Electrochimica Acta 64 (2012) 118–129

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Three-dimensional particle-resolved models of Li-ion batteries to assist the

evaluation of empirical parameters in one-dimensional models
Graham M. Goldin a , Andrew M. Colclasure b,1 , Andreas H. Wiedemann b , Robert J. Kee b,∗
a
Ansys Incorporated, Lebanon, NH 03766, USA
b
Mechanical Engineering Dept., Colorado School of Mines, Golden, CO 80401, USA

a r t i c l e i n f o a b s t r a c t

Article history: Li-ion batteries are frequently modeled using variants of the one-dimensional approach that was initially
Received 6 November 2011 developed by Newman and colleagues (e.g., [2]). Necessarily such an approach is based upon assumptions
Received in revised form about the electrode microstructure, and quantitative predictions depend upon empirical parameters such
29 December 2011
as effective conductivities and diffusion coefficients. The present paper develops a three-dimensional
Accepted 29 December 2011
model that can resolve electrode structure at the submicron scale. Although the three-dimensional model
Available online 8 January 2012
is capable of representing arbitrary electrode microstructure, the present paper considers regular arrays
of spherical particles. The model is applied to evaluate approximations in one-dimensional models and to
Keywords:
Li-ion battery
assist in establishing empirical relationships that can be used in reduced-dimension models. General rela-
Electrode microstructure tionships for effective particle radius in one-dimensional models are derived from the three-dimensional
Three-dimensional models simulations. The results also provide a basis for estimating the empirical Bruggeman exponents that affect
Effective properties Li-ion transport within electrolyte solutions.
© 2012 Elsevier Ltd. All rights reserved.

1. Introduction theory to represent effective conductivities. Charge–transfer chem-

With the rapid development of lithium-ion battery technology,
there is an ongoing need to extend, validate, and apply physi-
cal models that assist design and development. The objective of
this paper is to develop three-dimensional models that resolve
electrode structures at the particle scale and apply the results
to evaluate approximations and establish empirical relationships
for use in one-dimensional models. Because they are so efficient
computationally, one-dimensional models are widely used. In this
paper, both the one-dimensional and three-dimensional models
are based upon electrodes that are formed as packed spherical par-
ticles (Fig. 1).
Most one-dimensional models are derived from the early work
of Newman and colleagues [1,2]. Although numerous variants of
the approach have been developed, the underpinning compu-
tational algorithm is usually retained [3]. In this approach, the
anode-separator–cathode assembly is represented using trans-
port equations that describe Li and Li-ion mass and charge
conservation. The models consider dual-insertion cells with mono-
dispersed spherical cathode and anode particles immersed in an
electrolyte solution. Ion transport within the electrolyte is mod-
eled with concentrated solution theory, using porous-electrode
∗ Corresponding author. Tel.: +1 303 273 3379; fax: +1 303 2273 3602.
E-mail address: rjkee@mines.edu (R.J. Kee).
1
Current address: ITN Energy Systems, Littleton, CO, USA.
istry is represented with Butler–Volmer rate expressions. Li-ion
intercalation is modeled by solving one-dimensional spherical
diffusion equations for representative electrode particles. One-
dimensional models are computationally economical, but depend
upon assumptions about particle shape and empirical representa-
tions of effective properties. In addition to assuming that particles
are spherical, the intercalation models assume that any mass and
charge transport between particles is negligible.
As is evident from X-ray tomography [4] and focused ion beam-
scanning electron microscopy (FIB-SEM) [5], practical electrodes
are not simply assemblies of packed spheres. Nevertheless, a great
deal of practical and quantitative insight can be derived from three-
dimensional models that are based upon packed-sphere electrodes.
Within an actual composite electrode, needed parameters (e.g.,
tortuosity) may be difficult to measure. However, other attributes
are measurable. For example, electrode porosity and surface area
are measurable. An objective of the present paper is to use three-
dimensional simulations of electrodes composed of regular arrays
of spherical particles, but with a wide range of packing configura-
tions, to establish empirical relationships in terms of measurable
attributes of actual electrode microstructures.
The general approach is to use three-dimensional models to
simulate battery discharge performance (i.e., voltage versus state-
of-charge) as functions of electrode packing configurations and
discharge rate. Then, by direct comparison with one-dimensional
models, determine empirical relationships for needed parameters.
The effective solid-phase diffusion length scale for Li intercalation

