Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta
a r t i c l e
i n f o
Article history:
Received 29 April 2010
Received in revised form 29 June 2010
Accepted 5 August 2010
Available online 12 August 2010
Keywords:
Li-ion battery
Elementary charge transfer
Non-ideal thermodynamics
Modeling
a b s t r a c t
This paper is particularly concerned with the elementary reactions and transport processes that are
responsible for Li-ion battery performance. The model generally follows the widely practiced approach
developed by Newman and co-workers (e.g., Doyle et al., J. Electrochem. Soc. 140 (1993) 1526 [1]).
However, there are signicant departures, especially in modeling electrochemical charge transfer. The
present approach introduces systems of microscopically reversible reactions, including both heterogeneous thermal reactions and electrochemical charge-transfer reactions. All reaction rates are evaluated in
elementary form, providing a powerful alternative to a ButlerVolmer formalism for the charge-transfer
reactions. The paper is particularly concerned with the inuence of non-ideal thermodynamics for evaluating reversible potentials as well as charge-transfer rates. The theory and modeling approach establishes
a framework for extending chemistry models to incorporate detailed reaction mechanisms that represent
multiple competitive reaction pathways.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
Lithium-ion batteries are certainly making signicant impacts
on a range of applications from small portable devices to automotive traction. Fig. 1 illustrates the structure of a cylindrical Li-ion
cell over a range of length scales. The objective of the present
effort is to develop models at the electrode-particle scale that
incorporate fundamental thermodynamics and chemical kinetics.
Charge-transfer processes within lithium-ion batteries are usually
modeled using a ButlerVolmer representation [13]. The present
approach provides a potentially powerful alternative to representing electrochemical charge-transfer rates via global ButlerVolmer
expressions. Representing chemistry in terms of elementary reactions enables the study of competitive reaction pathways. For
example, potentially deleterious Li plating on anode surfaces competes with desired Li-ion intercalation into the electrode particle.
Details of the chemistry associated with solid electrolyte interfaces
(SEI) can be incorporated in the reaction mechanism [4,5]. Although
the present effort concentrates upon intercalation electrodes, the
fundamental approach to modeling kinetics is well suited to modeling conversion electrodes.
Before developing the details of the model, it is helpful to
review the broad concepts of Li-ion battery function. Consider the
electrode-particle scale (Fig. 1), with a composite anode on the
Corresponding author. Tel.: +1 303 273 3379; fax: +1 303 273 3602.
E-mail address: rjkee@mines.edu (R.J. Kee).
0013-4686/$ see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2010.08.018
(1)
8961
(2)
Here V(CoO2 ) is an intercalation vacancy within a cathode particle and Li(CoO2 ) is an intercalated Li. The electron e (c) is in the
electronically conducting phases of the cathode.
2. Model formulation
The modeling approach builds upon the foundation established
by Newman and co-workers [1,2,6]. Species- and chargeconservation equations are solved to predict temporal and spatial
proles of lithium concentration and electric potentials. Transport
through the composite electrodes is modeled using porouselectrode theory. Thus, the electrolyte and active electrode material
are treated as a superimposed continua [1]. Concentrated solution
theory is used to describe transport within the binary liquid electrolyte.
The present effort incorporates detailed reaction mechanisms
into Newmans framework to describe the charge-transfer kinetics, providing an alternative to the ButlerVolmer representation.
The approach to formulating charge-transfer chemistry builds
upon earlier work in modeling elementary charge-transfer reactions in fuel-cell electrodes [7,8]. Generally speaking, elementary
reactions involve species in three phaseswithin the electrolyte,
on the electrode surfaces, and within the bulk of the electrode. Evaluating reaction rates depends upon the activities of
species and, for charge-transfer reactions, the electric potentials
of the participating phases. To enforce microscopic reversibility,
self-consistent thermodynamic properties are required for all participating species.
The elementary-reaction formulation facilitates the incorporation of reactions among surface-adsorbed species. Such
heterogeneous reactions may compete with the charge-transfer
(3)
Ck zk = 0,
(4)
eff = e ,
eff
=
D
2RTeff
F
(t 0 +
Li (e)
1)
1+
d(ln f )
d(ln CLi+ (e) )
(5)
.
