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Computational Studies of Solubilities of LiO2 and Li2O2 in Aprotic

Solvents
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E3696 Journal of The Electrochemical Society, 164 (11) E3696-E3701 (2017)

JES FOCUS ISSUE ON MATHEMATICAL MODELING OF ELECTROCHEMICAL SYSTEMS AT MULTIPLE SCALES IN HONOR OF JOHN NEWMAN
Computational Studies of Solubilities of LiO2 and Li2 O2 in Aprotic
Solvents
Lei Cheng,a,b,z Paul Redfern,b Kah Chun Lau,a,b,c Rajeev S. Assary,a,b Badri Narayanan,a,b
and Larry A. Curtissa,b,z
a Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA
b Joint Center for Energy Storage Research, Argonne National Laboratory, Argonne, Illinois 60439, USA
c Department of Physics and Astronomy, California State University, Northridge, California 91330, USA

Knowledge of the solubilities of Li2 O2 and LiO2 in aprotic solvents is important for insight into the discharge and charge processes
of Li-O2 batteries, but these quantities are not well known. In this contribution, the solvation free energies of molecular LiO2 and
Li2 O2 in various organic solvents were calculated using various explicit and implicit solvent models, as well as ab initio molecular
dynamics (AIMD) methods. The solvation energies from these calculations along with calculated lattice energies of Li2 O2 and
LiO2 were used to determine the solubility of bulk LiO2 and Li2 O2 . The computed solubility of LiO2 (1.8 × 10−2 M) is about
15 orders higher than that of Li2 O2 (2.0 × 10−17 M) due to a much less negative lattice energy of bulk LiO2 compared to that of
Li2 O2 . The difference in solubilities between LiO2 and Li2 O2 likely will affect the nucleation and growth mechanisms and resulting
morphologies of the products formed during battery discharge, influencing the performance of the battery cell. The calculated LiO2
and Li2 O2 solubilities provide important information for fundamental studies of discharge and charge chemistries in Li-O2 batteries.
© The Author(s) 2017. Published by ECS. This is an open access article distributed under the terms of the Creative Commons
Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/),
which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any
way and is properly cited. For permission for commercial reuse, please email: oa@electrochem.org. [DOI: 10.1149/2.0721711jes]
All rights reserved.

Manuscript submitted April 3, 2017; revised manuscript received August 4, 2017. Published August 12, 2017. This paper is part of
the JES Focus Issue on Mathematical Modeling of Electrochemical Systems at Multiple Scales in Honor of John Newman.