0013-4686/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2011.12.119
 G.M. Goldin et al. / Electrochimica Acta 64 (2012) 118–129
Fig. 1. Section of a membrane-electrode assembly, showing boundary conditions at
the interfaces between the electrodes and current collectors.
within the electrodes is found to be the most important parame-
ter.
The present paper has much in common with the Wang and
Sastry approach [6]. Electrodes are composed of spherical parti-
cles, using alternative packing structures. Although the present
paper uses spherical particles, the software is written gener-
ally to accommodate arbitrary electrode microstructures. Several
different packing structures are considered. Intercalated lithium
transport between particles is fully accommodated, but any poten-
tial contact resistance between particles is neglected. Although the
three-dimensional results use global charge–transfer chemistry,
the software is written to accept more complex thermodynamics
and chemistry.
As is typical of Newman-type models, the present paper does not
explicitly incorporate models of solid–electrolyte interface (SEI)
layers nor does it explicitly include the effects of binders and
conductive additives. SEI layers are typically tens of nanometers
thick [7], and cannot be directly resolved by three-dimensional
meshes on the micron scale. However, the effective resistance of SEI
layers could be incorporated by modification of the charge–transfer
rate expressions. Relatively thick binder and additive structures
could be incorporated, but is not done in the present paper
Representing actual electrodes with ordered arrangements of
overlapping spheres is clearly a major approximation of actual
electrode microstructures. Nevertheless, the ordered structures
provide a computationally efficient means to predict the influences
of three-dimensional structures and to derive empirical relation-
ships that are useful in calibrating one-dimensional models. It
should be noted that the ordered arrangements have no stochas-
tic content, as is the case with randomly arranged spheres or
actual reconstructed electrodes. Thus, numerous simulations are
119
Fig. 2. Illustration of the four packing geometries analyzed.
not required to achieve statistical significance of the results. More-
over, the algorithms developed for ordered structures are directly
extendable to modeling actual reconstructed electrodes [8–11].
2. Rate-limiting processes
The establishment of empirical parameters depends signifi-
cantly upon the identification of rate-limiting processes. Generally
speaking, Li-ion battery performance may be controlled by Li+
transport within the electrolyte solution, electrochemical charge
transfer at electrolyte–electrode surfaces, or intercalation diffu-
sion within the electrode volume. Three-dimensional simulations
will be used to explore the relative influence of potentially rate-
limiting processes, and to develop empirical relationships for use
in one-dimensional models.
If Li+ transport within the electrolyte solution is rate-limiting,
then the battery performance should be sensitive to electrode
microstructures that impede transport. For example, low poros-
ity or high tortuosity should degrade performance. If this were
the case, then empirical parameters such as Bruggeman expo-
nents would be important in calibrating one-dimensional models.
If charge–transfer chemistry were rate limiting, then the effec-
tive specific surface area (i.e., surface area per unit volume) of the
composite electrode would be an important parameter. If the inter-
calation diffusion were rate-limiting, then the battery performance
should depend upon the effective solid-state diffusion length scales
within the composite electrode.
3. Packing configurations
Fig. 2 illustrates four packing geometries that are simulated,
with all packing configurations forming regular lattices. Two of
the packing configurations are labeled “rectangular” and two are
labeled “triangular.” In both cases, an “aligned” packing and a “stag-
gered” packing are considered. The aligned packing is produced by
stacking rectangular or triangular unit cells directly on top of one
120 G.M. Goldin et al. / Electrochimica Acta 64 (2012) 118–129
Fig. 3. Illustration of the unit cell associated with the rectangular staggered (RS)
packing. The upper panel shows the electrode particles and the lower panel shows
the electrolyte solution.
another. The staggered packing inserts a particle in the centers of
the unit cells, which decreases porosity and effective surface areas.
Each three-dimensional packing configuration has a certain
combination of attributes that affects battery performance. Poros-
ity is usually the parameter that appears most prominently in
the one-dimensional models. Measures such as tortuosity are fre-
quently inferred from porosity, using, for example, a Bruggeman
exponent. Lithium ion transport through the electrolyte solu-
tion can significantly affect performance. High tortuosity increases
transport length scales, and thus increases transport resistance.
However, tortuosity is difficult to evaluate unambiguously within
the packed-sphere configurations. Moreover, narrow necks of elec-
trolyte solution between closely packed spheres can produce very
high transport resistance, even for packing configurations in which
the overall porosity may be high and tortuosity low.
Because the packing configurations are regular, the models take
advantage of repeating unit cells. Recognizing symmetry planes in
the various packing configurations assists in mesh generation and
in reducing computational effort. In the case of aligned configura-
tions, the unit cells are relatively easy to understand. The staggered
geometries, however, can be more difficult to see. Fig. 3 shows the
unit cells associated with the RS packing. As illustrated in Fig. 3a
Fig. 4. Porosity and surface-area ratio as functions of overlap angle for alternative
packing configurations.
only 1/16 of each spherical particle participates in the unit cell.
There is also a 45◦ symmetry plane associated with the RS pack-
ing. Each flat surface in Fig. 3a mates with a corresponding surface
with the mirror-image face of neighboring particle. The relatively
small flat circular symmetry planes are formed at the spherical
overlapping interfaces with neighboring particles. Fig. 3b illustrates
the electrolyte volume that fills the spaces between overlapping
spherical particles.
Because electric current is conducted through the electrode
particles, particles must overlap to ensure contiguous conduction
pathways. As illustrated by the inset in Fig. 4, the particle over-
lap is specified by a overlap angle . The packing configurations
considered here are formed such that all particles have a common
overlap angle with all their neighbors. The present study consid-
ers overlap angles ranging between 15◦ and 45◦ . Fig. 4 shows that
porosity (i.e., electrolyte volume fraction) and surface-area ratio
(i.e., surface area of the connected particles relative to the areas of
the particles if there were no overlap) are strong functions of the
packing geometry and the overlap angle.
The effective area primarily affects charge–transfer chemistry
through which lithium that is intercalated in the electrodes is trans-
ferred as lithium ions into the electrolyte solution, and vice versa. As
the overlap between electrode particles increase, electrode surface
area is reduced compared to isolated spherical particles.
4. Three-dimensional model
4.1. Conservation equations
The model represents mass and charge conservation within both
the electrode and electrolyte phases. Within the electrode particles,
Li mass concentration and electronic charge conservation may be
represented as
∂CLi
= ∇ · (Ded ∇ CLi ), (1)
∂t
∇ · (ed ∇ ␾ed ) = 0, (2)
 G.M. Goldin et al. / Electrochimica Acta 64 (2012) 118–129
where CLi is the intercalated Li concentration, Ded is the diffusivity
of the Li within the electrode, ed is the electric potential within
the electrode and  ed is the electronic conductivity of the electrode
phase.
Within the electrolyte phase, the Li-ion mass concentration and
ionic charge conservation are represented using concentrated solu-
tion theory as [12]:
  
∂CLi+ 2(1 − tLi+ )tLi+ RT
=∇ · Del − ∇ CLi+
∂t CLi+ F 2
∇ · (∇ ␾el ) + ∇ · (D ∇ ln(CLi+ )) = 0,
where CLi+ is the Li-ion concentration, Del is the experimentally
measured electrolyte diffusion coefficient, C = tLi+ /F, el is the
electric potential of the electrolyte phase, and  is the ionic con-
ductivity. The diffusional conductivity, D , is evaluated as,
 