(6)
8962
more than one surface site [12]. The site fractions are determined
by solving
charge movement is entirely the result of electric-potential gradients. The mean molar activity coefcient of the electrolyte is f ,
which is assumed to be constant in the present paper.
n k
= s k .
k (n) t
(10)
Li (e)
Li (e)
(7)
Deeff = De e .
(8)
The electrolyte diffusion coefcient De is a function of local concentrations, species charges, and binary diffusion coefcients within
the electrolyte phase. The last term represents the effects of lithium
ions entering the electrolyte via heterogeneous charge-transfer
chemistry at the electrode surfaces. In the limit of the lithium-ion
transference being unity, the charge-transfer chemistry does not
affect the electrolyte concentration. Hence the electrolyte composition would be spatially uniform. Conversely, if the transference
number is zero, then the charge-transfer chemistry causes signicant lithium-ion variations throughout the electrolyte [2].
Unlike the charge-conservation equation (Eq. (3)), the speciesconservation equation (Eq. (7)) retains the transient term. Species
transport through the electrolyte proceeds on time scales that are
commensurate with charge and discharge times.
Eqs. (3), (7), and (9) are spatially second order and thus
each require boundary conditions. Fig. 2 summarizes the conservation equations and the boundary conditions, illustrated in a
one-dimensional conguration. In the present model, the same
electrolyte solution is presumed to be used throughout the cell.
Therefore, Eqs. (3) and (7) span the entire cell, although with
different parameters (e.g., diffusion coefcients, conductivities,
porosities, reaction rates, etc.) in the anode, separator, and cathode regions. Composition and ux continuity must be preserved
at the material interfaces. Assuming the current collectors are pure
electronic conductors, the charge and concentration uxes through
the electrolyte must vanish at the current-collector interfaces.
Charge conservation within the solid electrode-particle network
is described by Eq. (9). At the anode current collector, the anodephase electric potential is set to a reference voltage a,cc = Vref . At
the cathode current collector, the cathode-phase electric-potential
gradient is set to meet the specied current density
ie = ceff c .
(11)
( eff b ) As ie = 0,
(9)
3. Particle intercalation
For the purposes of modeling lithium intercalation, lithium
transport between particles is neglected. That is, intercalatedlithium diffuses within a particle, but not from particle to particle.
Additionally the electrode particles are presumed to be spherical.
With these assumptions, the intercalated-lithium transport within
an electrode particle can be represented as
CLiI
t
1
= 2
r r
2
r DLiI
CLiI
r
,
(12)
CLiI
r
= s LiI .
(13)
8963
Fig. 2. Section of a lithium-ion cell, showing cell-scale conservation equations and boundary conditions.
4. Chemical kinetics
as
Although charge transfer is central to battery function, the overall charge-transfer process is comprised of both charge-neutral
heterogeneous reactions and charge-transfer reactions. Thus, the
detailed reaction mechanisms that describe the process must
accommodate both types of reactions. Species that participate in
the reactions are presumed to reside in one of three possible phases,
the electrolyte phase, the electrode-surface phase, or the electrodebulk phase. Evaluation of thermodynamic properties, including
chemical activities, depends upon the phase in which the species
resides. In general there are Ke species in the electrolyte phase,
Ks species in the electrode-surface phase, and Kb species in the
electrode-bulk phase.
The species activities are evaluated differently depending upon
the phase in which they reside. It is assumed here that the effective concentration for a species in the electrolyte solution is its
molar volumetric concentration. The activity of an adsorbed species
on an electrode particle is evaluated as the fraction of available
sites occupied (i.e., the site fraction). Evaluating the activities of
the intercalated species and intercalation vacancies is a somewhat
more complex task, which is discussed in subsequent sections.
