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Lithium-Ion Transport through Complex Interphases in Lithium

Metal Batteries
Stefany Angarita-Gomez and Perla B. Balbuena*
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ABSTRACT: Lithium metal is one of the best anode candidates for next-generation batteries.
However, there are still many unknowns regarding the structure and properties of the solid
electrolyte interphase (SEI) formed due to electron transfer reactions between the Li metal surface
and the electrolyte. In addition, because of the difficulties to study amorphous and dynamic phases
and interphases, there are many questions about the ion diffusion mechanism through complex
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multicomponent materials and interphases. In this study, using first-principles theory and
computation, we focus on developing a better understanding of the ion motion mechanisms in the
vicinity of a SEI formed when a seed Li2O or LiOH cluster nucleates on the Li metal surface. We
study the role of charge transfer at the interface between charged surfaces and the electrolyte, and
we investigate the evolution of inhomogeneous Li metal deposits present in the neighborhood of
the SEI nuclei, aiming to fundamentally understand how these events modify the ion transport
through complex electrochemically active materials.
KEYWORDS: lithium-ion, batteries, SEI, complex interphases, diffusion, density functional theory, ab initio molecular dynamics

■ INTRODUCTION
Lithium metal batteries (LMB) have been the focus of many
research activities due to their high theoretical capacity and
low electrochemical potential.1,2 LMB is a great candidate to
overcome many of the challenges regarding the capacity and
energy density requirements of modern society. However,
there are some key issues regarding uneven dendrite deposition
and unstable solid electrolyte interphase (SEI) that have led to
LMB having poor cyclability and safety issues that have
hindered its mass implementation.3−5 Therefore, elucidating
the reactivity and properties of the Li metal anode becomes
essential as we move toward the use of next-generation
batteries such as lithium−sulfur and lithium−air batteries that
show high promise for electric vehicles and other energy
storage applications.6−9
Strategies have been implemented to overcome some of the
challenges regarding the prevention of dendrite formation as
well as engineering of the SEI structure and properties.
Electrolyte design is directly related to promote the formation
of an effective SEI layer structure and properties, aiming to
improve the overall battery performance.10−12 The next natural
question is what the main characteristics of such effective SEI
are. Many studies have highlighted the expectations of the SEI
as a passivation layer to mitigate the electron leakage from the
electrode to the electrolyte and as a good ion conductor to
facilitate the ion electrodeposition reaction.13−17 But the
correlation between SEI structure/composition and electron/
ion transfer interfacial properties is not yet fully developed.
Therefore, achieving a proper electrolyte and SEI design
requires additional research emphasizing the ionic and
electronic transport characterization through the SEI that
could allow a prediction of its behavior and eventually help
improving the battery performance.18 Regarding ion transport
through the SEI, research indicates that it can be greatly
affected by the SEI’s structure, composition, and thick-
ness.13−17 Indeed, the characterization of the ion transport
mechanisms in such changing environment poses some
additional challenges. Many modern characterization techni-
ques19,20 have been developed to attempt decoding the
physical and chemical properties of the SEI, aiming to provide
a more accurate and real-time insight into the SEI structure
and dynamics. However, questions remain that demand further
comprehensive studies of the Li-ion transport mechanisms.
Theoretical and computational work is a great tool that has
yielded numerous insights into the SEI formation, growth, and
relevant properties.21 New methods and analyses to properly
describe the complexity of SEI phases add a new dimension to
their theoretical characterization.22−24 Recently, we were able
to describe SEI formation and evolution for a given anode/
electrolyte interface using first-principles simulations.25 The
current work adds a new perspective into the fundamental
understanding of the Li-ion motion through or near SEI
Received: September 14, 2022
Accepted: December 6, 2022
Published: December 15, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acsami.2c16598

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ACS Applied Materials & Interfaces
Figure 1. (a) Initial structure of 1 M LiPF6 in DME. (b) AIMD structure after 11 ps and 10 electrons added sequentially every 1 ps, the Li ion in
the electrolyte is fixed in the initial position. (c) Charge map distribution of the structure shown in (b). (d) Total net charges of structures shown in
(b) and (c).