2RT  d(ln f± )
D = (1 − tLi+ ) 1+ , (5)
F d(ln CLi+ )
where R is the universal gas constant, T is the temperature, F is
the Faraday constant, tLi+ is the lithium ion transference number
(defined as the fraction of current carried by lithium ions relative
to the total current carried by all ionic species in an electrolyte solu-
tion with uniform composition) and f± is the mean molar activity
coefficient of the electrolyte. For the results presented in this paper,
f± is assumed to be constant and hence the derivative term in Eq. (5)
vanishes.
During discharge, electrochemical charge–transfer reactions at
the cathode–electrolyte interfaces cause Li ions to be reduced
and enter the electrode phase as intercalated Li. At the
anode–electrolyte interfaces, charge–transfer chemistry causes Li
ions to enter the electrolyte phase as Li+ and release an electron into
the electrode. The processes are reversed during charging. Globally,
such chemistry may be represented as a reversible reaction
LiV (ed) + Li+ (el) + e− (ed)  Li(ed),
where “ed” and “el” represent electrode and electrolyte phases,
respectively, and LiV (ed) is a lithium vacancy within the electrode
phase. In the three-dimensional model, the electrode and elec-
trolyte phases are distinct and dispersed throughout the entire
model domain. Thus, the charge–transfer chemistry is an interface
constraint that serves to couple Eqs. (1)–(4).
Rates of the electrochemical charge–transfer reactions are mod-
eled with a Butler–Volmer formulation as
  ˛ F   ˛ F 
a c
i = io exp − exp − , (7)
RT RT
where i is the Faradaic current density, io is the exchange cur-
rent density, and ˛a and ˛c are the anodic and cathodic symmetry
factors.
The overpotential  is defined as
eq
 = ed − el − Eed ,
where ed and el represent electric potentials of the electrode and
eq
electrolyte phases, respectively, and Eed is the equilibrium electric-
potential difference. The exchange current density is modeled as
 ˛a
io = kr FCLi+ ˛a CLi
max
− CLi ˛c
CLi ,
where kr is a constant, CLi+ is the local Li-ion concentration in the
electrolyte solution adjacent to the electrode interface, CLi is the
intercalated Li concentration at the outer edge of the electrode
max is the saturated (maximum) intercalated Li con-
phase, and CLi
centration within the electrode phase.
121
4.2. Boundary conditions
Eqs. (1)–(4) require boundary conditions at the interfaces
between the electrode structures and the current collectors.
Because intercalated Li within the electrode particles cannot diffuse
into the current collectors, ∇ CLi = 0 at the interfaces between the
electrode particles and the current collectors. Similarly, because Li
ions within the electrolyte solution cannot diffuse into the current
collectors, ∇ CLi+ = 0 at the interfaces between the electrolyte and
+ ∇ · (C ∇ ␾el ), (3) the current collectors. As a reference potential, the electric poten-
tial at the anode current-collector is set to be ed = 0. The electric
current density is is specified at the cathode current collector, with
(4) the boundary condition being − ed ∇ ed = is .
Although the electrode microstructure is fully resolved in three
dimensions, the model assumes lateral symmetry normal to the
plane of the separator and current collectors. In other words, the
model is one-dimensional at the macroscale, but three dimensional
at the microscale. All the three-dimensional microstructures are
synthesized such that both the electrode and electrolyte phases
percolate between the current collectors and the separator.
The model does not explicitly consider a separator material. The
electrolyte solution is presumed to be the same within the anode
and cathode structures, with the anode and cathode separated by
a region of pure electrolyte solution (Fig. 1). Thus, the ion trans-
port within the electrolyte is modeled using Eq. (3) throughout
the entire domain, albeit with different charge–transfer interac-
tions between electrode and electrolyte in the anode and cathode
regions. If the separator region used a non-conducting porous
matrix to support the electrolyte, then an effective diffusivity of the
electrolyte within the separator region would be affected by the
support’s microstructure. Although the three-dimensional model
is capable of resolving a support structure, the present model does
not do so.
The electrode–electrolyte interfaces can be thought of as inter-
nal “boundaries.” The local rates of mass and charge transport
across these depend upon the local Li-ion concentration in the
electrolyte adjacent to the interface, the Li concentration on the
(6) electrode side of the interface, and the electric-potential differ-
ence across the electrode–electrolyte interface. Charge–transfer
reaction rates are represented in the Butler–Volmer setting (Eqs.
(7)–(9)). Section 4.3 provides more details about the numerical
treatment of these Faradaic interfaces.
4.3. Computational solution
During discharge, Eqs. (1) through (4) describe the flow of Li
from its intercalated state within the anode, through the electrolyte
as Li-ion, and finally Li intercalation into the cathode. Simultane-
ously, charge conservation within the anode and cathode, and ionic
conservation within the electrolyte is solved using electric and ionic
potentials. In the three-dimensional model, Li mass is modeled
using a single scalar representing Li-ion within the electrolyte and
Li within the electrodes. Similarly, a second single scalar is used to
represent potentials in the electrolyte, anode, and cathode phases.
(8) Numerically, these two scalars are discretized using unstruc-
tured polyhedral with a second-order finite-volume spatial scheme
and a bounded implicit second-order temporal scheme. Fig. 5 illus-
trates the electrolyte and electrode mesh network for a section with
RS packing.
(9) The scalars are solved in a segregated manner, using an Alge-
braic Multigrid algorithm for the linearized system and Picard
outer-iterations to converge nonlinearities [13]. Each scalar (e.g.,
Li concentration or electric potential) is solved implicitly over the
entire anode, cathode and electrolyte domain. Solving the charge-
conservation equation requires solving for potential jumps across
the electrode–electrolyte interfaces. The electrochemical aspects
122 G.M. Goldin et al. / Electrochimica Acta 64 (2012) 118–129

density. Thus, the one-dimensional simulation represents the

Li-ion and ionic-potential profiles as functions of one spatial dimen-
sion through the thickness of the battery.
Because the active particles are represented within the sub-
grid of the electrolyte domain, the Faradaic current at the
electrode–electrolyte interfaces appear as source terms in the elec-
trolyte conservation equations (i.e., Eqs. (10) and (11)). This is in
contrast to the three-dimensional model where both electrode and
electrolyte phases are spatially resolved. In the three-dimensional
model, charge transfer is modeled as an interface condition, not as
a source term.
The electrode particles impede ion diffusion and charge con-
duction within the electrolyte. A Bruggeman approach is used to
evaluate effective electrolyte properties as

eff = εbel , (12)

where represents Del , , and D , and b is the Bruggeman exponent.

A common assumption is that b = 1.5.
In addition to C Li+ and el which are solved over the entire
Fig. 5. Mesh network illustrated on a section of the RS packing geometry. one-dimensional electrolyte domain, two transport equations are
solved for the electric potentials within the anode particles on the
upper sub-domain anode and the cathode particles on the lower
of the problem (e.g., non-ideal thermodynamic properties and
Butler–Volmer charge transfer rates) are implemented using User sub-domain cathode :
Defined Functions (UDF) within the Fluent framework. ∇ · ( eff ∇ ␾anode ) = As i, (13)
Uncoupled linear diffusion equations (e.g., Eq. (10) or (2)), can be
solved easily and efficiently on large, complex, three-dimensional ∇ · ( eff ∇ ␾cathode ) = As i. (14)
mesh networks. However, the strong nonlinearity introduced by
the electrochemistry (i.e., Eqs. (7)–(9)) and ion transport (i.e., Because the electronic conductivity of the electrode particles is
migration terms in Eqs. (3)–(4)) causes the computational solution assumed to be high, electric potentials are not resolved within
to be much more difficult. The present algorithm uses a segregated individual electrode particles. Thus, in contrast to the three-
approach in which the partial differential equations are solved indi- dimensional model, the charge–transfer current density i appears
vidually, then iteratively coupled. Computational stability demands as a source term in Eqs. (13) and (14).
significant under-relaxation in coupling the conservation equa- Within every discretized cell of the anode and cathode sub-
tions. As many as 1000 iterations are found to be needed to achieve domains, an intercalation diffusion equation is solved for a
full convergence and to ensure that the total current through the representative spherical electrode particle as
electrode–electrolyte interfaces is consistent with the specified
 