= (a e ) (a e )
ie = i0 exp
F
a
RT
F
c
exp
RT
(14)
eq
eq
= (a e ) Ea ,
(15)
eq
eq
= (c e ) Ec ,
(16)
8964
(17)
where (b) means the species is in the bulk electrode phase and
(e) means the species is in the electrolyte phase. The bulk electrode phase and surface of the electrode are modeled as having
the same electric potential. By denition a charge-transfer reaction
moves charge from one phase to another. An elementary chargetransfer reaction transfers a single electron. For example, Reaction
(17) moves the charge from the anion B (e) in the electrolyte to
an electron e (b) in the electrode phase. Reaction (17) is written
in the anodic direction, meaning the forward reaction delivers a
negative charge into the electrode phase. The usual case produces
an electron in the electrode phase. However, a negatively charged
species moving from the electrolyte phase to the electrode phase
(e.g., A (e) A (b)) or a positively charged species moving from
the electrode to the electrolyte phase (e.g., B+ (B) B+ (e)) are both
anodic reactions.
The anodic and cathodic rates of progress q depend upon
thermal rate expressions, species activities, and electric-potential
differences as
qa = ka CA aA CB aB exp
qc = kc CC aC CD aD exp
a F(b e )
RT
c F(b e )
RT
(18)
,
(19)
Li (e)
Li
(20)
The net production rates for species k are found by summing the
rates of progress qi over all reactions I
s k =
I
ki qi ,
(24)
i=1
qi = qf qr ,
I
e ,i qi ,
qf = kf CA aA CB aB ,
(21)
where k
qr = kr CC aC CD aD .
(22)
G
RT
(23)
This relationship is valid for both charge-transfer and chargeneutral reactions. Evaluating the equilibrium constant requires
species thermodynamic properties such that
G can be evaluated.
(26)
i=1
In this case, the forward and reverse rates of progress may be written as
(25)
(27)
is the standard-state chemical potential. The species electrochemical potential may be written as
k = k + zk F,
(28)
LiV (b),
(29)
Li+ (e)
The species
and
represent: an intercalated
lithium within the bulk phase of the electrode, a lithium vacancy
within the bulk phase of the electrode, and a lithium ion within the
Li (e)
Li
+ e
+ RT ln ae Fb .
(30)
G29
RT
ln
F
(31)
where
G is the change in Gibbs free energy for Reaction (29).
The electric potential of the electrolyte phase is not easily measured. Therefore, the potential of the intercalation electrode is
usually measured relative to a reference pure lithium-metal electrode. The global reaction at the reference lithium electrode is
Li Li+ (e) + e ,
(32)
(33)
Li (e)
(34)
Eref = b ref =
G33
RT
ln
F
aLiV
RT ln LiV =
aLiI
(36)
RT
ln
F
(1 XLiI )
LiV
XLiI
LiI
E
GLiV
(37)
(nt GE )
nLiV
(38)
(39)
T,P,n V
Li
T,P,n I
Li
GE = XLiI XLiV
N
Am (XLiI XLiV )m ,
(40)
m=0
where Am are coefcients that can be t from equilibrium electricpotential measurements. After substituting Eq. (40) into Eqs. (38)
and (39) and some algebraic manipulation, the following relationships are obtained for the activity coefcients:
RT ln
LiI = (1 XLiI )
N
m
Am (2XLiI 1)
m=0
RT ln LiV = X 2 I
N
Am (2XLiI 1)m
m=0
1+
2mXLiI
,
2XLiI 1
2m(1 XLiI )
2XLiI 1
(41)
.
(42)
The activity expressions (Eqs. (41) and (42)) can be substituted into
the expression for the reversible electric-potential difference (Eq.
(37)) and simplied to give
eq
Eref =
(nt GE )
nLiI
total moles. The overbar (Gk ) indicates the partial molar excess free
energy. The excess Gibbs free energy must vanish when XLiI = 0 or
XLiV = 0.
Alternative models have been proposed to represent the excess
Gibbs free energy [13,16]. The semi-theoretical RedlichKister
expansion is used here to model the complexity of a lithium intercalation electrode as
Li
G33
E
GLiI
8965
Eref =
G33
RT
ln
F
1 XLiI
XLiI
1
+
Am (2XLiI 1)m+1
F
N
m=0
2mXLiI (1 XLiI )
(2XLiI 1)1m
(43)
Eref =
G33
RT
ln
F
1 XLiI
XLiI
(44)
8966
Table 1
RedlichKister coefcients for mesocarbon microbeads (MCMB) and cobalt-oxide
intercalation electrodes. All of the coefcients have units of J kmol1 . These coefcients are taken from Karthikeyan et al. [13].