Lithium-O2 battery technology has received much research inter-
est due to its high theoretical gravimetric energy density compared to
conventional Li-ion batteries.1 The system uses oxidation of lithium
at the anode and reduction of oxygen at the cathode to induce a cur-
rent flow. Depending on the reaction kinetics of different discharge
mechanisms, the discharge products are generally composed of Li2 O2
with a low solubility and in some cases different ratios of LiO2 and
Li2 O2 .2–6 Much of research focus has been on the cathode. One of
the challenges of Li-O2 batteries is the incomplete utilization of the
active materials due to the insulating nature of the discharge prod-
ucts and the clogging the porous carbon cathode. The formation of
these products may involve a nucleation and growth mechanism from
the solution phase.2,7–13 Nazar reported a Li2 O2 formation mecha-
nism by disproportionation reaction of a limited amount of LiO2 in
solution.2 A through-solution mechanism was also proposed involving
heterogeneous nucleation from a supersaturated solution of LiO2 .10
There is other evidence that LiO2 is soluble in the electrolyte prior
to deposition on the surface based on a quartz microbalance study.14
Results from several research groups suggest that the composition
and morphology of the discharge products have a significant effect on
charging overpotential and rechargeability of the Li-O2 battery.10,15,16
Therefore, understanding the chemistry and growth mechanism of
discharge products in the cell is crucial for improving Li-O2 battery.
The study and modeling of nucleation and crystal growth requires
knowledge of bulk solubility.17,18 However, there are limited experi-
mental solubility measurements reported in the literature on discharge
products LiO2 and Li2 O2 . Solubility also highly depends on the size
and morphologies of the solid as well as impurities so the values will
depend on the experimental conditions.
The solubility of Li2 O2 has been reported in various studies; how-
ever, the values cover a very wide range. Lodge et al.19 reported a
solubility product constant of Li2 O2 of 10−51 in a pyrrolidinium-based
ionic liquid, which corresponds to a solubility of 10−17 M. This low
solubility of Li2 O2 is consistent with the value found in the Handbook
of Inorganic Compounds20 where Li2 O2 is reported to be insoluble
in ethanol. In contrast, there have been other reports of much larger
solubilities for Li2 O2 . The Li2 O2 solubility in 0.1 M LiTFSI/DMSO
z
E-mail: leicheng@anl.gov; curtiss@anl.gov
solution was measured to be 2.5 mM using ionic-coupled plasma
mass spectroscopy,21 <0.2 mM in dimethyl formamide,22 1 mM in
acetronitrile/propylene carbonate mixture23 and 0.02 mM in propylene
carbonate and dimethyl carbonate mixture.24 The reason for the wide
range of values for the solubility is unclear. The solubility of LiO2
has not been reported in literature since it is inherently unstable and
quickly disproportionates under ambient condition. However, Lodge
et al.19 estimated a solubility product of greater than 10−15 based on
electrochemical measurements, which would correspond to a solubil-
ity of greater than 10−7 M. Also, a recent mesoscale model study of
Li-O2 discharge product growth used a LiO2 solubility of 1 mM to suc-
cessfully simulate particle size evolution observed experimentally.18
Predicting solubility using ab initio computational methods is chal-
lenging due to the difficulties of modeling both crystalline and solution
phases. In this paper we report on density functional calculations of
the solvation free energies of Li2 O2 and LiO2 to provide theoretical
predictions of solubility of these species, for which there is con-
flicting experimental data. The solvation energies were calculated in
dimethoxyethane (DME), a common solvent used in Li-O2 battery
that has been shown with improved performance, as a model solvent
using implicit and a mixed explicit solvent and implicit model, as well
as benchmark results from ab initio molecular dynamics (AIMD) sim-
ulations. These values are then used along with calculated bulk lattice
energies to obtain solubilities of bulk LiO2 and Li2 O2 using a ther-
modynamic cycle. We also make predictions of solubilities for a large
number of solvent molecules with differing dielectric constants. In
section Computational methods we present the quantum mechanical
methods used for energy calculations. In section Calculation of solu-
bility we discuss the method used to determine solubility, including
the models used for the calculation of the solvation energy and the
derivation of sublimation energies. In section Results and discussion
the results for the solvation energies and solubilities are given along