∂C Li 1 ∂ 2 ∂C Li
galvanostatic current. Depending on mesh size and C-rate, the tran- = 2 r Ded , (15)
∂t r ∂r ∂r
sient three-dimensional solutions in the present paper demand
approximately 100 h using 8 parallel processors. The algorithm where r is the radial coordinate within the particle.
scales well with numbers of processors, so large parallel-processing
computers are advantageous. It may be possible to reduce the 5.2. Boundary conditions
computation cost significantly by implementing a fully coupled
algorithm, which is the subject of current research. Boundary conditions for the homogenized one-dimensional
model are equivalent to those in the three-dimensional model. On
5. One-dimensional model the upper and lower current-collector boundaries, the electrolyte
fluxes of Li-ions and ion electric potential vanish. The gradients
5.1. Conservation equations of anode and cathode potential are set to zero at the electrode-
separator interfaces (Fig. 1). The anode electric potential at the
Porous-electrode theory is used to form homogenized govern- current-collector boundary is specified to be anode = 0, and the
ing equations. Three domains are defined – electrolyte, cathode and cathode electric potential flux is specified to deliver a certain gal-
anode domains. As illustrated in Fig. 1, the anode is positioned on vanostatic current-density as
the upper side of the domain, with the upper boundary being the
anode current collector. The cathode is on the lower side, with the is = − eff ∇ cathode , (16)
cathode current collector at the bottom. The electrolyte domain where the specified current is is positive when the cell is discharg-
extends over the anode, separator and cathode. Homogenizing the ing.
electrolyte (i.e., Eqs. (3) and (4)) for the averaged Li-ion concentra- For the Li intercalation Eq. (15), the exchange rate of Li at r = rp
tion (C Li+ ) and averaged ionic potential (el ) within the electrolyte (where rp is the particle radius) is determined by the Faradaic cur-
yields rent density i as follows
∂(εel C Li+ ) A i ∂C Li i
= ∇ · (Del
eff
∇ C Li+ ) + (1 − tLi+ ) s , (10) Ded =− . (17)
∂t F ∂r F

∇ · (eff ∇ ␾el ) + ∇ · (Deff ∇ ln(C Li+ )) + As i = 0, (11) Due to symmetry, the Li flux at the particle center (r = 0) vanishes,

where εel is the electrolyte phase volume fraction, As is specific ∂C Li

= 0. (18)
electrode surface area (i.e., m2 /m3 ) and i is the Faradaic current ∂r
 G.M. Goldin et al. / Electrochimica Acta 64 (2012) 118–129 123

Table 1 Table 2
Three-dimensional geometry parameters for 30◦ overlap. Model parameters.

Parameter Anode Separator Cathode Parameter Anode Separator Cathode

Rectangular aligned, RA Ded (m2 s−1 ) 2 × 10−16 3.7 × 10−16

Thickness (␮m) 29.01 8.0 19.35 Del (m2 s−1 ) 2.6 × 10−10 2.6 × 10−10 2.6 × 10−10
Particle radius (␮m) 1.0 1.0  (S m−1 ) 100 10
d
Electrode porosity 0.4220 0 0.4220 Electrolyte conductivity,  = ACLi+ (e) exp(k(CLi+ (e) ) )
Rectangular staggered, RS A (S m2 kmol−1 ) 1.58 1.58 1.58
Thickness (␮m) 21.09 8.0 14.26 k (m4.2 kmol−1.4 ) 0.85 0.85 0.85
Particle radius (␮m) 1.0 1.0 d 1.4 1.4 1.4
Electrode porosity 0.1868 0 0.1868 t0 + 0.363 0.363 0.363
Li (e)
Triangular aligned, TA max
CLi (kmol m−3 ) 16.1 23.9
Thickness (␮m) 29.01 8.0 19.35 0%
CLi (kmol m−3 ) 2.029 22.37
Particle radius (␮m) 1.0 1.0 100%
CLi (kmol m−3 ) 10.88 10.56
Electrode porosity 0.3338 0 0.3338
CLi+ initial (kmol m−3 ) 1.2 1.2 1.2
Triangular staggered, TS

Ged (J kmol−1 ) 11.652 × 106 395.4616 × 106
Thickness (␮m) 24.34 8.0 16.35
˛a 0.5 0.5
Particle radius (␮m) 1.0 1.0
˛c 0.5 0.5
Electrode porosity 0.1028 0 0.1028
kr (m2.5 kmol−0.5 s−1 ) 4.52 × 10−8 2.07 × 10−8
Bruggeman exponent, b 1.5 1.5

5.3. Computational solution

The equations for the one-dimensional system (Eqs. (10)–(15))
are discretized using a second-order finite-volume scheme
and solved using the Sundials Integral–Differential–Algebraic
solver [14]. The total number of dependent variables is
Neqns = 2(Na + Ns + Nc ) + Na (NaR + 1) + Nc (NcR + 1),
where Na , Ns and Nc represent the number of axial cells in the anode,
The physical parameters used in the present study are based on
the FreedomCAR cell [15], which consists of a graphite anode and
an NCAO (Lix Niy Coz Al1−y−z O2 ) cathode. Table 2 lists parameters for
the electrode properties and Butler–Volmer equations. The elec-
trolyte diffusivity is assumed to be Del = 2.6 × 10−10 m2 s−1 and the
electrolyte conductivity (S m−1 ) is evaluated as
(19)  
 = ACLi+ exp kC d + , (21)
Li

separator and cathode; NaR and NcR denote the number of radial cells where A = 1.58 S m2 kmol−1 , k = 0.85 m4.2 kmol−1.4 and d = 1.4.
used to discretize the representative anode and cathode particles The semi-empirical Redlich–Kister expansion is used to model
within an axial cell, respectively. The first term on the right-hand the electrode equilibrium electric-potential (Eq. (8)):
side of Eq. (19) corresponds to the number of variables for the Li-

Ged RT
1 − X 
ion concentration and ionic potential in the electrolyte (Eqs. (10) eq ed
Eed = + ln
and (11)). The last two terms on the right-hand side correspond to F F Xed
1