Parameter
MCMB anode
LiCoO2 cathode
1.660 108
2.857 109
A0
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
3.580 108
3.501 108
3.525 108
3.569 108
3.863 108
3.591 108
2.879 108
1.498 108
3.991 108
9.617 108
6.326 108
6.483 109
6.517 109
6.566 109
6.579 109
6.302 109
5.047 109
2.711 109
6.905 108
N/A
N/A
N/A
Li
Karthikeyan et al. [13], who reported results for mesocarbonmicrobead (MCMB) anodes and lithium cobalt-oxide (Lix CoO2 )
cathodes. These coefcients were established by measuring
the reversible potential as a function of intercalation fraction. Table 2 provides coefcients for a graphite anode and a
nickelcobaltaluminum-oxide (NCAO) cathode with chemical
composition Lix Niy Coz AL1yz o2 . These coefcients were t using
empirical expressions for reversible potential reported by Doyle
and Fuentes [18] and Smith and Wang [3]. In both tables, the
standard-state chemical potential of intercalated lithium I is relLi
metal Li .
Figs. 3 and 4 illustrate the relatively complex behavior of lithium
intercalation electrodes. These gures are produced using Eq. (43)
and the parameters contained in Tables 1 and 2. Fig. 3 shows that
the MCMB electrode has three slight plateaus in the reversible
potential, which are likely caused by a mixture of solid phases
[16,19]. The graphite reversible potential (Fig. 4) is very close to
that of the MCMB electrode, but does not show the plateau features. Perhaps the graphite electrode has similar plateaus, but the
empirical expression provided by Doyle et al. does not capture such
features. The Liy CoO2 has a reversible-potential plateau between
0.8 < x < 0.9. The NCAO cathode has a reversible potential that is
Table 2
RedlichKister coefcients for a graphite anode and a NCAO cathode. All of the coefcients have units of J kmol1 . The graphite parameters are established by tting
an empirical expression for reversible potential [18]. The parameters for the NCAO
cathode are based upon an empirical expression reported by Smith and Wang [3].
Parameter
Graphite anode
NCAO cathode
1.165 107
3.955 108
A0
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
A11
A12
A13
A14
A15
A16
A17
A18
A19
3.268 106
3.955 106
4.573 106
6.147 106
3.339 106
1.117 107
2.997 105
4.866 107
1.362 105
1.373 108
2.129 107
1.722 108
3.956 107
9.302 107
3.280 107
N/A
N/A
N/A
N/A
N/A
7.676 107
3.799 107
2.873 107
1.169 107
1.451 107
8.938 107
1.671 108
7.236 107
1.746 108
4.067 108
9.534 108
5.897 108
7.455 108
1.102 109
2.927 108
7.214 108
9.029 108
1.599 108
6.658 108
1.084 109
Li
8967
(45)
(46)
(47)
Fig. 5. Cell voltage as a function of state-of-charge for various charging and discharging rates computed using ButlerVolmer equations and the two-step reaction
mechanisms.
properties is needed for all species to assure microscopic reversibility. Table 5 provides the standard-state free energies for all the
species in Table 4.
The internal energy of Li(NCAOs ) for a surface that is almost completely covered with lithium and the internal energy of Li(NCAO)
for a intercalation fraction close to unity are approximately 368
and 395 kJ mol1 , respectively. Conversely, the internal energy of
Li(Cs6 ) for a surface that is almost completely covered with lithium is
nearly equal to the internal energy of Li(C6 ) for a intercalation fraction close to unity (i.e., approximately 10 kJ mol1 ). The chemical
potential of an intercalated-lithium species (i.e., Li(NCAO) or Li(C6 ))
is a stronger function of the intercalation fraction than is the chemical potential of a surface lithium species (i.e., Li(NCAOs ) or Li(Cs6 ))
as a function of the adsorbed lithium site fraction.
