest that EC molecules decompose rapidly during
the initial phase of SEI formation through a CCOE dissociation
after the 2e electron reduction. Such decomposition leads to an
initial deposition of polymeric compounds on the anode surface
which then slows electron transfer to the electrolytes.46Under
these circumstances, the 1e electron reduction mechanism
dominates SEI formation. As shown earlier, the 1e induced
decomposition leads to the formation of sodium carbonates
(−CO3) or sodium alkyl carbonates. A recent study has
suggested that the chemical stability of the decomposition
products can further change the characteristics of the SEI.37
Keeping this in mind, we have investigated the chemical
stability of two major decomposition products Na2BDC and
Na2EDC against radical attack. Our calculations suggest (see
the Supporting Information) that the interaction of the OH
radical with one of the sodium ions of Na2BDC considerably
weakens the C1−O1 bond compared to the bare Na2BDC
molecule, and only 4.82 kcal/mol energy is needed to break this
bond. This homolytic dissociation results in the formation of a
new radical OC2H4CO3 and CO2. In the case of Na2EDC, the
same bond-dissociation reaction is even exothermic and −9.62
kcal/mol is released upon homolytic dissociation of the C1−
O1 bond. These new radicals will interact with other solvent
molecules initiating additional decomposition reactions and
contribute to additional SEI growth. In comparison, lithium
counterparts of the same salts are more stable and bond
dissociation energies for the homolytic dissociation of the C1−
O1 bond is 7.43 kcal/mol for Li2EDC and 3.92 kcal/mol for
Li2BDC. These results suggest that alkyl carbonate salts in SIBs
will decompose easily in the vicinity of radicals and have higher
propensity for decomposition than in LIBs. This is consistent
with the experimental observations of thicker SEI in SIBs. In
addition, two distinct reduction states (A and B) were identified
for all monomers and these reduction states have preferences
over which bond is likely to dissociate after reduction.
Dissociation of the CEOC bond (preferred in state A) is more
likely to produce carbonate salts while dissociation of the CCOC
bond (preferred in state B) is more like to produce molecules
containing the −O−R−O− group. We have also shown that
the preferred reduction state of EC changes from A to B in the
presence of additives (Figure 8b); this suggests that additives
may also change the decomposition products by changing the
preferred reduction state. Additional studies involving explicit
solvent molecules with different proportions of additive
molecules are needed to further investigate this aspect.
DOI: 10.1021/acs.chemmater.6b03403
Chem. Mater. 2016, 28, 8930−8941
Chemistry of Materials
Free energy of solvation of sodium ions suggests that additive
molecules are more likely to be present as individual molecules
rather than in a solvation shell with EC molecules. The
reductive decomposition of individual additive molecules such
as VC and FEC in bulk EC solvent show that not only are the
reduction potentials of both VC and FEC molecules higher
than that of the EC (55.96 kcal/mol for VC and 58.47 kcal/mol
for FEC), but also the barrier for the ring opening through the
CCOC bond dissociation along its most probable pathway is
small compared to the barrier for the EC ring opening. This
leads to early decomposition of both molecules. Intermediate
products generated from the dissociation of CCOC bonds are
very susceptible to oligomerization and are more likely to form
oxygen-rich polymeric compounds.32 In addition, the decom-
position of FEC generates NaF which is a very good passivating
agent. Not only do the additive molecules decompose first, but
also the decomposition pathways of EC molecules are affected.
The reduction potential of the EC increases in the presence of
both VC and FEC, indicating EC molecules will be easily
reduced in the vicinity of these additive molecules. However,
the free energy barrier to the ring opening also increases and
makes reductive decomposition kinetically unfavorable.
In summary, several aspects of the reductive decomposition
of cyclic carbonates in SIB have been studied to explain
experimentally observed characteristics of SEI in SIBs. In
addition, a new pathway to tailor SEI composition by changing
the preferred reduction states of electrolyte molecules has been
elucidated. More detailed studies involving electrolyte salt
molecules and the anode surface will shed additional light and
will be the subject of future research.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.chemma-
ter.6b03403.