N
the number of Li particle intercalation variables (Eq. (15)) which are
+ Am (2Xed − 1)m+1 (22)
solved in every electrode cell, plus the electrode electronic potential F
variables (Eqs. (13) and (14)). m=0 
2mXed (1 − Xed )
− ,
6. Discharge rate and state of charge (2Xed − 1)1−m

where Xed is the intercalation fraction at the electrode particle sur-

The current density (measured as C rate) is represented as the face, calculated as Xed = CLi /CLimax . The polynomial coefficients in
ratio is /is,1C . At a specified current density of 1C (i.e., is,1C ), the limit- Eq. (22) for the graphite anode and an NCAO cathode are provided
ing electrode’s state of charge (SOC) varies from 1.0 to 0.0 over 1 h. by [3] and listed in Table 3. Further details about the Redlich–Kister
The SOC is a measure of the battery’s available current capacity. The formulation may be found in Colclasure and Kee [3].
SOC for an electrode is calculated as follows
 0%
(1/Ve,s ) Ve,s
CLi dV − CLi Table 3
SOC = 100% − C 0%
(20) Redlich–Kister coefficients.
CLi Li
Coefficient (J kmol−1 ) Graphite anode NCAO cathode
where Ve,s is the volume of the active solid phase within the elec- A0 −3.268 × 10 6
−7.676 × 107
100% and C 0% are the average intercalated lithium
trode. The terms CLi Li A1 3.955 × 106 3.799 × 107
concentration at 100% and 0% SOC. A2 −4.573 × 106 −2.873 × 107
A3 6.147 × 106 1.169 × 107
A4 −3.339 × 106 1.451 × 107
7. Model parameters A5 1.117 × 107 −8.938 × 107
A6 2.997 × 105 1.671 × 108
Table 1 provides details of the alternative electrode structures. A7 −4.866 × 107 −7.236 × 107
A8 1.362 × 105 −1.746 × 108
The one-dimensional model is set to have the same number of
A9 1.373 × 108 −4.067 × 108
cathode (10) and anode (15) particles as three-dimensional model. A10 −2.129 × 107 9.534 × 108
Hence, the only input parameters to the one-dimensional model A11 −1.722 × 108 5.897 × 108
that vary over the four lattice configurations are the anode and A12 3.956 × 107 −7.455 × 108
cathode thicknesses, and porosities, as listed in Table 1. For all four A13 9.302 × 107 −1.102 × 109
A14 −3.280 × 107 −2.927 × 108
cases, the anode capacity (from 100% to 0% SOC) is 20% greater than A15 0 7.214 × 108
the cathode capacity. To prevent lithium plating during fast charg- A16 0 9.029 × 108
ing, the anode capacity (from 100% to 0% SOC) for all four cases is A17 0 −1.599 × 108
20% greater than the cathode capacity. Thus, the cell SOC is equal A18 0 6.658 × 108
A19 0 −1.084 × 109
to the cathode SOC.
124 G.M. Goldin et al. / Electrochimica Acta 64 (2012) 118–129
The battery temperature and electrolyte transference number
are assumed to be constant at T = 298 K and tLi+ = 0.363. For the
discharge conditions simulated, the initial Li-ion concentration in
the electrolyte is 1.2 kmol m−3 . The discharge simulation begins
with a SOC equal to one. Thus, the initial intercalated Li concen-
trations within the anode and cathode particles are 10.88 and
10.56 kmol m−3 , respectively. The initial potentials in the elec-
trolyte, anode and cathode are −0.0808 V, 0 V and 3.892 V,
respectively. Note, however, that because the charge- conservation
equations are algebraic, the solution at later times are independent
of these initial values.
Because the one-dimensional model has a representative inter-
calation particle within each grid cell in the electrode sub-domains,
it is reasonable that the cell size should be approximately equal to
the particle diameter. The present model uses Na = 15, Ns = 4, Nc = 10
and NaR = NcR = 10 (Eq. (19)).
8. Effective particle radius
The general approach is to use three-dimensional models to
simulate battery discharge performance as functions of electrode
packing configurations and discharge rate. The transient behav-
ior of the cell voltage as a function of state-of-charge is used as
the primary measure of performance. By direct comparison with
one-dimensional models, it is possible to determine empirical rela-
tionships for needed parameters. The results show that the effective
solid-phase diffusion length scale for Li intercalation within the
electrodes is the most important parameter.
If the solid-phase intercalation diffusion is rate-limiting, then
the diffusion length scale L should be proportional to electrode solid
volume Ve and surface area Ae as L ∝ Ve /Ae . If the electrode particles
were detached spheres, then the appropriate length scale would be
the particle radius,
(4/3)rp3
Ve
rp = 3 =3 . (23)
Ae 4rp2
This expression can be easily written in terms of the porosity εel
and the specific surface area As . The electrode volume and specific
surface area can be expressed as
Ae
Ve = (1 − εel )V, As = , (24)
V
where V is the total volume (i.e., solid and pore volume) of
the porous electrode. Assuming a one-dimensional Newman-type
model, and intercalation diffusion being rate-limiting, the effective
particles radius rp should be adjusted as
1 − εel
rp = 3 . (25)
As
Assuming that both εel and As are measurable in an actual electrode,
this simple formula provides a straightforward way to set the effec-
tive particle radius for a 1D simulation. Note that Eq. (25) always
leads to rp > rp , where rp is the radius of overlapping spheres.
If the charge–transfer rate were rate limiting, then the effec-
tive particle radius should be evaluated to make the surface area of
packing configurations are regular, the volumes and areas can be
calculated exactly.
9. Results
9.1. Illustrative three-dimensional simulation
Fig. 6 shows the intercalated Li concentration within the elec-
trode particles during a 5C discharge using the RS packing. At the
cathode–electrolyte interfaces and anode–electrolyte interfaces,
the intercalated Li concentration is high and low, respectively, due
to charge–transfer chemistry. However, at particle–particle inter-
sections, the Li concentration is lower in the cathode and higher
in the anode since there is no Faradaic current generated at these
intersections, and Li diffusion within the electrode particles is rel-
atively slow. Because galvanostatic discharge is specified, the total
current through an electrode–electrolyte interface must equal the
specified current through the current-collectors at all times. In the
three-dimensional geometries the particles intersect and the total
active particle–electrolyte area is less than in the one-dimensional
models, which assume disconnected particles. Thus, the current-
density through the active electrode–electrolyte area is higher in
the three-dimensional models than the one-dimensional models.
At higher current densities, intercalated Li has less time to dif-
fuse into/from the particle center, as well as the inactive zones at
particle–particle intersections, and hence voltage drops off faster
as the Li concentration saturates/approaches zero near the active
particle–electrolyte interface. This effect is accentuated in the Stag-
gered packings, which have more particle–particle intersections
per unit volume than the Aligned packings.
9.2. Rate-limiting intercalation diffusion
The diffusion coefficient for Li intercalation within the electrode
particles is some six orders of magnitude smaller than the diffusion
coefficient for Li+ transport in the electrolyte solution (Table 2).
Thus it is reasonable to anticipate that intercalation could be the
rate-limiting process.
The slow diffusion of intercalated lithium within the cathode
particles causes the steep voltage drop off at high discharge rates
(cf., 5C profiles in Figs. 7–9). Because the intercalated lithium dif-
fusion coefficient within graphite (2 × 10−16 m2 s−1 ) is lower than
the diffusion coefficient for NCAO (3.7 × 10−16 m2 s−1 ), one might
expect that slow diffusion within the anode particles causes the
voltage drop off. However, the anode capacity is 20% higher than
the cathode capacity. Thus, the flux of lithium into cathode surfaces
is 20% higher. Also, the concentration difference between 0% SOC
and the maximum concentration for the cathode is smaller than the
difference between 0% SOC and zero concentration for the anode
(see Table 2). In summary, the capacity and 0% SOC differences out-
weigh the diffusion coefficient differences and the cathode surfaces
usually saturate before the anode particles are depleted of Li.
Figs. 7–9 compare 3D simulations with two variations of 1D sim-
ulations. The “baseline” 1D simulations use the same particle radius
and porosity as the 3D simulations. The “adjusted” 1D simulations
overlapping particles to be the same as it would be with detached
spheres. That is, rp = Ae /4. Assuming that the 3D electrode
is composed of overlapping spheres, the effective particle radius
would always be smaller than the primary radius of the overlapping
spheres.
Using a range of 3D simulations with different packing con-
figurations provides a means to test the validity of Eq. (25). In all
cases, the 3D simulations use particles with 1 ␮m radius. However,
depending upon the overlap angle and the packing geometry, the
net electrode volume and surface area vary greatly. Because the
use Eq. (25) to set the representative particle radii. Over a wide
range of packing configurations and discharge rates, the results
show that Eq. (25) provides a very good approximation for setting
the effective particle radius in 1D simulations.
Fig. 10 is simply a graph of Eq. (25), with the markers show-
ing the effective particle radii for the one-dimensional simulations
shown in Figs. 7–9. For close packing with high overlap (e.g., RS
packing, 45◦ overlap angle) the effective one-dimensional particle
radius is nearly double that of the primary particles in the three-
dimensional simulations. On the other hand, with small overlap
 G.M. Goldin et al. / Electrochimica Acta 64 (2012) 118–129 125