Fig. 5 compares model-predicted results for cell voltage as
functions of state-of-charge, using ButlerVolmer formulations
and two-step charge-transfer mechanisms (Table 4). Because the
overall charge-transfer process remains close to equilibrium, the
voltage curves for the two chemistry formulations are virtually indistinguishable. Even for charge/discharge rates of 10C, the
highest activation overpotential is only around 4 mV. Such low
polarization is consistent with the high efciency of lithium-ion
batteries. Setting the elementary-reaction rates to be consistent
with the ButlerVolmer equation is equivalent to setting individual reaction rates sufciently high as to maintain reactions near
partial equilibrium.
8. Exchange current density and reversible potential
The exchange current density and reversible potential for
lithium intercalation both depend upon the activities of intercalated lithium and lithium vacancies. The functional form of the
exchange current density is usually derived by assuming that the
intercalation process depends upon species activity in an elementary fashion. By further assuming ideal activity, the exchange
8968
Table 3
Model parameters for FreedomCAR cell as derived from Smith and Wang [3].
Graphite
NCAO cathode
Anode
Separator
Cell geometry
Thickness (m)
Particle radius, rp (m)
Electrode volume fraction, s
Electrolyte volume fraction, elyt
Active specic area, As = 3s /rp (m1 )
Electrode area, A (m2 )
50
1
0.58
0.332
1.74 106
1.045
25.4
Lithium intercalation
Cmax (kmol m3 )
XLiI at 0% SOC
XLiI at 100% SOC
CLi+ (e) initial (kmol m3 )
16.1
0.126
0.676
1.2
Electrode surface
Available sites, (kmol m2 )
2.6 108
2.6 108
100
10
Transport parameters
Electrode conductivity, b (S m1 )
36.4
1
0.50
0.330
1.5 106
1.045
0.5
23.9
0.936
0.442
1.2
1.2
1.58
0.85
1.4
1.58
0.85
1.4
1.58
0.85
1.4
2.0 1016
2.6 1010
1.5
0.363
2.6 101
1.5
0.363
3.7 1016
2.6 101
1.5
0.36
Li (e)
s e = kf,29 C I aLiI exp
Li
a EF
RT
exp
c EF
RT
a EF
RT
Li (e)
exp
c EF
RT
.
(49)
,
(48)
K29
kf,29
=
= C + exp
Li (e)
kr,29
G29
RT
(50)
Table 4
Two-step reaction mechanisms for the anode and cathode of a cell with a graphite anode and a NCAO cathode. The available site density for both electrode surfaces is
= 2.6 108 kmol m2 . The superscript s denotes a surface site. The rate expressions and thermodynamic properties are adjusted to match results using the ButlerVolmer
expressions given by Smith and Wang [3].
kf (kmol, m, s)
Li(Cs6 ) + (C6 )
(e) + (Cs6 ) + e (C6 )
2.3 10
N/A
4.74
0.5
2.1 109
N/A
1.6 1029
0.5
Reaction
Li(C6 ) +
(Cs6 )
+
Li(Cs6 ) Li
G (kJ mol1 )
2.45
9.2
27.5
368.0
8969
Table 5
Thermodynamic properties for species that participate in the
two-step reaction mechanisms shown in Table 4.
G (kJ mol1 )
Surface species
Anode
Li(Cs6 )
(Cs6 )
Li(C6 )
V(C6 )
Li+ (e)
e (C6 )
9.2
0.0
11.65
0.0
0.0
0.0
Cathode
Li(NCAOs )
(NCAOs )
Li(NCAO)
V(NCAO)
Li+ (e)
e (NCAO)
368.00
0.0
3.95.5
0.0
0.0
0.0
exp
G29
a EF
RT
RT
c EF
RT
.
(51)
G
29
RT
a E eq F
RT
exp
a F
RT
c E eq F
RT
exp
c F
RT
.
(52)
After substituting Eq. (31) for the equilibrium electric potential and
some further algebraic manipulation, the net electron production
rate becomes
exp
a F
RT
G29
a
RT
a aa aa
a1
+
I
V
Li
exp
c 1c ac exp
a1
V a +
I
Li (e) Li
Li
Li
Li (e)
(1 c a )
G29
RT
c F
RT
(53)
exp
a F
RT
G29
a
RT
aaV aa+
Li
exp
ac
Li (e) LiI
c F
RT
.