Energetics for the decomposition reactions of Na2EDC
and Na2BDC with and without OH radical (PDF)
■ AUTHOR INFORMATION
ORCID
Hemant Kumar: 0000-0003-4339-5711
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work is supported by the Grants EFMA-542879, CMMI-
1363203, and CBET-1235870 from the US National Science
Foundation.
■
REFERENCES
(1) Yabuuchi, N.; Kubota, K.; Dahbi, M.; Komaba, S. Research
Development on Sodium-Ion Batteries. Chem. Rev. 2014, 114, 11636−
11682.
(2) Xu, K. Electrolytes and Interphases in Li-Ion Batteries and
Beyond. Chem. Rev. 2014, 114, 11503−11618.
(3) Zhang, Q.; Pan, J.; Lu, P.; Liu, Z.; Verbrugge, M. W.; Sheldon, B.
W.; Cheng, Y. T.; Qi, Y.; Xiao, X. Synergetic Effects of Inorganic
Components in Solid Electrolyte Interphase on High Cycle Efficiency
of Lithium Ion Batteries. Nano Lett. 2016, 16, 2011−2016.
(4) Shi, S.; Qi, Y.; Li, H.; Hector, L. G. Defect Thermodynamics and
Diffusion Mechanisms in Li2CO 3 and Implications for the Solid
8940
Article
Electrolyte Interphase in Li-Ion Batteries. J. Phys. Chem. C 2013, 117,
8579−8593.
(5) Slater, M. D.; Kim, D.; Lee, E.; Johnson, C. S. Sodium-Ion
Batteries. Adv. Funct. Mater. 2013, 23, 947−958.
(6) Philippe, B.; Valvo, M.; Lindgren, F.; Rensmo, H.; Edström, K.
Investigation of the Electrode/Electrolyte Interface of Fe 2 O 3
Composite Electrodes: Li vs Na Batteries. Chem. Mater. 2014, 26,
5028−5041.
(7) Muñoz-Márquez, M. A.; Zarrabeitia, M.; Castillo-Martínez, E.;
Eguía-Barrio, A.; Rojo, T.; Casas-Cabanas, M. Composition and
Evolution of the Solid-Electrolyte Interphase in Na 2 Ti 3 O 7
Electrodes for Na-Ion Batteries: XPS and Auger Parameter Analysis.
ACS Appl. Mater. Interfaces 2015, 7, 7801−7808.
(8) Weadock, N.; Varongchayakul, N.; Wan, J.; Lee, S.; Seog, J.; Hu,
L. Determination of Mechanical Properties of the SEI in Sodium Ion
Batteries via Colloidal Probe Microscopy. Nano Energy 2013, 2, 713−
719.
(9) Cheng, X.-B.; Zhang, R.; Zhao, C.-Z.; Wei, F.; Zhang, J.-G.;
Zhang, Q. A Review of Solid Electrolyte Interphases on Lithium Metal
Anode. Adv. Sci. 2016, 3, 1500213.
(10) Baggetto, L.; Ganesh, P.; Meisner, R. P.; Unocic, R. R.; Jumas, J.
C.; Bridges, C. a.; Veith, G. M. Characterization of Sodium Ion
Electrochemical Reaction with Tin Anodes: Experiment and Theory. J.
Power Sources 2013, 234, 48−59.
(11) Iermakova, D. I.; Dugas, R.; Palacín, M. R.; Ponrouch, A. On the
Comparative Stability of Li and Na Metal Anode Interfaces in
Conventional Alkyl Carbonate Electrolytes. J. Electrochem. Soc. 2015,
162, A7060−A7066.