Fig. 6. Li concentration (kmol m−3 ) within the electrode particles during a 5C discharge for the RS packing.

4.0 4.0
3D simulation 3D simulation
3.8 1D baseline 1C 3.8 1D baseline 1C
1D adjusted rp 1D adjusted rp
Cell voltage (V)

Cell voltage (V)

3.6 3.6
5C 5C
3.4 3.4

3.2 3.2
RS packing, 15° overlap RA packing, 15° overlap
3.0 3.0
4.0 4.0
3D simulation 3D simulation
3.8 1D baseline 1C 3.8 1D baseline
1D adjusted rp 1D adjusted rp 1C
Cell voltage (V)

Cell voltage (V)

3.6 3.6
5C 5C
3.4 3.4

3.2 5C 3.2
RS packing, 30° overlap RA packing, 30° overlap
3.0 3.0
4.0 4.0
3D simulation 3D simulation
3.8 1D baseline 1C 3.8 1D baseline 1C
1D adjusted rp 1D adjusted rp
Cell voltage (V)

Cell voltage (V)

3.6 3.6
5C 5C
3.4 3.4

3.2 5C 3.2
RS packing, 45° overlap RA packing, 45° overlap
3.0 3.0
0 0.2 0.4 0.6 0.8 1.0 0 0.2 0.4 0.6 0.8 1.0
State of charge State of charge

Fig. 7. Comparison of 3D and 1D simulations for the RS packing. The 1D simulations Fig. 8. Comparison of 3D and 1D simulations for the RA packing. The 1D simulations
show the effects of adjusting the particle size based upon 3D surface-to-volume show the effects of adjusting the particle size based upon 3D surface-to-volume
ratio. ratio.
126 G.M. Goldin et al. / Electrochimica Acta 64 (2012) 118–129

4.0 4.0
3D simulation RS packing, 30° overlap
3.8 1D baseline 1C 3.8
1D adjusted rp 5C discharge

Cell voltage (V)

Cell voltage (V)

3.6 3.6
5C
3.4 3.4
3D simulation
3.2 3.2 1D with Bruggeman exponent
TA packing, 15° overlap 1.5 < b < 3.5
3.0 3.0
0 0.2 0.4 0.6 0.8 1.0
4.0
State of charge
3D simulation
3.8 1D baseline 1C Fig. 11. Comparison of 3D and 1D simulations for the RS packing and 5C discharge.
1D adjusted rp
Cell voltage (V)

The Bruggeman exponent in the 1D model is varied between 1.5 < b < 3.5.
3.6
5C
requires an effective particle radius that is larger than the three-
3.4
dimensional particle radius. This provides convincing evidence that
the charge–transfer chemistry and the effective surface area are
3.2
TA packing, 30° overlap not rate-limiting. If surface chemistry were rate limiting the effect
of particle overlap would require that the one-dimensional model
3.0
use an effective particle radius that is smaller than the three-
4.0 dimensional particle radius (cf., Section 8).
3D simulation The nominal particle radius in the present study is rp = 1 ␮m.
3.8 1D baseline 1C As the particle sizes decrease, the intercalation diffusion tends
1D adjusted rp
Cell voltage (V)

to be less rate-limiting. If the nominal particle size were very

3.6 much smaller (i.e., on a nanometer scale), then it is possible that
5C charge–transfer could become rate-limiting compared to interca-
3.4 lation diffusion. The formation of solid–electrolyte interface films
5C will tend to increase charge–transfer resistance, which would tend
3.2 to increase the importance of surface area. However, these effects
TA packing, 45° overlap were not considered in the present study.
3.0
0 0.2 0.4 0.6 0.8 1.0
State of charge 9.4. Rate-limiting Li+ transport

Fig. 9. Comparison of 3D and 1D simulations for the TA packing. The 1D simulations
show the effects of adjusting the particle size based upon 3D surface-to-volume
ratio.
angles, where the three-dimensional configuration approaches that
of disconnected spheres, the effective particle radius is nearly the
same as the primary particle radius in the three-dimensional sim-
ulations.
If Li+ ion transport would be rate-limiting, then the 1D simula-
tions would be sensitive to the Bruggeman exponent that modifies
the ion diffusion. However, as illustrated in Fig. 11 the Bruggeman
exponent has a very small effect on the discharge curves. Varying
the Bruggeman exponent in the range 1.5 < b < 3.5 does not change
the discharge curve within the width of the lines in the plot. By con-
trast, Fig. 7b shows a very significant effect of varying the effective
particle radius.