with an assessment of the different solvation models used. Finally,
comparison with experiment is discussed.
Computational Methods
All density functional theory (DFT) and MP2 calculations on
solvated Li2 O2 and LiO2 clusters were done with Gaussian 09.25
 Journal of The Electrochemical Society, 164 (11) E3696-E3701 (2017)
Structures were optimized at the B3LYP/6-31G(2df,p) level and fre-
quencies were scaled by 0.9854 as in G4(MP2) theory. Single-point
calculations with PBE/6-31G(2df,p) were performed at the B3LYP
geometries for comparison. The PCM,26 CPCM,27,28 and SMD29 con-
tinuum solvation models implemented in Gaussian09 were used to
calculate solvation energies implicitly. Single-point MP2 calculations
were done in addition to the DFT calculations. The MP2 calculations
were done with frozen core according to the G4 convention30 using
the G3MP2LargeXP basis set as in G4(MP2) theory.30
AIMD calculations were done using DFT methods with plane
wave basis sets as implemented in the VASP code.31–34 All the cal-
culations were spin-polarized and carried out using the gradient cor-
rected exchange-correlation functional of Perdew, Burke and Ernzer-
hof (PBE)35 under the projector augmented wave (PAW)36,37 method,
with plane wave basis sets up to a kinetic energy cutoff of 300 eV to
accommodate the large number of atoms (up to 324 in the simulation).
A comparison of total radial distribution function vs radial distance
calculated using 300 eV and 400 eV shows that the lower cutoff energy
is sufficient for the system (Figure S4). The PAW method was used to
represent the interaction between the core and valence electrons, and
the Kohn-Sham valence states (i.e. 1s for H, 2s for Li, 2s 2p for C and
O) are expanded in plane wave basis sets. The convergence criterion
of the total energy was set to be within 1 × 10−4 eV within a single
K-point grid (i.e. -point). For the simulations, supercells of 12.0 Å
× 12.0 Å × 12.0 Å containing 10 DME molecules and 15.0 Å ×
15.0 Å × 15.0 Å containing 20 dimethyoxyethane (DME) molecules
are adopted throughout the work. The DME densities corresponding
to such a model are ∼0.88 and 0.90 g/cm3 , respectively, close to
the reported DME solvent density, i.e. 0.87 g/cm3 . To investigate the
thermodynamic stability of the system at room temperature, the 20
DME solvent molecules were initially randomly arranged inside the
simulation box and were then thermally equilibrated at T = 300 K for
about 2 ps using AIMD simulations based on an NVT-ensemble with
a time step of 1 fs. For the production run, the sampling is obtained
from a 4 ps AIMD simulation run.
Calculations of Solubility
Solubility is determined by the intrinsic stability of the species in
its solid form and solvation by the particular solution. The solubility
of substance A (S A ) can be calculated using the following equation:38
G ∗dissolution,A = G ∗sub,A + G ∗solv,A = −RT ln(S A V A ),
where the dissolution free energy G ∗dissolution,A is the summation of
sublimation free energy G ∗sub,A and solvation free energy G ∗solv,A .
This is a thermodynamic cycle in which molecules of the crystal are
first sublimed into the gas phase and then dissolved in the solvent.
The G ∗sub,A is the free energy change of one unit of A dissociating
from a bulk entity and it is typically endothermic. The G ∗solv,A is the
solvation free energy of one unit of A and can be calculated using either
an implicit continuum model, or an explicit solvent model where the
solvent-solute interaction is calculated using ab initio methods. The
computational details of these two terms are discussed further below.
R and T are the gas constant and the temperature, respectively. S A and
V A are the solubility (mol/L) and the molar volume (L/mol) of A in
its solid structure, respectively. The molar volume V A of LiO2 in this
work was obtained from a theoretical crystal structure39 since there is
no available experimental data in literature due to the instability of the
structure under normal condition, and that of Li2 O2 from the density
and molecular weight.
Solvation energy.—In this work, we use both implicit and explicit
models to calculate solvation free energies of LiO2 and Li2 O2 in DME.
With implicit solvation models, the free energy of the molecule in so-
lution can be calculated directly from a dielectric continuum model.
The solvation energy is calculated by subtracting the gas phase elec-
tronic energy from the energy in solution. In the continuum models,
because DME is not a standard solvent for the method, we specified
E3697
the solvent as dichloroethane which has the same shape as DME,40
and the dielectric constant is the literature value of 7.2.
With the explicit models including 1∼4 DME solvent molecules,
several different cluster structures constructed based on chemical in-