(12) Komaba, S.; Murata, W.; Ishikawa, T.; Yabuuchi, N.; Ozeki, T.;
Nakayama, T.; Ogata, A.; Gotoh, K.; Fujiwara, K. Electrochemical Na
Insertion and Solid Electrolyte Interphase for Hard-Carbon Electrodes
and Application to Na-Ion Batteries. Adv. Funct. Mater. 2011, 21,
3859−3867.
(13) Ponrouch, A.; Dedryvere, R.; Monti, D.; Demet, A. E.; Ateba
Mba, J. M.; Croguennec, L.; Masquelier, C.; Johansson, P.; Palacin, M.
R. Towards High Energy Density Sodium Ion Batteries through
Electrolyte Optimization. Energy Environ. Sci. 2013, 6, 2361−2369.
(14) Leung, K.; Rempe, S. B.; Foster, M. E.; Ma, Y.; Martinez del la
Hoz, J. M.; Sai, N.; Balbuena, P. B. Modeling Electrochemical
Decomposition of Fluoroethylene Carbonate on Silicon Anode
Surfaces in Lithium Ion Batteries. J. Electrochem. Soc. 2014, 161,
A213−A221.
(15) Shkrob, I. A.; Wishart, J. F.; Abraham, D. P. What Makes
Fluoroethylene Carbonate Different? J. Phys. Chem. C 2015, 119,
14954−14964.
(16) El Ouatani, L.; Dedryvère, R.; Siret, C.; Biensan, P.; Reynaud, S.;
Iratçabal, P.; Gonbeau, D. The Effect of Vinylene Carbonate Additive
on Surface Film Formation on Both Electrodes in Li-Ion Batteries. J.
Electrochem. Soc. 2009, 156, A103.
(17) Wang, Y.; Nakamura, S.; Tasaki, K.; Balbuena, P. B. Theoretical
Studies to Understand Surface Chemistry on Carbon Anodes for
Lithium-Ion Batteries: How Does Vinylene Carbonate Play Its Role as
an Electrolyte Additive? J. Am. Chem. Soc. 2002, 124, 4408−4421.
(18) Kim, S.-P.; van Duin, A. C. T.; Shenoy, V. B. Effect of
Electrolytes on the Structure and Evolution of the Solid Electrolyte
Interphase (SEI) in Li-Ion Batteries: A Molecular Dynamics Study. J.
Power Sources 2011, 196, 8590−8597.
(19) Ji, L.; Gu, M.; Shao, Y.; Li, X.; Engelhard, M. H.; Arey, B. W.;
Wang, W.; Nie, Z.; Xiao, J.; Wang, C.; Zhang, J. G.; Liu, J. Controlling
SEI Formation on SnSb-Porous Carbon Nanofibers for Improved Na
Ion Storage. Adv. Mater. 2014, 26, 2901−2908.
(20) Shkrob, I. a.; Zhu, Y.; Marin, T. W.; Abraham, D. Reduction of
Carbonate Electrolytes and the Formation of Solid-Electrolyte
Interface (SEI) in Lithium-Ion Batteries. 1. Spectroscopic Observa-
tions of Radical Intermediates Generated in One-Electron Reduction
of Carbonates. J. Phys. Chem. C 2013, 117, 19255−19269.
(21) Bhide, A.; Hofmann, J.; Katharina Dürr, A.; Janek, J.; Adelhelm,
P. Electrochemical Stability of Non-Aqueous Electrolytes for Sodium-
DOI: 10.1021/acs.chemmater.6b03403
Chem. Mater. 2016, 28, 8930−8941
Chemistry of Materials Article

Ion Batteries and Their Compatibility with Na 0.7 CoO 2. Phys. Chem. (39) Borodin, O.; Bedrov, D. Interfacial Structure and Dynamics of
Chem. Phys. 2014, 16, 1987−1998. the Lithium Alkyl Dicarbonate SEI Components in Contact with the
(22) Singh, G.; Aguesse, F.; Otaegui, L.; Goikolea, E.; Gonzalo, E.; Lithium Battery Electrolyte. J. Phys. Chem. C 2014, 118, 18362−18371.