9.3. Rate-limiting charge transfer 9.5. Li-ion spatial profiles

For the range of conditions simulated, to achieve com- Although the Li+ transport has a small influence on the dis-
parable discharge curves, the one-dimensional model always charge characteristics, there are variations in the spatial Li+ profiles.
The homogenized one-dimensional model uses a Bruggeman for-
mulation to represent effective transport properties through the
2.0 porous particle matrix (Eq. (12)). Figs. 12a and 13a show the axial
RS packing θ=45° variation of Li-ion concentration within the electrolyte for the RA
Effective radius (μm)

1.8 RA packing and RS packing configurations near the end of discharge (t = 3200
TA packing s) at a 1C rate. One-dimensional predictions using Bruggeman
1.6 exponents of b = 1.5, b = 2.5 and b = 3.5 are compared with the
θ=45° equivalent three-dimensional model. The default Bruggeman expo-
1.4
θ=45° nent b = 1.5 is reasonably accurate for the RS packing. However,
θ=30° 3D spheres for the aligned packing, b = 1.5 over-predicts the effective Li-ion
1.2
θ=15° θ=30° rp = 1 μm diffusivity. Figs. 12b and 13b show similar behaviors at the higher
5C discharge rate. For both the one- and three-dimensional models,
1.0
0.30 0.35 0.40 0.45 0.50 0.55 0.60 there is more variation in the Li-ion concentration profiles for the
(1-ε) / As (μm) RS packing compared to the RA packing. Considering the 3D model
with a 5C rate, the maximum and minimum Li-ion concentrations
Fig. 10. Relationship of effective particle radius rp as a function of (1 − εel )/As for for the RA packing are 1.23 and 1.17 kmol m−3 , respectively. For
different packing configurations and overlap angles. the RS packing, these concentrations are 1.27 and 1.14 kmol m−3 .
 G.M. Goldin et al. / Electrochimica Acta 64 (2012) 118–129 127

1.23
Li+ (kmol m-3)
1.22 1D, b=3.5 RA packing
3D 1D, b=2.5 30° overlap
1.21
1C discharge
1.20
1D, b=1.5
1.19
1.18
a)
1.17
1.35
1.30 1D, b=3.5 RA packing
Li+ (kmol m-3)

3D 1D, b=2.5 30° overlap

1.25
5C discharge
1.20
1D, b=1.5
1.15
1.10
b)
1.05
0 10 20 30 40 50 60
Axial position (microns)

Fig. 12. Average Li-ion concentration in the electrolyte as a function of axial distance
at discharge rates of 1C and 5C for the RA geometry.
Visualizations of actual electrode geometries (e.g., [4,5]) imply
more tortuous pathways than would be expected with sparsely
connected spheres, with high Bruggeman exponents being
arguably more appropriate for realistic electrode geometries.
Figs. 12 and 13 confirm that the cell voltage drop off at
high discharge rates (Figs. 7–9) is very weakly related to elec-
trolyte transport. Even at a discharge rate of 5C, the lithium-ion
concentration profile for the 3D cases near the end of discharge is
fairly uniform (RS case is between 1.27 and 1.14 kmol m−3 ). Only
the exchange current density (Eq. (9)) and electrolyte conductivity
(Eq. (21)) are affected by changes in the lithium-ion concentration.
However, the exchange current density and ionic conductivity are
relatively high and do not lead to any significant voltage loss. Thus,
small changes in the electrolyte concentration do not noticeably
Fig. 14. Diffusion ratio as functions of overlap angle for alternative packing config-
urations.
affect the cell voltage. For instance, consider the RS case which
has the lowest effective electrolyte diffusivity of the three particle
packings. Even at 5 C, the one-dimensional cell-voltage profiles for
simulations with Bruggeman coefficients of 1.5 and 2.5 are nearly
indistinguishable from one another.
Although the discharge performance is very weakly related to
the Li-ion profiles, it should not be concluded that the Li-ion vari-
ations are generally unimportant. Other performance measures,
such as the formation and growth of solid–electrolyte interface
(SEI) films depend directly upon the Li+ concentrations [7]. Thus,
spatial variations in Li+ lead to variations in SEI thickness, and hence
charge–transfer resistance, capacity fade, etc.

1.40 9.6. Packing configuration and Bruggeman exponent

1.35 1D, b=3.5 RS packing
Li+ (kmol m-3)

1.30 3D 1D, b=2.5 30° overlap It is interesting to investigate how the packing configurations
1.25 1C discharge affect ordinary diffusion through the pore spaces. A diffusivity ratio
Rdiff can be defined as
1.20
1.15 1D, b=1.5 J
Rdiff = , (26)
1.10 Jintrinsic
1.05 a) where J is the diffusive transport flux through the electrolyte vol-
1.00 ume of a particular packing configuration and Jintrinsic is the flux that
2.50 would be conducted through electrolyte solution alone, without
any electrode particles. For each packing configuration, J is eval-
1D, b=3.5 RS packing
Li+ (kmol m-3)

2.00 uated by computationally solving the ordinary diffusion problem

1D, b=2.5 30° overlap through the actual three-dimensional electrolyte geometry (i.e.,
3D 5C discharge ∇ 2 X = 0, with X specified as boundary values at each extremity
1.50
of the electrolyte domain). The diffusivity ratio can also be inter-
1.00 preted as an effective diffusion coefficient in a one-dimensional
1D, b=1.5
simulation. Fig. 14a shows the diffusivity ratios computed by the
0.50 three-dimensional model as functions of the overlap angle for each
b) of the packing configurations.
0 Although the behavior of the porosity and the diffusivity ratio is
0 10 20 30 40 50
Axial position (microns) qualitatively similar (cf., Figs. 4a and 14a, there are important dif-
ferences. At high overlap angles, the diffusivity ratio can approach
Fig. 13. Average Li-ion concentration in the electrolyte as a function of axial distance zero (i.e., the diffusion flux vanishes), while the porosity at the
at discharge rates of 1C and 5C for the RS geometry. same overlap angle can be in the range of 5–10%. Sufficiently high
128 G.M. Goldin et al. / Electrochimica Acta 64 (2012) 118–129