tuition of the molecular interactions were tried and the lowest energy
ones were used. It has been shown before that the complete of the first
solvation shell is satisfactory for calculating solvation free energies of
lithium-oxygen species.41 Since 4 DME molecules complete the first
solvation, we did not calculate structures with more than 4 solvent
molecules. These structures are shown in Figure 1. The first solvation
shell of the Li2 O2 from a snapshot from AIMD is also shown in Figure
1. Two different thermodynamic cycles, the monomer cycle and the
cluster cycle,41,42 were used to derive the solvation free energy. The
two models use different reference energies. In the monomer cycle
the solute is treated as binding to n solvent molecules while in the
cluster cycle the solute binds to a cluster of n solvent molecules. Cor-
rection factors are added so that all reactants and products are in the
same standard states, namely 1 M ideal gas and 1 M solution. For the
monomer cycle, the solvation free energy is calculated as:
G ∗solv,A = G obind,g,A + G ∗solv,[A(D M E)n] − nG ∗solv,D M E
−n RT ln C D M E − nG o−>∗
where G obind,g,A is the gas phase binding free energy between the
solute and n DME molecules. Solvation free energies of the solute A
with n surrounding explicit solvent DME molecules G ∗solv,[A(D M E)n]
and the solvation energy of DME molecule G ∗solv,D M E were calcu-
lated with PCM by subtracting the gas phase electronic energy from
the corresponding SCRF energy.C D M E is the concentration of 1 mol
of DME and it is 9.6 mol/L. G o−>∗ is the free energy change to
convert one mol of ideal gas from 1 atmosphere (24.46 L/mol) to 1M
(1mol/L), which is 1.9 kcal/mol at 298 K.42 For all continuum models
used (PCM, CPCM and SMD), this G o−>∗ correction is added.
For the cluster cycle, the solvation free energy is:
G ∗solv,A = G obind,g,A + G ∗solv,[A(D M E)n] − G ∗solv,(D M E)n
−RT ln(C D M E /n) − nG o−>∗
where G ∗solv,(D M E)n is the solvation energy of a cluster of DME sur-
rounding the solute calculated using a continuum model and C D M E /n
is the concentration of the solvent cluster.
We also calculated the solvation energy using the AIMD method.
The computed solvation energy is approximated as the formation en-
∗
ergy E solv,A (T ) from direct AIMD sampling at a given temperature
(T) defined as the following:
∗
E solv,A (T ) = E sol(D
tot
M E,A) (avg, T ) − E sol(D M E) (avg, T )
tot
−E tot
A (avg, T )
tot
where E sol(D M E,A) (avg, T ) is the statistical average of the total energy
of a solution from AIMD sampling of the solute A with 10 or 20
surrounding DME solvent molecules thermally equilibrated at T =
tot tot
298 K. Similarly, the E sol(D M E) (avg, T ) and E A (avg, T ) are the total
energies of a solution from AIMD sampling of the 10 or 20 DME
solvent molecules and one A solute molecule thermally equilibrated
at T = 298 K, respectively. More statistical information on the AIMD
simulations can be found in the Supplemental Materials. In this work,
we compared all other methods against the AIMD results as the model
captures more complete solvation shell information and thus is the
most physical and likely the most accurate. It has also been shown in
literature that the solvation energies calculated using PBE AIMD are
in good agreement with the experimental values.43
Sublimation energy.—The standard sublimation free energy
G osub,A must be corrected for isothermal expansion of an ideal gas:42
G ∗sub,A = G osub,A − RT ln(V A Po /RT )
where Po is the standard condition pressure. Molar volumes V A for
LiO2 and Li2 O2 are 0.0173 and 0.0199 L/mol, respectively.
E3698 Journal of The Electrochemical Society, 164 (11) E3696-E3701 (2017)
Figure 1. Optimized structures of LiO2 and Li2 O2 interacting with 1∼4 dimethoxy ethane (DME) molecules DMEs. A structure of Li2 O2 interacting with 6
DME molecules (Li2 O2 . . . 6DME) obtained from a snapshop of AIMD simulation with 20 DMEs in a box is also shown.
The G osub,A of bulk is the summation of Hsub,A
o
and Ssub,A
o
. the 10 DME (Row 11) box (−40.3 vs −38.4 kcal/mol). Li2 O2 has a
The Hsub,A can be calculated according to:
o
Hsub,A
o
= −(Ulatt + 2RT )
where Ulatt is the lattice energy calculated from crystal structures de-
fined as Ulatt = (E cr
tot
ystal,A − n E mol,A )/n with E cr ystal,A being the total
tot tot
energy of the A crystal that consists of n basic A molecular units in a
tot
crystal cell, and E mol,A being the corresponding total energy of a basic
A molecular unit from a DFT calculation. Based on this relation, we
obtained −1.85 and −3.26 eV for Ulatt for LiO2 and Li2 O2 , respec-
tively. The 2RT term arises by including lattice vibrational energy and
energy of the vapor.38 The Ssub,A o
is approximated by the difference
