Electrochimica Acta xxx (2018) xxx-xxx

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Electrochimica Acta

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journal homepage: www.elsevier.com

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Fundamental parameters governing ion conductivity in polymer electrolytes
A. Kisliuka, V. Bocharovaa, I. Popova, C. Gainarub, A.P. Sokolova, c, ∗
a
Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, United States
b
Fakultät Physik, Technische Universität Dortmund, D-44221, Dortmund, Germany
c

PR
Department of Chemistry, University of Tennessee, Knoxville, TN, 37996, United States

ARTICLE INFO ABSTRACT

Article history: We analyze conductivity of polymerized ionic liquids with focus on fundamental limitations hindering faster
Received 25 October 2018 charge transport in polymer electrolytes. We emphasize that to achieve the required ionic conductivity
Received in revised form 19 December 2018 ∼10−3 S/cm in dry polymer electrolytes, a decoupling of ion transport from segmental dynamics is required.
Accepted 25 December 2018

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We demonstrate that two competing mechanisms control decoupling of ion transport: electrostatic interactions
Available online xxx
that dominates for small ions such Li, and elastic force that dominates for large ions. Our experimental results
indeed confirm significant contribution of the elastic force to the energy barrier controlling transport of large
Keywords: ions. We also emphasize importance of ion-ion correlations that strongly affect charge transport (conductiv-
Polymer electrolytes ity) even at the same ion diffusivity. Our analysis suggests that these correlations suppress ion conductivity
Ion conductivity in polymer electrolytes by about ten times. At the end, we formulate some ideas on design of polymer elec-
Shear modulus trolytes with high ion conductivity.
Haven ratio
CT
© 2018.

1. Introduction 2. What controls ionic conductivity in polymer electrolytes

It is widely recognized that use of polymer electrolytes instead of We start with the analysis of ionic conductivity σ using classical
traditional liquid electrolytes will significantly improve performance Nernst-Einstein equation [7,8]:
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and safety of current batteries [1–4]. Among polymer electrolytes,

polymerized ionic liquids (PolyILs), where one ion remains mobile
while the counter ion is attached to the polymer chain, attract signif- (1)
icant attention due to their single-ion conductivity [5,6]. PolyILs do
not require any addition of salts for conductivity because they have
intrinsic ions. Single ion conductance is beneficial for many applica- Here n is the conducting ion concentration, q is their charge, D is
tions, including flow and conventional batteries. It also simplifies data
R

their diffusion coefficient presented as a random-walk terms with the

analysis and theoretical treatment of PolyILs, and make them ideal length of the ion jumps λ divided by the time between ion jumps τi
model systems to study microscopic parameters controlling conduc- (inverse ion jumps rate) and by 6, which accounts for dimensional-
tivity. ity [8]. Mobile ions concentration in PolyILs is usually in the range
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In this contribution we discuss the fundamental parameters control- 2–5 nm−3 [9]. Ion jump length in condensed matter should be λ ∼
ling conductivity in polymer electrolytes. We emphasize that decou- 1–2 Å. Using eq. (1) and assuming that all mobile ions contribute to
pling of ion transport from segmental (structural) relaxation is criti-
the conductivity, we can estimate the rate of ion jumps needed to
cal for achieving high ionic conductivity in dry polymer electrolytes.
achieve ion conductivity σ∼10−3 S/cm, usually presented as a mini-
There are two contributions, electrostatic and elastic forces, control-
mum value required for many applications [10]. To achieve this value
ling the decoupled ion transport. We demonstrate that reduction in
corresponding characteristic time between the ion jump should be
elastic force contribution indeed decreases the energy barrier for ion
τi ∼ (0.4–4)*10−10s–40–400 ps. According to the classical approxima-
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conductivity in glassy PolyILs. In addition ion-ion correlations signif-