Segalini, J.; Rojo, T. Electrochemical Performance of NaFex- (40) von Cresce, A.; Xu, K. Preferential Solvation of Li+ Directs
(Ni0.5Ti0.5)1−xO2 (X = 0.2 and X = 0.4) Cathode for Sodium-Ion Formation of Interphase on Graphitic Anode. Electrochem. Solid-State
Battery. J. Power Sources 2015, 273, 333−339. Lett. 2011, 14, A154.
(23) Ming, J.; Ming, H.; Yang, W.; Kwak, W.-J.; Park, J.-B.; Zheng, J.; (41) Von Wald Cresce, A.; Gobet, M.; Borodin, O.; Peng, J.; Russell,
Sun, Y.-K. A Sustainable Iron-Based Sodium Ion Battery of Porous S. M.; Wikner, E.; Fu, A.; Hu, L.; Lee, H. S.; Zhang, Z.; Yang, X. Q.;
carbon−Fe3O4/Na2FeP2O7 with High Performance. RSC Adv. 2015, Greenbaum, S.; Amine, K.; Xu, K. Anion Solvation in Carbonate-Based
5, 8793−8800. Electrolytes. J. Phys. Chem. C 2015, 119, 27255−27264.
(24) Mortazavi, M.; Wang, C.; Deng, J.; Shenoy, V. B.; Medhekar, N. (42) Takamatsu, D.; Orikasa, Y.; Mori, S.; Nakatsutsumi, T.;
V. Ab Initio Characterization of Layered MoS2 as Anode for Sodium- Yamamoto, K.; Koyama, Y.; Minato, T.; Hirano, T.; Tanida, H.;
Arai, H.; Uchimoto, Y.; Ogumi, Z. Effect of an Electrolyte Additive of
Ion Batteries. J. Power Sources 2014, 268, 279−286.
Vinylene Carbonate on the Electronic Structure at the Surface of a
(25) Lee, J.; Chen, Y.-M.; Zhu, Y.; Vogt, B. D. Tuning SEI Formation
Lithium Cobalt Oxide Electrode under Battery Operating Conditions.
on Nanoporous Carbon−titania Composite Sodium Ion Batteries
J. Phys. Chem. C 2015, 119, 9791−9797.
Anodes and Performance with Subtle Processing Changes. RSC Adv. (43) Chen, L.; Wang, K.; Xie, X.; Xie, J. Effect of Vinylene Carbonate
2015, 5, 99329−99338. (VC) as Electrolyte Additive on Electrochemical Performance of Si
(26) Schmidt, M. W.; Baldridge, K. K.; Boatz, J. A.; Elbert, S. T.; Film Anode for Lithium Ion Batteries. J. Power Sources 2007, 174,
Gordon, M. S.; Jensen, J. H.; Koseki, S.; Matsunaga, N.; Nguyen, K. A.; 538−543.
Su, S.; Windus, T. L.; Dupuis, M.; Montgomery, J. A. General Atomic (44) Komaba, S.; Ishikawa, T.; Yabuuchi, N.; Murata, W.; Ito, A.;
and Molecular Electronic Structure System. J. Comput. Chem. 1993, 14, Ohsawa, Y. Fluorinated Ethylene Carbonate as Electrolyte Additive for
1347−1363. Rechargeable Na Batteries. ACS Appl. Mater. Interfaces 2011, 3, 4165−
(27) Han, Y. K.; Lee, S. U. Performance of Density Functional for 4168.
Calculation of Reductive Ring-Opening Reaction Energies of Li+-EC (45) Han, M. H.; Gonzalo, E.; Singh, G.; Rojo, T. A Comprehensive
and Li+-VC. Theor. Chem. Acc. 2004, 112, 106−112. Review of Sodium Layered Oxides: Powerful Cathodes for Na-Ion
(28) Li, H. Quantum Mechanical/molecular Mechanical/continuum Batteries. Energy Environ. Sci. 2015, 8, 81−102.