between the rotation and translation contributions to the entropy of
the gas phase at 298 K and the intermolecular vibrational contribution
to the entropy of the crystal at 298 K. Details of these calculations
were described in a previous publication.39 With these entropy terms,
G osub,A of LiO2 and Li2 O2 , are calculated to be 1.47 and 2.83 eV,
respectively.
Results and Discussion
Calculated free energies of solvation for the various methods,
including the AIMD results, are reported in Table I with the opti-
mized structures of Li+ -DMEn cluster binding shown in Figure 1.
The B3LYP and PBE energies for the cluster cycles (Table I, Rows
5–7) and the continuum models (Row 8–10) are very comparable
(∼1 kcal/mol). With a monomer cycles (Table I, Row 1–4), the differ-
ences between G ∗solv,A with different numbers of DME molecules
are noticeable (6–12 kcal/mol for B3LYP). When clusters of DME are
used instead (cluster cycle), G ∗solv,A (Table I, Row 5–7) calculated
using different cluster sizes are more similar. However, G ∗solv,A cal-
culated using monomer cycles (Table I, Row 1–4) are in better agree-
ment with the AIMD results (Row 11–12) with the 4DME monomer
cycle (Row 4) giving the best agreement. For cluster and monomer
cycles (Table I, row 1–7), MP2 solvation energies for LiO2 are slightly
more negative than the B3LYP results except for the 1DME monomer
model (Row 1), while for Li2 O2 the MP2 energies are less negative
and the deviation is larger.
For the implicit solvation models PCM and CPCM, the results
with both DFT and MP2 methods (Table I, Row 8 and 9) are similar to
the AIMD results (Row 11 and 12), while for the SMD model (Row
10) results deviate more. This is because SMD is not parameterized
for Li. The AIMD simulations using a larger box of 20 DME (Table
I, Row 12) gives a slightly more negative G ∗solv,A for Li2 O2 than
higher (more negative) G ∗solv,A than LiO2 due to its stronger binding
to DME. Considering the computational cost, the PCM and CPCM
methods are preferable to cluster or monomer cycles for solvation
energy calculation. In addition, it is not always clear if the lowest
energy structure has been found.
Solubilities were calculated and are reported in Table II by com-
bining theoretical G ∗sub,A and G ∗solv,A as outlined in the methods
section. The AIMD solubility (Table II, Row 11 and 12) of LiO2 is 1.8
× 10−2 mol/L and that of Li2 O2 is 9.1 × 10−19 mol/L (2.0 × 10−17
mol/L with the larger 20 DME box), indicating that bulk LiO2 is more
soluble than Li2 O2 in DME. The PCM and CPCM values as well as the
monomer cycle in Table II based on 4MDE are in agreement with these
values. We note that because the solubility is an exponential function
of solvation energies, small errors in solvation energy calculation will
lead to a significant difference in the calculated absolute solubility.
Our calculations showing that Li2 O2 is very insoluble in DME and
other solvents is consistent with some studies19,20 and in disagree-
ment with others21–24 which are many orders of magnitudes larger
(details on these experimental measurements were discussed earlier).
For example, the solubility of 10−17 M reported by Lodge et al.19
and the insolubility of Li2 O2 in ethanol reported in the Handbook of
Inorganic Compouds20 are consistent with our calculated results. Our
calculations indicate that although the solvation energy of Li2 O2 is
quite large, it is the stability of Li2 O2 (large lattice energy) that makes
it insoluble. Although the solvation energies of the differing levels
of theory differ, they all are in agreement on this qualitative result
with values of 10−21 to 10−17 mol/L. The reports of large solubility of
Li2 O2 in the literature21–24 could be for several reasons. One possibil-
ity is that since Li2 O2 is known to react with H2 O, trace amounts of
water contamination in solution might result in erroneous solubility
measurement and in one case the solubility closely matched the ppm
of water reported in the solvent.22 Another possibility is that solubil-
ity measurements may depend on particle size or surface effects that
increase solubility.
As mentioned earlier, the experimental solubility of LiO2 is not
available. However, a recent investigation that uses LiO2 solubility of
1 mM to model particle growth successfully simulated the particle size
evolution observed experimentally.18 The solubility used for modeling
is close to our AIMD result of 1.8 × 10−2 mol/L, supporting our
calculation result.
Solvation free energies of Lix O2 in some other common organic
solvents with dielectrics ranging from 2 to 109 were also calculated
using the CPCM model and are reported in Table III. Also included
 Journal of The Electrochemical Society, 164 (11) E3696-E3701 (2017) E3699