icantly affect charge diffusion and thus the conductivity. This effect is
not actively discussed in literature, but according to our analysis it re-
duces ionic conductivity in PolyILs by almost 10 times.
∗
Corresponding author. Chemical Sciences Division, Oak Ridge National Laboratory,
Oak Ridge, TN, 37831, United States.
Email address: sokolov@utk.edu (A.P. Sokolov)
tion for ion transport in liquids, τi is defined by the characteristic struc-
tural relaxation time τα, i.e. τi ∼ τα [11]. The same is assumed to be
valid for polymer electrolytes above their glass transition temperature
(Tg) with τα being segmental relaxation time [11,12]. While so fast
structural relaxation time at room temperature is easily achievable for
many liquid electrolytes (e.g. τα in water is ∼1 ps [13,14]), it is not
feasible for the segmental relaxation in dry polymer electrolytes.

https://doi.org/10.1016/j.electacta.2018.12.143
0013-4686/ © 2018.
2 Electrochimica Acta xxx (2018) xxx-xxx

The best way to accelerate segmental dynamics is to decrease the

glass transition temperature, and many efforts were focused on devel-
oping polymer electrolytes with reduced Tg. Recent studies [15–17]
suggested that Tg in PolyILs depends on the size of structural units
(monomer plus mobile ion), dielectric constant, and chain rigidity. De-

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tailed analysis emphasized that it will be difficult, if not impossible
to develop dry PolyIL with Tg below 200 K [17]. In that case, it will
be impossible to have segmental relaxation time faster than ∼10−10 s.

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However, it was shown that plasticizing polymer with a solvent can
effectively speed up ion dynamics reaching the desired rate of the ion
transport. As a result, there are many polymer gels that provide suffi-
cient level of ion conductivity, although they lose many advantages of
solid polymer electrolytes [18,19].
There is, however, another mechanism of ion transport that domi-
nates in superionic crystals and glasses [20–22]. In this case ion jumps
in a frozen structure and the rate of their jumps is controlled by a char-

acteristic energy barrier Eσ separating ion sites, τi = τ0*exp(Eσ/kT),
where τ0∼10−12-10−14 s is a characteristic attempt time. Indeed, decou-
pling of ion transport from segmental dynamics has been observed
in crystalline poly(ethylene oxide) (PEO) [23–30], where segmental
mobility is essentially frozen, while ions still exhibit decent mobility.
Analysis demonstrates that Li ions move inside the PEO helix [23–25]
with the energy barrier that depends on the counterion [24,26,27]. The
PR
Fig. 1. Temperature dependence of ion conductivity for PolyILs clearly demonstrates a
crossover from a Vogel-Fulcher-Tamman (VFT) behavior to an Arrhenius-like behav-
ior at T ∼ Tg. Data are from Refs. [9,37], where detailed description of the PolyILs is
presented. The mobile ions are TFSI− and Br−. The structures of polymethylhydrosilox-
ane-graft-5-imidazolium-1-pentene trifluoromethanesulfonimide (polyMHSIm TFSI−),

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latter is positioned between the chain helixes [23,24]. Using shorter polyN-vinyl ethyl imidazolium trifluoromethanesulfonimide (PolyEtVIm TFSI−),
PEO chains [24] or orienting PEO chains by stretching or external polyN-vinyl diethylene glycol ethyl methyl ether imidazolium bromide and trifluo-
romethanesulfonimide (PolyEGVIm Br− and TFSI−) are presented in Table 1.
magnetic field [25,28–30] leads to an increase of ion conductivity,
emphasizing again a decoupling of ion motion from segmental dy-
namics. Decoupling of ion conductivity from segmental dynamics has
been also reported for many amorphous polymer electrolytes, includ-
ing PolyILs [12,31–34]. Understanding microscopic parameters that
CT
Table 1
can increase the decoupling and thus enhance ion transport is critical Chemical structure of PolyILs presented in Figs. 1 and 3.
for achieving high ionic conductivity in polymer electrolytes, and we
will discuss possible mechanisms below.