complex interphases. We unveil possible Li-ion transport
mechanisms in complex interphases, including charged
surfaces, multicomponent SEIs, and surface heterogeneities,
to reveal detailed mechanisms of the ion deposition on the
anode, the SEI effects on the charge and ion transfer, as well as
the diffusion of Li ions through the SEI. To achieve this goal,
we use first-principles atomistic simulations including density
functional theory (DFT), ab initio molecular dynamics
(AIMD), and thermodynamic integration constrained AIMD
simulation (c-AIMD) tools. These computational tools allow
us to get new insights about SEI behavior and properties,
building the ground to establish a correlation between SEI
structure/composition and interfacial electron and ion trans-
port.
■ COMPUTATIONAL AND SYSTEM DETAILS
Calculations were performed using the Vienna ab initio
Simulation Package (VASP).26−28 Calculations include ground
state optimizations, ab initio molecular dynamics (AIMD), and
constrained ab initio molecular dynamics (c-AIMD). For the
initial ground state optimization, electronic and structural
optimization were carried out using density functional theory
(DFT). The electron−ion interactions were described by the
projector augmented wave (PAW) pseudopotentials,29,30 and
Perdew−Burke−Ernzerhof generalized gradient approximation
(GGA-PBE)31 was used as an exchange−correlation func-
tional.
The convergence criteria for electronic self-consistent
iteration and ionic relaxation were set to 10−4 and 10−3 eV,
respectively. In addition, the surface Brillouin zone integration,
a 2 × 2 × 1 Monkhorst−Pack k-point mesh,32 and the
Gaussian smearing with a width of 0.05 eV were used. The
energy cut-off for the plane-wave basis expansion was chosen
to be 400 eV. After optimization, some structures are run in
AIMD simulations with the canonical NVT ensemble at 300 K
with a time step of 1 fs. The Nose thermostat33,34 was used to
keep the temperature constant with a damping parameter set
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to 0.5. The c-AIMD simulations were carried out using the
Blue Moon ensemble method to calculate the potential of
mean force (PMF) as a free-energy profile as a function of the
reaction coordinate ξ, which allows identifying relevant steps
during the trajectory.35,22
Nuclei SEI nanoclusters of Li2O and LiOH used in this
study were grown and optimized as reported in previous
work.36 New integrated SEI/surface configurations are created
after these SEI nanoclusters are placed on top of the Li metal
surface. The resulting structure is optimized, and the
electrolyte is added up as needed to achieve the desired liquid
electrolyte density. Another optimization is carried out before
running other additional calculations. Bader charge analyses
were performed to study the charge distribution in the
system.37,38 The selection of the specific Li2O and LiOH
nanoclusters to represent the SEI was based on the availability
of these clusters from our previous published work. However,
these chemical species are usually found in native SEIs and also
after battery cycling. Similarly, the electrolyte components
were selected to facilitate the comparative analysis with our
previous work. Additional specific computational details are
described in the Results and Discussion section.
■ RESULTS AND DISCUSSION
Ion Transport from the Electrolyte Diffuse Layer to a
Charged Li Metal Surface. In previous work,39−41 we
evaluated barriers for ion transport from the electrolyte to the
Li metal surface at open circuit conditions, and this is natural
corrosion of the surface. The presence of excess charge in the
structure allows us to compare changes in ion pathway
mechanisms due to this surface charge. We start with the
structure shown in Figure 1a with a 1 M LiPF6 in a DME
electrolyte placed on top of the Li metal slab, where the cell is
initially electrically neutral. We note that the cell keeps neutral
after insertion of excess charge due to an additional
background charge of the opposite sign being added by
VASP. During the addition of electrons to the structure shown
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in Figure 1a, an initial 1 ps AIMD is performed to allow

relaxation of the atoms in their initial positions, except for the
Li cation of the LiPF6 salt that is fixed in its initial position
during the charging process of the structure. After the initial
AIMD, electrons are added sequentially to the simulation cell
at a rate of 1 electron/ps. The atoms are allowed to move, and
the excess charge redistributes in the cell, based on the atomic
and molecular electron affinities of the electrolyte and
electrode surface. After the charging process, the resulting
structure is shown in Figure 1b and its corresponding charge
distribution is illustrated by the color code in Figure 1c. Figure
1c shows localized charges in the solvent molecules in the
primary solvation complex near the Li cation in the electrolyte
diffuse-layer region, as well as in the free solvent molecules
located closer to the Li metal slab surface. During fast
equilibration, Figure 1c suggests redox activity taking place at
the surface Li atoms as indicated by the color spectra in the top
surface layers. Figure 1d shows the total net charge distribution
in the system. From the 10 electrons added as excess charge,
the Li metal slab is partially charged with ∼4|e−| and the rest
are distributed in the solvent molecules in the electrolyte phase
mainly in the primary solvation complex. A small amount of
charge is also localized in the He layer that is added to the
simulation cell to avoid the interactions of the top electrolyte
molecules with the bottom Li metal layers due to periodic
boundary conditions.