Table I. Solvation free energies (kcal/mol) of molecular Lix O2 calculated using different models. For DFT calculations, 6–31G(2df,p) basis sets
were used. For MP2 calculations, the GTMP2LargeXP basis sets were used.

B3LYP/6-31(2df,p)e PBE/6-31(2df,p)f MP2/GTMP2LargeXPg

Method x=1 x=2 x=1 x=2 x=1 x=2

1 a DME + Lix O2 → DMELix O2 −35.1 −42.4 −34.0 −42.1 −30.4 −37.0
2 a 2DME + Lix O2 → DME2 LixO2 −32.9 −46.4 −34.7 −47.4 −34.2 −37.5
3 a 3DME + Li O → DME LixO −28.1 −40.2 −31.5 −44.8 −31.1 −36.5
x 2 3 2
4 a 4DME + Li O → DME LixO −23.5 −36.8 −27.6 −43.4 −29.5 −35.8
x 2 4 2
5 b DME + Li O → DME LixO −36.6 −50.1 −37.1 −49.9 −37.3 −40.5
2 x 2 2 2
6 b DME + Li O → DME LixO −36.5 −48.7 −36.6 −49.9 −38.4 −43.9
3 x 2 3 2
7 b DME + Li O → DME LixO −35.2 −48.4 −35.8 −50.2 −37.7 −43.9
4 x 2 4 2
8 c Li O PCM
x 2 −25.2 −34.7 −24.4 −34.2 −26.7 −34.6
9 c Li O CPCM
x 2 −26.4 −36.6 −25.5 −36.0 −28.1 −36.5
10 c Li O SMD
x 2 −13.9 −16.4 −13.3 −16.0 −15.2
11 d 10DME + Li O → DME Li O −29.4 −38.4
x 2 10 x 2
12 d 20DME + Li O → DME Li O −40.3
x 2 20 x 2

a Monomer model.
b Cluster model.
c Continuum model.
d AIMD.
e At B3LYP/6-31G(2df,p) optimized geometries.
f AllPBE results are with the 6–31G(2df,p) basis set at the B3LYP/6-31G(2df,p) geometries, except for the AIMD results (see text for details of those
calculations).
g At B3LYP/6-31G(2df,p) optimized geometries.

Table II. Solubilities (mol/L) of bulk Lix O2 calculated using different solvation models. For DFT calculations, 6–31G(2df,p) basis sets were used.
For MP2 calculations, the GTMP2LargeXP basis sets were used. For easy comparison, the row labels shown in the first column are consistent
with the label numbers for the same methods in Table I.

MP2/GTMP2Large
B3LYPa AIMD XP//B3LYPa

Method x=1 x=2 x=1 x=2 x=1 x=2

4 4DME + Lix O2 → DME4 Lix O2 8.8E-07 5.7E-20 2.2E-02 1.0E-20
8 Lix O2 PCM 1.5E-05 1.8E-21 2.0E-04 1.6E-21
9 Lix O2 CPCM 1.1E-04 4.2E-20 1.9E-03 3.8E-20
11 10DME + Lix O2 → DME10 Lix O2 1.8E-02 9.1E-19
12 20DME + Lix O2 → DME20 Lix O2 2.0E-17

a Using the optimized geometries at the B3LYP/6-31G(2df,p) level of theory.

Table III. Solvation free energies (kcal/mol) and solubilities (mol/L) of Lix O2 in different organic solvents calculated using B3LYP/6-31G(2df,p)
and CPCM model.