3. Mechanisms controlling decoupling of ion transport from

segmental dynamics
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For simplicity we will start with the analysis of ionic conductiv-

ity in PolyILs at temperatures below Tg, i.e. in their glassy state. In
this case segmental relaxation is essentially frozen and ions moves by
over-barrier jumps. Indeed polymer electrolytes show an Arrhenius
temperature dependence of conductivity at T < Tg, σ = σ0*exp(-Eσ/kBT)
R

[16,35,36] (Fig. 1). Thus, studies of ionic conductivity in polymer

electrolytes at T < Tg might reveal microscopic details controlling de-
coupling and the activation energy barrier for ion transport. Advantage
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of PolyILs in this study is that only mobile ions provide conductivity

while counter ions are attached to the chain and cannot move at T < Tg.
Detailed analysis of literature data for energy barrier controlling
conductivity below Tg in PolyILs was presented in Ref. [9]. It an-
alyzed polycations with mobile anions and polyanions with mobile
cations. We emphasize that no salt was added to PolyILs in these
studies, and the measured conductivity is intrinsic property of Poly-
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ILs provided exclusively by the mobile ions. This analysis reveals that
Eσ has non-monotonous dependence on the size of the mobile ions
Rion: It goes through a minimum, and strongly increases at smaller
and larger Rion (Fig. 2). This behavior can be explained by two com-
peting mechanisms controlling ion transport: electrostatic ion-ion in-
teractions and elastic force. The electrostatic contribution decreases
with increase in Rion while the elastic part increases. This idea has
been proposed by Anderson and Stuart to describe ion con
Fig. 2. Dependence of the activation energy for conductivity at T < Tg on the mobile ion
size in polymerized ionic liquids, mobile ions are named in the Figures. The data are
from Ref. [9], and references therein. The dashed line shows contribution of electrosta-
tic interactions with ε = 6 and R1+R2 = 2*Rion. Figure (A) presents elastic force follow-
ing shoving model with αG∞ = 1 GPa and 1.5 GPa (eq. (4)), while figure (B) presents
Anderson-Stuart Model with G = 1 GPa and 1.5 GPa, λ∼1 Å and RD = 0 (eq. (3)). The
solid lines show the sum of electrostatic and elastic force contributions for the corre-
sponding models.
 Electrochimica Acta xxx (2018) xxx-xxx
Fig. 3. BLS spectra of studied PolyILs measured at T ∼ Tg. Spectrum for PolyEtVIm Br
is presented at 297 K due to the very poor signal at Tg. In this case, several spectra
below Tg were measured and peak position was extrapolated to Tg. The solid lines rep-
resent fits to the damped harmonic oscillator model.
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ductivity in superionic glasses [38]. It predicts that the energy barrier
for conductivity can be presented as:
(2)
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Here the first term presents the electrostatic interaction of mobile
ion with charge q1 and radius R1 with the matrix ion with charge q2
and radius R2, ε is the dielectric constant, and β is the ‘Madelung’
constant, which indicates charge neutralization between the ion and its
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surroundings. The second term presents the elastic force contribution,
where G is the shear modulus, and RD is an effective radius of unopen
‘doorway’ for mobile ion to move from one site to another. This model
assumes that elastic contribution to the energy barrier can be approx-
imated by an opening of a ‘doorway’ with the size of the mobile ions
[38]. Later the model was modified by McElfresh & How it by includ-
R
ing ion jump length (λ) as a more appropriate parameter [39]:
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(3)
A similar model was recently proposed in Ref. [9], where elas-
tic contribution was described following the shoving model [40]. This
model assumes that the energy barrier is controlled by fluctuations
needed to create a volume increase, Eel ≈ G∞V, where G∞ is the
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high-frequency shear modulus and V is a volume comparable to the
volume of the moving molecule. As a result, the activation energy
controlling ionic conductivity can be presented as [9]:
(4)
Here α is a constant, α < 1, that accounts for a possible decrease in the