After the simulated charging process is completed, a c-
AIMD calculation is performed where the Li cation is under
constrain to approach the Li metal surface, while the rest of the
atoms in the system are unrestricted and are free to move in
whichever direction according to the AIMD trajectory. The c-
AIMD calculation allows us to identify the energy barriers Figure 2. Free-energy profile of lithium cation diffusion and
present in the ion motion pathway from the electrolyte to its deposition in 1 M LiPF6 in DME after the structure has been
final location after reduction and deposition in the Li metal charged with 10 electrons. Frames 1 through 8 in the energy pathway
surface. Figure 2 shows the free-energy profile of the Li+ are solvation shells found around the lithium cation shown at the
diffusion and deposition in 1 M LiPF6 in DME after the bottom. Li is highlighted in purple, and DME molecules involved in
structure has been charged with 10 electrons and the snapshots the primary solvation complex are highlighted in different colors
that showcase the solvation shells that surround the cation (green, yellow, blue, and red).
during this path. It is useful to compare this energy profile with
the one for the uncharged surface in our previous study.40 The
comparison shown in Figure S1 illustrates that the main In the mechanism for the ion motion in the charged
differences are in the much easier deposition steps in the structure, the highest negatively charged DME molecule (blue
charged surface (energy barrier from step 6 to step 8 in the in Figure 2) moved with the Li cation during the whole path,
charged surface ∼0.3 eV vs ∼0.52 from 5 to 6 in the uncharged and it is responsible for partially reducing the Li cation because
surface) and in the mechanism for charge transfer in the not all charge is transferred from the Li metal slab to the
charged structure, which may have contributions from cation. This is a very important point and makes a significant
intermolecular electron transfer as discussed below. Figure 2 difference in the observed ion transport in the charged surface.
shows the solvation shells numbered 1 through 8 involved in To further characterize the charge transfer dynamics, Figure
the ion path from the diffuse layer to the charged surface; 3 shows the charge transfer evolution in the reference frames
frame 1 shows three different solvent molecules in the primary shown in Figure 2. The reduction of the cation starts in frame
solvation complex (colored green, yellow, and blue). From 6 and is completed by frame 8, where the charge received by
frames 1−3, the identities of the solvation shell molecules the cation (red line) comes both from the solvent (pink line)
remain the same, while small changes in the configuration can in the primary solvation complex and from the Li metal slab
be observed. In frame 4, a new DME molecule (colored in red) (purple line). A schematic view of the charge distribution in
closer to the Li metal surface joins the primary solvation the system during the Li+ path can be found in Figure 4. The
complex, while one of the initial DME molecules (green) black arrow in Figure 4 shows the cation in the electrolyte with
moves out of this complex. By frame 6, only the most partially a positive charge and the primary solvation shell partially
charged solvent molecules (blue and red) are part of the charged, as the cation moves closer to the Li metal, the solvent
solvation complex, and they reorient toward the surface loses its charge and partially reduces the cation. In the last
facilitating the Li cation reduction and deposition by frame 8 frame 8 (Figure 4), the Li ion is on top of the Li metal and has
with small energy barriers (from 6 to 8 energy barrier of ∼0.3 been reduced and the charge in the electrolyte phase is equally
eV). distributed in all solvent molecules.