Solvation energy Solubility

Solvent Dielectric constant x=1 x=2 x=1 x=2

1,4-Dioxane 2.2 −14.9 −20.3 4.2E-13 5.0E-32
DiButylEther 3.0 −18.7 −25.6 2.4E-10 3.7E-28
Anisole 4.2 −21.7 −29.8 4.0E-08 4.7E-25
Dimethoxy ethane(DME)a 7.2 −26.4 −36.6 1.1E-04 4.2E-20
TetraHydroFuran 7.4 −25.4 −34.9 2.0E-05 2.6E-21
2,4-DiMethylPyridine 9.4 −26.5 −36.4 1.3E-04 3.3E-20
3-MethylPyridine 11.6 −27.3 −37.5 4.9E-04 2.1E-19
Pyridine 13.0 −27.6 −38.0 8.8E-04 4.7E-19
ButanoNitrile 24.3 −29.1 −40.0 1.0E-02 1.4E-17
BenzoNitrile 25.6 −29.2 −40.1 1.2E-02 1.7E-17
PropanoNitrile 29.3 −29.4 −40.4 1.7E-02 2.7E-17
Acetonitrile 35.7 −29.6 −40.8 2.6E-02 4.9E-17
n,n-DiMethylAcetamide 37.8 −29.7 −40.9 2.9E-02 5.7E-17
DiMethylSulfoxide 46.8 −29.9 −41.1 4.2E-02 9.3E-17
Formamide 108.9 −30.4 −41.9 1.0E-01 3.1E-16

a DME is not one of the standard solvents in the solvation model of Gaussian 09 software. A dielectric constant of DME was specified with other parameters
set to dichloroethane (similar shape as DME) in the calculation.
E3700 Journal of The Electrochemical Society, 164 (11) E3696-E3701 (2017)
in Table III are the computed solubilities of LiO2 and Li2 O2 in these
solvents. The solubilities in various other solvents are found to vary
greatly (up to 15 orders of magnitude) depending on the dielectric
constant. The solubility of Li2 O2 ranges from 10−16 to 10−32 and that
of LiO2 ranges from 10−1 to 10−13 .
Conclusions
The solvation energies and solubilities of LiO2 and Li2 O2 in aprotic
solvents were calculated using density functional theory and various
solvent models for dimethoxy ethane (DME). The following conclu-
sions are drawn:
1. The AIMD simulations give free energies of solvation of −29.4
and −40.3 kcal/mol for LiO2 and Li2 O2 , respectively. Solvation
energies calculated using the monomer cycles with 4 DME sol-
vent molecules and continuum models PCM and CPCM were
found to be comparable with the AIMD results. The PCM and
CPCM methods are recommended to be used for solvation energy
calculation due to their relatively lower computational cost.
2. The solvation energies were used with calculated free energies of
sublimation to determine solubilities. The calculated solubilities
of LiO2 (1.8 × 10−2 mol/L) and Li2 O2 (2.0 × 10−17 mol/L) in
DME indicates that bulk LiO2 is slightly soluble and Li2 O2 is
very insoluble.
3. The computed solubilities of Lix O2 (x = 1 or 2) in various organic
solvents vary significantly depending on the dielectric constant
of the solvent. For example, the computed solubility of LiO2 in
1,4-dioxane (ε = 2.2), DME (ε = 7.2) and DMSO (ε = 46.5)
is 10−13 , 10−4 and 10−2 mol/L, respectively. The solubilities of
Li2 O2 in the three solvents above are 10−32 , 10−20 and 10−17
mol/L, respectively.
4. Experimental solubilities for Li2 O2 range from 10−17 mol/L or
“insoluble” to 10−3 mol/L. Our calculations agree with the former.
The results giving larger solubilities may be due to impurities
or surface effects. The results for LiO2 agree with a mesoscale
model for particle growth that successfully simulated particle size
evolution observed experimentally.
The calculated LiO2 and Li2 O2 solubilities provide important in-
formation for fundamental studies of discharge and charge chemistries
in Li-O2 batteries. Since solubility is an important parameter that de-
termines nucleation and growth of the discharge product,18 tuning the
solubility of the LiO2 and Li2 O2 using different electrolytes by design
can help achieving desired product morphology.
Acknowledgment
This work was supported by the Joint Center for Energy Storage
Research (JCESR), an Energy Innovation Hub funded by the U. S.
Department of Energy, Office of Science, Basic Energy Sciences. We
gratefully acknowledge the computing resources provided on Blues
and Fusion, a high-performance computing cluster operated by the
Laboratory Computing Resource Center at Argonne National Lab-
oratory. This research also used resources of the National Energy
Research Scientific Computing Center, a DOE Office of Science User
Facility supported by the Office of Science of the U. S. Department
of Energy.
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