elastic energy barrier due to frustration in polymer chain packing.
3
These simplistic models indeed provide a good description of the
dependence of Eσ on the mobile ion radius Rion [9,38,41], with rea-
sonable for polymer electrolytes parameters ε = 6, and αG∞ or G
∼1–1.5 GPa (Fig. 2). These two model approaches provide different
dependence of the elastic energy barrier on the mobile ion size Rion:
It should increase as ∼ Rion2 in Anderson-Stuart model (eq. (3)), while
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it should increase as ∼ Rion3 in shoving model (eq. (4)). However, both
models predict the same dependence on the shear modulus.
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To verify the latter prediction we measured Brillouin Light Scat-
tering (BLS) spectra of several PolyILs. The synthesis and charac-
terizations of these PolyILs have been described in Ref. [17]. BLS
spectra were measured in symmetric geometry at 90° angle using
a tandem Fabry-Pérot interferometer and a solid state laser (Verdi,
λlaser = 532 nm). The samples were measured in cryostat Janis ST-100
with Lakeshore controller. The power of the incident laser beam was
∼5 mW. The HV polarization was used to measure the transverse
PR
modes (TA). The advantage of the symmetric scattering geometry is in
the compensation of the refractive index that provides an estimate of
the sound velocity VTA from the Brillouin peak frequency νTA without
knowledge of the materials refractive index [42], VTA = νTA*λlaser/√2
(this equation is valid for symmetric scattering at 90°). The spec-
tra (Fig. 3) show clear TA mode, that allows estimate G∞ = VTA2*ρ,
where ρ is the density of the material reported in Ref. [17].
Analysis of the Eσ vs. shear modulus (Fig. 4A) shows no corre-
lation: PolyIL with Br mobile ion has higher shear modulus than the
same PolyIL with TFSI mobile ion, but has lower Eσ. However, it is
important to realize that elastic contribution to Eσ depends also on the
size of the mobile ion (Eqs. (3) and (4)). We estimated expected elas-
tic contribution to the activation energy, assuming α = 1 for the shov-
ing model (eq. (4)), and assuming jump length λ∼1 Å and RD = 0 in the
Anderson-Stuart model (eq. (3)). Comparison of the experimental Eσ
with estimated elastic contribution (Fig. 4B) shows good agreement
of both models for the case of TFSI ion, while they both significantly
underestimate energy barrier for Br ion. This is consistent with sig-
nificantly larger electrostatic contribution to Eσ in the case of smaller
Br anion than in the case of larger TFSI- anion (Fig. 2). Unfortu-
nately experimental data cannot differentiate whether Anderson-Stu-
art or shoving model describes better the elastic force contribution.
Both models have enough adjustable parameters, and the difference in
ion size is not large enough to differentiate between ∼ Rion2 or ∼ Rion3
{{}}dependence.
To describe the ion transport above Tg we need to include two
possible mechanisms of conductivity: (i) the liquid-like mechanism
with ion diffusion being controlled by polymer segmental mobility,
i.e. τi ∼ τα; and (ii) the quasi-solid-like mechanism with ions jumping
Fig. 4. The measured energy barrier for conductivity below Tg vs shear modulus at Tg
(A) and vs elastic contribution estimated using eq. (3) (open squares) with λ∼1 Å and
RD = 0, and eq. (4) with α = 1 (open triangles) (B). The line in (B) presents Eσ = Elastic
Contribution. Strong difference for the Br anion is related to a significant electrostatic
contribution to Eσ for this ion.
4 Electrochimica Acta xxx (2018) xxx-xxx
over energy barriers in a slowly rearranging environment. In that case
conductivity can be expressed as:
(5)
Here the first term in square brackets presents Vogel-Fulcher-Tamman
(VFT) temperature dependence of the segmental dynamics, while the
second term presents over-barrier relaxation with constants C1(Rion)
and C2(Rion) that depend on the mobile ion size (eqs. (3) and (4)); n(T)
is an ‘effective’ concentration of ions contributing to conductivity and
reflects temperature dependent ion-ion correlations (will be discussed
in the next section). We want to emphasize that shear modulus G∞(T)
has significant temperature dependence above Tg [43], leading to a
ED
VFT-like behavior of conductivity even in the case of strongly decou-
pled ion transport. Thus VFT-like behavior of σ(T) itself is not a sign