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Figure 3. Total net charges during the ion pathway shown in Figure 2.
Therefore, for this diluted electrolyte in an electron-rich
environment, the reduction and deposition pathway for the Li
cation is guided by the partially charged primary solvation
complex, and the charge transfer comes from the accompany-
ing solvent along with the Li metal slab when it is close to its
deposition.
Ion Transport through a Solid Electrolyte Interphase.
In the previous section, the metal surface was pristine.
However, SEIs arise naturally because of the electrolyte/
metal surface interaction. Although it is still not fully
Figure 4. Charge map distribution of the structures shown in Figure 2. Labels 1 through 8 represent the snapshots highlighted in Figure 2. Note:
the cation reduction is evidenced by its change of color (from orange to dark blue) in the locations indicated by the black arrow, while the
accompanying solvent gives up charge (goes from dark blue to green).
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understood, the SEI is an expected and necessary component
for the lithium metal battery that affects ion transport and its
electrochemical deposition. An ideal SEI should have good
ionic conductivity and electron-blocking capabilities to
promote the relatively easy passage of ions while preventing
further parasitic reactions and electrolyte decomposition.42
The SEI could be formed by a variety of components as it
strongly depends on the electrolyte composition, including
salts, solvents, and additives.16,43−47 Here, we incorporate
previously optimized nanoclusters of LiOH, and Li2O on the
pristine surface representing SEI nuclei, and investigate their
integration with the surface and their effect on the Li-ion
transport and deposition dynamics.36 Figure S2 shows the
initial structure used to study the Li-ion transport from and
toward the Li metal slab in the presence of an SEI nanocluster.
After the initial placement of the SEI nanocluster on top of
the Li metal slab, an optimization is performed. Next, c-AIMD
is carried out and results can be observed in Figure 5. When
the Li ion moves from the Li metal to the electrolyte across the
SEI region (Figure 5a), relatively low energy barriers are found
when the ion walks over the surface of the SEI nanocluster
while coordinating with oxygen in the Li2O nanocluster (steps
2−4). The largest energy barrier in this path can be found from
4 to 5 in Figure 5a and represents the Li ion completely
dissolving from the SEI structure into the electrolyte phase
(∼0.8 eV).
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Figure 5. Li-ion (green) motion pathway when Li2O (pink SEI nuclei) is present as part of a nascent SEI. (a) Free-energy profile of lithium-ion
motion from the metal surface to the electrolyte (arrow shows ion direction). Images 1 through 5 in the energy pathway show environments found
around the traveling Li ion at each step. (b) Free-energy profile of Li-ion motion from the electrolyte to the metal surface. Marks 1 through 3 in the
energy pathway are environments found around the Li ion at each step. The light blue atom indicates the target final position of the Li ion imposed
by the c-AIMD.

For the pathway from the electrolyte to the surface, the Li+
ion in Figure 5b encounters relatively high energy barriers.
From 1 to 2, the anion is pulled toward the primary solvation
complex to facilitate the diffusion of the Li cation to the surface
and help lowering the transport resistance. The complex Li+−
PF6− anion moves along with other solvent molecules toward
the surface (2−3), and by frame 3, in Figure 5b, the solvated
cation joins the SEI nanocluster surface. The main energy
barrier that the Li ion encounters while in the vicinity of Li2O
is the final desolvation step and integration to the surface O of
the SEI, whereas the motion through the SEI is relatively easy
and it is done by walking over the surface of the particle.
Interestingly, comparing the barriers in Figure 5a,b, the barrier
for desolvation (5b) is larger than the barrier for solvation
(5a), which reveals the differences of the Li−O interaction
strengths between the solvent O and the surface O anions.