(54)
The current density (A m2 ) is the product of the net electron production rate and Faradays constant. Thus, in ButlerVolmer form,
the current density may be written as
i = i0 exp
a F
RT
exp
c F
RT
(55)
ac .
Li (e) LiI
(56)
G29
a
RT
aaV aa+
Li
i0 = Q (T )aaV aa+
Li
ac ,
Li (e) LiI
(57)
where Q(T) is a function of temperature alone. The exchangecurrent-density expression that is typically used in the literature
(i.e., Eq. (47)) can be derived from Eq. (57) by assuming that the
activity coefcients for intercalated lithium and lithium vacancies
are unity and that the effective Li-ion concentration is evaluated as
its actual concentration [3,2022]. Thus, the most frequently used
formulation for the exchange current density is based upon a defacto assumption of ideal activities. However, as can be seen from
the reversible-potential data, the intercalation process is not ideal.
Although self consistency requires the use of non-ideal activities,
most lithium-ion battery models use non-ideal empirical functions
for the reversible potential, but assume ideal activities to evaluate charge-transfer rates. Zhang et al. investigated the effect of this
inconsistency [19]. An analogous approach is used here to evaluate
the inuence of using RedlichKister expansions to model activity
coefcients.
Written in terms of mole fractions and activity coefcients, the
exchange current density is
i0 = L(T )C a+
C a C c
a
c ,
Li (e) LiV LiI LiV LiI
(58)
8970
Fig. 8. Cell voltage as a function of state-of-charge for various discharge rates, comparing the use of ideal activities and using the RedlichKister expansion to evaluate
the exchange current density for a global one-step charge-transfer reaction.
Fig. 7. Exchange current density for a graphite electrode and a NCAO cathode as
functions of Li intercalation fraction [3]. The exchange current densities are calculated using ideal activities and using the RedlichKister expansion. The exchange
current densities have been normalized so that the maximum current densities are
the same as those reported by Smith and Wang [3]. Also, the electrolyte concentra3
tion is set to be CLi+ (e) = 1.2 kmol m .
L(T ) a
c
C + C a C c exp
(1 XLiI )2
i0 =
RT Li (e) LiV LiI
RT
m=0
exp
Am (2XLiI 1)m
1+
2XLiI 1
a 2
X
Am (2XLiI 1)m
RT LiI
N
m=0
2mXLiI
1
approach full intercalation, the exchange current density calculated with the RedlichKister expansion is signicantly lower than
the exchange current density calculated with ideal activities. The
lower exchange current density with non-ideal activities causes a
signicant increase in the cathode activation overpotentials at high
discharge rates. At low discharge rates (i.e., low current density),
only a small overpotential is required to compensate for the lower
exchange current density.
Lithium diffusion within the electrode particles usually limits
battery performance. Thus, only a small overpotential is required to
drive charge-transfer processes. As a result, under ordinary operating conditions, the functional form of the exchange current density
is not too important. At low to moderate discharge rates, the modeling error introduced by assuming ideal activity for the exchange
current density is small. However, the error is more signicant for
high discharge rates. However, under off-nominal operating conditions (e.g., very low temperature) the charge-transfer process
could become more rate limiting. In these cases, using the correct
functional form for the exchange current density is increasingly
important.
2m(1 XLiI )
2XLiI 1
.
(59)
Fig. 7 illustrates the relationship between exchange current density and intercalated-lithium fraction using a graphite anode and
NCAO cathode that represent the cell modeled by Smith and Wang
[3]. The exchange current densities are evaluated with two different assumptionsone assuming that the activity coefcients are
unity (Eq. (47)) and the other using RedlichKister expansions (Eq.
(59)). It is evident that non-ideal activities produce a functionally
different exchange current density, especially for the cathode.
To evaluate the importance of the non-ideal activities, the
battery model is implemented with the exchange current density calculated using ideal activity and using the RedlichKister
expansion. Fig. 8 compares constant-current discharge proles as
calculated using the two methods. At low to moderate discharge
rates, the two exchange-current-density formulations produce
nearly identical results. At discharge rates greater than 5C, the
two approaches begin to produce small, but noticeable, differences. At the higher rates the differences are greatest as the
cathode intercalation fraction nears unity. As the cathode particles
i0 = Fkf,46 exp
a I
Li
RT
1
ac aa aa+ .
aLiI + (aLiV /Keq,45 ) LiI LiV Li (e)
(60)
8971
Fig. 10. Lithium-ion concentration along the length of the cell at the end of the
discharge cycle.