22
a)
20 RA packing Max.
30° overlap Ave. 1D
18
5C discharge

Li concentration (kmol m-3)

16
Min.

14

12
Fig. 15. Predicted effective diffusivity ratios as functions of porosity for RA, RS,
and TA packing configurations and comparison with the expression inferred from 24
tortuosity measurements reported by Thorat et al. [16].
22 b)
Max.
particle overlap causes the diffusion flux to vanish when the elec- 20 RS packing
Ave.
trolyte fails to percolate throughout the entire domain. 30° overlap
18
1D
The diffusivity ratio can be used to investigate the approxima-
5C discharge
tion associated with of Eq. (12). For each packing configuration, the
16 Min.
Bruggeman exponent can be evaluated as
ln(Rdiff ) 14
b= . (27)
ln(εel ) 12
0 0.2 0.4 0.6 0.8 1.0
The porosity is a purely geometric function of the packing con-
figuration (Fig. 4a). Fig. 14b shows that the Bruggeman exponents
Radial position (microns)
evaluated based on pure diffusion are consistent with those shown
Fig. 16. Radial profiles of intercalated Li concentration in the positive particles after
in Figs. 12 and 13. The TA and TS packings show higher and non- 500 s at 5C discharge for the RA and RS geometries. The concentration profiles are
constant Bruggeman exponents. Because of its the low porosity and averaged over the entire cathode domain. However, the concentration profile within
high tortuosity the TA packing is probably unrealistic for practical an electrode particle does not vary significantly with position inside the electrode
electrodes. domain.

The results here are in some respects consistent with those

reported by Thorat et al. [16], who reported b ≈ 1.5 for Li-ion bat-
tery electrodes and separators. Thorat et al. reported an expression
are disconnected. It appears that the low Li concentration near
that relates tortuosity and porosity as  = 1.8ε−0.53 . Assuming, as
ed inter-particle connections balances the higher Li concentration
Thorat et al. note, that Rdiff = εed /, it follows that
Deff
Rdiff = ≈ Aεbel ,
Dintrinsic
with A ≈ 1/1.8. In other words, the porosity dependence is b ≈ 1.5,
but the factor A =/ 1 as implied by the standard Bruggeman analysis
(e.g., Eq. (12)).
Fig. 15 plots the computed diffusivity ratio for RA, RS, and TA
packing configurations as functions of porosity. Also plotted is
the expression derived from the Thorat et al. tortuosity measure-
ments [16]. The idealized configurations, especially the RS and RA
packings, provide qualitatively the same trends as those reported
by Thorat et al. However, although the Bruggeman exponent is
essentially the same, the magnitude of the diffusivity ratio is differ-
ent. Nevertheless, it should be recognized that there is some scatter
in the Thorat et al. tortuosity data and the expression in Fig. 15
near electrode–electrolyte interfaces, with the average being close
to the concentration profile in disconnected particles. However,
(28) localized maximum Li concentration causes decreased utilization
in the three-dimensional geometries. The higher maximum CLi in
the RS geometry (Fig. 16b) compared to the RA geometry (Fig. 16a)
results in the accelerated voltage drop-off for the RS packing (Fig. 7)
compared to RA packing (Fig. 8).
10. Summary and conclusions
Three dimensional simulations of a dual-insertion Li-ion cell
during galvanostatic discharge are compared with an equiva-
lent one-dimensional model. The three-dimensional model fully
resolves the electrode particles, which are assumed spherical
but are packed into alternative lattice arrangements. The three-
is based upon a further assumption that Rdiff = εed /. Overall, the
idealized spherical packing provides a reasonable approximation
to actual electrodes. Moreover, as discussed earlier, battery dis-
charge (and charge) characteristics depend only weakly on the Li+
transport within the electrolyte solution.
9.7. Intercalated Li concentration profiles
Fig. 16 shows the radial profiles of intercalated Li within cathode
particles for the three-dimensional models (average, minimum,
maximum), as well as the one-dimensional model for the RA
and RS geometries. The cell state is at 370 s after discharging
at a 5C rate, which is close to the end of discharge for the RS
geometry. Because the cathode solid phase volume is slightly
lower in the three-dimensional model due to particle overlap,
the average three-dimensional intercalated Li concentration is
slightly higher than the one-dimensional model where particles
dimensional model also fully resolves the porous electrolyte
volume between the electrode particles. The present study consid-
ers electrode particles that have a nominal radius of 1 ␮m. Under
all conditions studied, intercalation diffusion is the rate-limiting
process that controls discharge characteristics.
With intercalation diffusion being rate-limiting, it is possible to
use three-dimensional simulations to determine effective particle
radii to be used in Newman-type one-dimensional models. Over a
very wide range of electrode structures, the effective particle radius
can be evaluated with a simple formula rp = 3(1 − εel )/As , where
εel is the porosity and As is the specific surface area of the electrode.
Because these physical attributes can be measured in actual elec-
trodes, the effective particle radius can be used to assist calibrating
one-dimensional models. Because the effective radius is valid for
significantly different spherical configurations, it is at least reason-
able to anticipate that the approach will be valid for more complex
actual electrodes.
 G.M. Goldin et al. / Electrochimica Acta 64 (2012) 118–129
Although the Li+ diffusion plays a small role in the cell-voltage
transients, there can be significant variations in the Li+ spatial
profiles. These Li+ variations can affect local cell degradation due
to lithium plating and SEI film growth. The packing configuration
affects the ion transport, with lower porosity and higher tortuosity
impeding the transport. The commonly used Bruggeman exponent
of b = 1.5 is a reasonably good approximation. However, for the
more tightly packed configurations, a Bruggeman exponent closer
to b ≈ 2 is found to be better aligned with the three-dimensional
results.
A model based upon ordered spheres is clearly a significant
simplification of actual electrode microstructure. Nevertheless, the
relatively efficient computational costs enable parameters studies
that can suggest new or improved microstructures. The compu-
tational approach is applicable to modeling actual reconstructed
electrodes, but the computational cost is greatly higher. More-
over, because the experiments are time consuming and expensive,
there is limited availability of reconstructed electrode data. And,
modeling a specific electrode structure does not directly provide a
predictive capability to suggest alternative microstructures. Thus,
modeling synthesized microstructures provides valuable insight
and predictive capabilities.
Acknowledgements
This work was supported by the Office of Naval Research
through a Research Tools Consortium grant number N00014-05-
1-0339.
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