When the SEI is LiOH, the overall free-energy profiles are
qualitatively similar to the Li2O case. Figure 6a shows the Li-
ion free-energy profile from the Li metal to the electrolyte
phase. The largest barrier can be found from 1 to 2 (∼0.91 eV)
and is the motion of the Li ion from the metal structure to
coordinating with the first oxygen in the LIOH SEI. From
there, the Li ion coordinates with multiple surface oxygens
until it reaches the top of the SEI in frame 4.
When traveling in the opposite direction, the whole path
from 1 to 4 in Figure 6b has similar energy barriers than those
found in the Li2O case. However, the mechanism of ion
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transport through the LiOH structure differs from the one
found in Li2O. In LiOH, the incoming Li ion gets trapped in
the SEI network and a different Li ion is released from LiOH at
the bottom surface maintaining the SEI structure. This
mechanism can be observed in Figure 6b, frames 4 and 5
(highlighted with black arrows). We note that the observed
barriers will have contributions from the relaxation of the
cluster environment because they will affect the ion motion.
Although both Li2O and LiOH structures are built on ionic
bonding, the different anion chemistry (OH vs O) and the
layered structure of LiOH may allow for more flexibility for ion
transport through LiOH.
The SEI can also be formed by a combination of blocks of
different chemical compositions. To characterize the effect of
this morphology on the passivity of the composed layer, we
evaluated a case where nanoclusters of LiOH and Li2O are
located next to each other on top of the Li metal slab surface
with a more reactive electrolyte 1:2 EC/DMC. A regular
AIMD calculation was performed to observe the behavior of
the system free of constraints. Results are shown in Figure 7,
the color-coded initial and final structures shown in Figure 7b,c
show the reorganization and reduction of electrolyte
molecules. Indeed, taking a closer look at the final AIMD
structure after ∼11 ps (Figure 7d), there is a partial reduction
of two different EC molecules. Interestingly, these molecules
are reduced on top of the Li2O cluster, as well as in the grain
boundary separating both SEIs. No reduction products are
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Figure 6. Li-ion motion pathway when LiOH is part of the SEI (pink). (a) Free-energy profile of Li-ion motion from the metal surface to the
electrolyte. Images 1 through 4 in the energy pathway reveal the effect of environments found around the traveling Li ion. (b) Free-energy profile of
Li-ion motion from the electrolyte to the metal surface. Images 1 through 5 in the energy pathway are environments found around the traveling Li
ion. Black arrows point to the Li ion that detaches from LiOH after being substituted by the incoming Li ion.

Figure 7. AIMD Simulation in structure with SEI formed with Li2O and LiOH on top of a Li metal surface and in contact with a 1:2 EC/DMC
electrolyte. (a) Initial structure. (b) Initial structure color coded. (c) Final structure after ∼11 ps in AIMD at 300 K. (d) Close-up version of the
structure shown in (c). The red arrow highlights the reduced EC molecules, and the green arrow shows the motion of the Li metal atoms toward
the SEI surface.

located directly on top of the LiOH SEI, indicating different
electron transfer capabilities of both SEIs.42,48
Effect of Uneven Surfaces on Ion Transport and
Reactivity. The uneven deposition of lithium can modify the
Li-ion deposition mechanism. First, we analyzed the ion
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transport from the electrolyte diffuse layer to an uneven surface
represented by an inhomogeneous Li deposit located on top of
a pristine (100) facet of Li metal shown in Figure S3. However,
after c-AIMD calculations in the pristine surface (frames 1−2
in Figure S3), we observe that the inhomogeneous deposit was
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Figure 8. (a, b) Initial and final structures after c-AIMD (∼26 ps) of a Li cation in 1 M LiPF6 in DME moving to an uneven surface located next to
a Li2O nanocluster. (c, d) Initial and final structures after ∼19 ps of AIMD at 300 K, the electrolyte is a mixture of 1:2 EC/DMC.
unstable, the surface self-repaired, and even out to expose a
more uniform surface. It was found that the Li cation does not
approach the surface during this surface healing process. After
frame 3, in Figure S3, the surface has evened out and the cation
proceeds to its regular deposition mechanism.