Style Solvation Model: Linear Response Theory, Variational Treat- (46) Ponrouch, A.; Dedryvère, R.; Monti, D.; Demet, A. E.; Ateba
ment, and Nuclear Gradients. J. Chem. Phys. 2009, 131, 184103. Mba, J. M.; Croguennec, L.; Masquelier, C.; Johansson, P.; Palacín, M.
(29) Tasaki, K. Solvent Decompositions and Physical Properties of R. Towards High Energy Density Sodium Ion Batteries through
Decomposition Compounds in Li-Ion Battery Electrolytes Studied by Electrolyte Optimization. Energy Environ. Sci. 2013, 6, 2361.
DFT Calculations and Molecular Dynamics Simulations. J. Phys. Chem.
B 2005, 109, 2920−2933.
(30) Ho, J.; Ertem, M. Z. Calculating Free Energy Changes in
Continuum Solvation Models. J. Phys. Chem. B 2016, 120, 1319−1329.
(31) Wang, Y.; Nakamura, S.; Ue, M.; Balbuena, P. B. Theoretical
Studies to Understand Surface Chemistry on Carbon Anodes for
Lithium-Ion Batteries: Reduction Mechanisms of Ethylene Carbonate.
J. Am. Chem. Soc. 2001, 123, 11708−11718.
(32) Leung, K. Two-Electron Reduction of Ethylene Carbonate: A
Quantum Chemistry Re-Examination of Mechanisms. Chem. Phys. Lett.
2013, 568−569, 1−8.
(33) Shkrob, I. A.; Zhu, Y.; Marin, T. W.; Abraham, D. Reduction of
Carbonate Electrolytes and the Formation of Solid-Electrolyte
Interface (SEI) in Lithium-Ion Batteries. 2. Radiolytically Induced
Polymerization of Ethylene Carbonate. J. Phys. Chem. C 2013, 117,
19270−19279.
(34) Ushirogata, K.; Sodeyama, K.; Okuno, Y.; Tateyama, Y. Additive
Effect on Reductive Decomposition and Binding of Carbonate-Based
Solvent toward Solid Electrolyte Interphase Formation in Lithium-Ion
Battery. J. Am. Chem. Soc. 2013, 135, 11967−11974.
(35) Okuno, Y.; Ushirogata, K.; Sodeyama, K.; Tateyama, Y.
Decomposition of the Fluoroethylene Carbonate Additive and the
Glue Effect of Lithium Fluoride Products for the Solid Electrolyte
Interphase: An Ab Initio Study. Phys. Chem. Chem. Phys. 2016, 18,
8643−8653.
(36) Mogi, R.; Inaba, M.; Iriyama, Y.; Abe, T.; Ogumi, Z. Study of the
Decomposition of Propylene Carbonate on Lithium Metal Surface by
Pyrolysis-Gas Chromatography-Mass Spectroscopy. Langmuir 2003,
19, 814−821.
(37) Soto, F. A.; Ma, Y.; Martinez De La Hoz, J. M.; Seminario, J. M.;
Balbuena, P. B. Formation and Growth Mechanisms of Solid-
Electrolyte Interphase Layers in Rechargeable Batteries. Chem.
Mater. 2015, 27, 7990−8000.
(38) Yamada, Y.; Iriyama, Y.; Abe, T.; Ogumi, Z. Kinetics of Lithium
Ion Transfer at the Interface between Graphite and Liquid
Electrolytes: Effects of Solvent and Surface Film. Langmuir 2009, 25,
12766−12770.

8941 DOI: 10.1021/acs.chemmater.6b03403

Chem. Mater. 2016, 28, 8930−8941