Fig. 9. Exchange current densities for a graphite electrode and the NCAO cathode as
a functions of intercalation fraction [3]. The exchange current density is calculated
based upon a one-step ButlerVolmer reaction with ideal activities (Eq. (47)) and
based upon the proposed two-step mechanism with non-ideal activities(Eq. (60)).
3
The electrolyte concentration is set to be CLi+ (e) = 1.2 kmol m .
concentration of 1.2 kmol m3 . Changes in electrolyte concentration can affect the net rate of the charge-transfer reaction and
slightly affect the reversible potential. The reverse rate of progress
for Eq. (46) is proportional to the lithium-ion concentration within
the electrolyte phase. However, the 20% change in the electrolytephase concentration for a discharge rate of 10C only is overcome
by a slight change in the potential difference between electrode
and electrolyte phases. For instance, if the diffusion coefcient
for lithium ions within the electrolyte phase is increased by an
order of magnitude, then the maximum and minimum electrolyte
concentrations for the 10C discharge are 1.22 and 1.18 kmol m3 .
Even with this more uniform electrolyte concentration, the voltage discharge curve calculated with the higher electrolyte diffusion
coefcient is only slightly above the curve calculated with the nominal electrolyte diffusion coefcient (the maximum difference is
only 15 mV).
9.2. Electrode intercalation proles
9. Spatial proles
As the discharge/charge rates increase, the battery efciency
decreases, due primarily to relatively slower diffusion of intercalated lithium within electrode particles. As previously discussed,
the activation overpotentials are usually small, even for high currents. Therefore, the efciency loss is attributed primarily to lithium
diffusion within the electrolyte and/or solid electrode phase. The
diffusion coefcient for intercalated lithium within graphite and
NCAO particles are taken to be 2 1016 and 3.7 1016 m2 s1 ,
respectively [3]. The effective diffusion coefcient for lithium ions
within the electrolyte phase is around 5 1011 m2 s1 . Thus, the
diffusion coefcient for lithium ions in the electrolyte phase is
ve orders of magnitude higher than the diffusion coefcient for
intercalated lithium within solid electrode particles. However, the
average diffusion length for intercalated lithium is usually around
0.5 m and for lithium ions is around 70 m. Based upon these
diffusion coefcients and diffusion lengths, the polarization losses
are expected to be dominated by diffusion of intercalated lithium
within electrode particles.
During discharge/charge cycles, the surface coverages on electrode particles change considerably. Fig. 12 shows proles of the
the fractional surface coverage of adsorbed lithium Li(s) at different states of charge (SOC) during the 5C discharge cycle. During
discharge, intercalated lithium moves from the graphite particles
into the NCAO particles. Thus, the intercalated-lithium fraction
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Fig. 11. Intercalated-lithium concentration within anode and cathode particles near
the end of a discharge cycle. The representative particles are located near the middle
of the composite-electrode structure.
decreases inside graphite particles and increases inside NCAO particles. This process leads to a reduction in Li(C s ) and a rise in Li(NCAOs ) .
6
i0 exp
a G +
Li (e)
RT
Li (e)
(61)
Fig. 12. Lithium surface-coverage proles on graphite anode particles and NCAO
cathode particles as functions of state-of-charge (SOC) during a 5C discharge cycle.
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Acknowledgement
This effort was supported by the Ofce of Naval Research via
an RTC grant (N00014-05-1-03339). We gratefully acknowledge
many insightful discussions with Prof. David Goodwin (Caltech)
concerning the elementary-reaction representation and software
implementations of complex electrochemical charge-transfer processes. We also gratefully acknowledge benecial discussions with
Drs. Graham Goldin (ANSYS, Inc.), Harry Moffat (Sandia Natl.
Labs), Kandler Smith (NREL), and Huayang Zhu (Colorado School
of Mines).
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