Next, we analyzed the uneven deposition in the presence of
SEI. In Figure 8, an uneven growth of lithium was placed and
optimized near a nanocluster of Li2O SEI. Details on the
creation of this structure are in the Supporting Information,
Figure S4. Two different electrolytes were used: Figure 8a
shows the initial structure with 1 M LiPF6 in the DME
electrolyte. After the c-AIMD, Figure 8b illustrates the motion
of the Li cation through the border of the SEI nanoparticle into
the deeper structure of the Li metal instead of its integration
on the uneven surface.
Then, the uneven structure and SEI were studied with a
more reactive 1:2 EC/DMC electrolyte shown in Figure 8c.
After ∼19 ps of AIMD, Figure 8d shows a reduced EC
molecule (highlighted in green); as noted before, this
reduction happens on top of the Li2O structure. The
rearrangement of the surface can be observed as well in Figure
8d, where Li metal atoms have migrated to the top of the
surface and other Li atoms from the uneven formation have
been incorporated into the SEI nanocluster; that is, the SEI
grows at expenses of the uneven Li growth.
■ CONCLUSIONS
New fundamental understanding of ion transport and
deposition in complex interphases is derived from first-
principles simulations. Depending on the state of charge of
the surface, clear differences are observed in the behavior and
energetic profile for ion transport at the interface. In an
electron-rich environment provided by charged surfaces, the
final charge transfer that leads to the ion reduction and
deposition comes both from the partially charged solvation
shell that assisted ion transport in the diffuse interfacial layer
and from the Li metal surface.
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When the surface is partially covered by a Li2O SEI, it is
found that the ion motion occurs through the border of the
SEI structure, where the cation moves through coordination
with oxygen anions and displacement of the Li cations in the
oxide surface. On the other hand, for LiOH SEIs, the Li ion
enters the SEI structure and substitutes one of the SEI Li
atoms, with another Li being released from the SEI to the
electrolyte. Although the free-energy profiles for the ion
coming from the electrolyte into the Li surface look similar to
that of the ion traveling in the opposite direction, there is
asymmetry in the magnitude of the barriers for solvation and
desolvation, with the desolvation barrier for the ion to
integrate with the SEI being higher than the solvation of the
ion to enter the electrolyte phase.
The LiOH structure offers better passivation properties than
the Li2O; this was evident from the reactivity of solvent
properties on both surfaces.
Inhomogeneous Li deposits on pristine surfaces were found
to be unstable, triggering a surface self-healing mechanism.
However, uneven Li deposits were found to be stable if located
near SEI nuclei. Depending on the chemistry, the SEI block
might become the focus for further electrolyte reduction
(observed in Li2O) and ion motion is promoted through its
border.
This study also demonstrates that versatile computational
chemistry tools allow elucidation of transport mechanisms in
complex interphases, including SEI mixtures with various
degrees of crystallinity.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.2c16598.
Free-energy profile comparison between charged and
uncharged surfaces (Figure S1); initial structures for SEI
nanoclusters of Li2O and LiOH with two electrolytes:
pure DME and 1 M LiPF6 in DME (Figure S2); free-
energy profile and snapshots in the Li-ion pathway from
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the electrolyte to uneven surfaces (Figure S3); initial
structure creation process for Figure 8 (Figure S4)
(PDF)
■ AUTHOR INFORMATION
Corresponding Author
Perla B. Balbuena − Department of Chemical Engineering,
Texas A&M University, College Station, Texas 77843,
United States; orcid.org/0000-0002-2358-3910;
Email: balbuena@tamu.edu
Author
Stefany Angarita-Gomez − Department of Chemical
Engineering, Texas A&M University, College Station, Texas
77843, United States
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.2c16598
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the Assistant Secretary for Energy
Efficiency and Renewable Energy, Office of Vehicle Tech-
nologies of the US Department of Energy through the
Advanced Battery Materials Research (BMR) Program
(Battery500 Consortium phase 2) under DOE contract No.
DE-AC05-76RL01830 from the Pacific Northwest National
Laboratory (PNNL). Computational resources from the Texas
A&M University High Performance Research Computing are
gratefully acknowledged.
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