of ion transport being coupled to segmental dynamics, as often mis-
interpreted in literature. However, at T < Tg the structure is frozen and
the shear modulus has weak temperature variations, leading to an Ar-
rhenius-like temperature dependence of σ(T) (Fig. 1). eq. (5) also ex-
plains the observation that decoupling is usually stronger in high-Tg
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polymers than in low-Tg polymers: while segmental dynamics (first
term) slows down drastically with increase in Tg, the probability of the
over-barrier jump (second term) increases significantly with increase
in temperature.
As was discussed in the previous section, it is not feasible for dry
polymer electrolytes to achieve required ion jump rate τi∼10−10 s at
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ambient conditions based on the liquid-like mechanism of conduc-
tivity alone. To achieve this rate with the over-barrier jumps
(quasi-solid-like mechanism) at room temperature requires the energy
barrier to be less than ∼25 kJ/mol (assuming attempt time τ0∼10−14 s).
For PolyILs with large mobile ions, such as TFSI, where energy bar-
rier is dominated by elastic force it would require αG∞(T) ∼ 0.3 GPa
R
(eq. (4)). This might be possible at T > Tg where G∞(T) softens signif-
icantly. At the same time, electrostatic interactions dominate the en-
ergy barrier for small ions such as Li+ and Na+, and can be reduced
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by an increase of the dielectric constant. According to the present es-
timates (eq. (4) and Fig. 2), an increase of the dielectric constant to
ε > 40 might reduce the activation energy barrier for Li ion to the re-
quired value. Even smaller ε might work for Na ion.
4. Role of ion-ion correlations
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An important point often overlooked in studies of ionic conductiv-
ity in polymers is that conductivity is defined by a charge diffusion
and not directly by the ion diffusion [44–46]. The ion conductivity is
defined by the velocity-velocity correlation of ions [44–46]:
(6)
Here V is the volume of the system, sgn(qi) and vi(t) are the sign and
velocity of an ion i. Thus conductivity is defined by velocity-veloc-
ity correlations of all ions, while ion diffusion is defined by self-cor-
relation function. In that respect Nernst-Einstein equation (eq. (1)) is
valid only for dilute solutions where correlations between different
ions is negligible and only self-correlation (i = j) contributes to con-
F
ductivity. In concentrated ionic systems ion-ion correlations are not
negligible and might strongly affect ion conductivity [16,47,48]. It is
OO
usually characterized by the so-called inverse Haven ratio H−1 = Dσ/D
[44,49], where Dσ = σkT/(n0q2) is the averaged charge diffusion esti-
mated from DC conductivity assuming that all mobile ions (n0) con-
tribute. The inverse Haven ratio was analyzed for many ionic liquids
and is often called “ionicity”. It is always below 1 suggesting that not
all ions contribute to the conductivity [16,47,48]. In most cases this ef-
fect is ascribed to diffusion of ion pairs that does not contribute to con-
ductivity. However, recent simulations [45] suggested that anti-corre-
PR
lated motion of ions with the same charge also play an important role
in reducing conductivity in ionic liquids.
In that respect analysis of the inverse Haven ratio in PolyILs [9,50]
reveals an interesting puzzle (Fig. 5): Although motion of ion pairs
can be completely excluded in this case, the inverse Haven ratio is sig-
nificantly below 1, Dσ/D ∼0.1–0.2. This result clearly indicates sig-
nificant anti-correlated motion of mobile ions in PolyILs, and authors
of [9] suggested a kind of backflow motions of mobile ions that does
not contribute to the charge diffusion despite ion diffusion. Similar
idea was proposed to explain the low values of the inverse Haven ra-
tio for proton transport in oxides [51]. It is interesting that many su-
perionic crystals and glasses exhibit inverse Haven ratio larger than
1 [44,46,52]. In that case mobile ions correlation is positive lead-
ing to a chain-like motion that strongly enhances ionic conductivity
[44,46,52].
The presented analysis (Fig. 5) reveals that ionic conductivity in
polymer electrolytes suppressed by ∼10 times relative to that in su-
perionic ceramics due to negative mobile ions correlations. Over-
coming this problem is critical to achieve high ionic conductivity in
polymer electrolytes. However, it is not obvious how can one design
PolyILs with positive mobile ion correlations. It is possible that cre-
ating local channels with high mobile ion concentration will bring
these systems closer to superionic ceramics. Enhancement of ionic
conductivity in highly ordered crystalline PEO might be partially
Fig. 5. The inverse Haven ratio for several PolyILs calculated using diffusion measured
by NMR (open symbols) and estimated from the conductivity relaxation time [50]. Data
from Refs. [9,50].
 Electrochimica Acta xxx (2018) xxx-xxx
caused by positive ion-ion correlations, where Li ions moves prefer-
ably inside the PEO chain helix [23–25] and ‘backflow’ effects might
be excluded. Another important point is the extremely high concentra-
tion of mobile ions in superionic ceramics, much higher than what can
be achieved in polymers. However, one might be able to create local
concentration of mobile ions in ionic channels that will be comparable
to that in superionic ceramics. Another option might be an increase in
the dielectric constant of the polymer matrix. This should decrease Tg
[17], significantly reduce the energy barrier for decoupled ion motions
(eqs. (3) and (4)), especially for small ions such as Li+ and Na+, and
might additionally decrease the degree of mobile ions correlations.
5. Conclusions
Presented analysis demonstrates importance of two mechanisms of
ionic conductivity in polymer electrolytes, a liquid-like when ion mo-
tion is coupled to segmental dynamics, and a quasi-solid-like when
ion can jump over energy barriers in a frozen or slow moving en-
vironment. However, to achieve the required by many applications
conductivity σ∼10−3S/cm, the first mechanism requires extremely fast
segmental dynamics that is not feasible in dry polymer electrolytes.
Thus, employment of the second mechanism is critical. Energy barrier
ED
for ion transport in this case depends on electrostatic interactions that
dominate for small ions and on elastic force contribution that domi-
nates for larger ions (eqs. (3) and (4)). Increase in the dielectric con-
stant of the polymer matrix should strongly reduce electrostatic con-
tribution to the energy barrier and might significantly enhance trans-
port of small ions, such as Li and Na. Presented here studies revealed
a good agreement between the predictions for elastic force contribu-
CT
tion and the activation energy controlling ion conductivity at T < Tg.
Thus reducing shear modulus of glassy polymer matrix will enhance
ion transport, especially in the case of large ions, such as TFSI. An-
other important point we want to emphasize is that the ion conduc-
tivity is defined by a cumulative charge diffusion, not by individual
ion drift. Ion-ion correlations are not negligible in highly concentrated
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ionic systems, including polymer electrolytes, and unfortunately re-
duce by almost 10 times ionic conductivity in PolyILs. The micro-
scopic mechanism of mobile ion correlations in PolyILs is not obvi-
ous, and simulations might be critical in unraveling their details. Un-
derstanding this mechanism might be critical for design of polymer
electrolytes with positive mobile ion correlations that should enhance
R
ion conductivity at the same ion diffusivity.
Notice
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This manuscript has been authored by UT-Battelle, LLC under
Contract No. DE-AC05-00OR22725 with the U.S. Department of En-
ergy. The United States Government retains and the publisher, by ac-
cepting the article for publication, acknowledges that the United States
Government retains a non-exclusive, paid-up, irrevocable, world-wide
license to publish or reproduce the published form of this manuscript,
UN
or allow others to do so, for United States Government purposes. The
Department of Energy will provide public access to these results of
federally sponsored research in accordance with the DOE Public Ac-
cess Plan (http://energy.gov/downloads/doe-public-access-plan).
5
Acknowledgments
Authors thank K. D. Kreuer and C. A. Angell for helpful discus-
sions and suggestions. This work was supported by the U.S. Depart-
ment of Energy, Office of Science, Basic Energy Sciences, Materials
Science and Engineering Division.
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