Journal of The Electrochemical Society, 158 共3兲 A215-A222 共2011兲 A215

0013-4651/2010/158共3兲/A215/8/$28.00 © The Electrochemical Society

Modeling All-Solid-State Li-Ion Batteries

D. Danilov,a R. A. H. Niessen,b and P. H. L. Nottena,*,z
a
Eindhoven University of Technology, Den Dolech 2, 5600 MB Eindhoven, The Netherlands
b
Philips Research Laboratories, High Tech Campus 4, 5656 AE Eindhoven, The Netherlands

A mathematical model for all-solid-state Li-ion batteries is presented. The model includes the charge transfer kinetics at the
electrode/electrolyte interface, diffusion of lithium in the intercalation electrode, and diffusion and migration of ions in the
electrolyte. The model has been applied to the experimental data taken from a 10 ␮Ah planar thin-film all-solid-state Li-ion
battery, produced by radio frequency magnetron sputtering. This battery consists of a 320 nm thick polycrystalline LiCoO2
cathode and a metallic Li anode separated by 1.5 ␮m Li3PO4 solid-state electrolyte. Such thin-film batteries are nowadays often
employed as power sources for various types of autonomous devices, including wireless sensor nodes and medical implants.
Mathematical modeling is an important tool to describe the performance of these batteries in these applications. The model
predictions agree well with the galvanostatically measured voltage profiles. The simulations show that the transport limitations in
the solid-state electrolyte are considerable and amounts to at least half of the total overpotential. This contribution becomes even
larger when the current density reaches 0.5 mA cm−2 or higher. It is concluded from the simulations that significant concentration
gradients develop in both the positive electrode and the solid-state electrolyte during a high current 共dis兲charge.
© 2010 The Electrochemical Society. 关DOI: 10.1149/1.3521414兴 All rights reserved.

Manuscript submitted August 16, 2010; revised manuscript received November 5, 2010. Published December 28, 2010.

All-solid-state batteries are a quickly growing multimillion- on the conventional LiCoO2 chemistry. The electrodes are separated
dollar business, which nowadays have a large beneficial impact on by a solid-state electrolyte consisting of 共either or not N-doped兲 an
many applications, such as autonomous devices for ambient intelli- amorphous Li3PO4. Current collectors are placed on the outer sides
gence and medical implants. To describe the performance of these of each electrode. Their influence on the electrochemical processes
batteries under various conditions, mathematical modeling of the is considered to be negligible. In line with the battery morphology
Li-ion system was initiated in the mid-1980s. Simulating discharge 共Fig. 1a兲, a one-dimensional approach is adopted in the present
voltage curves of Li-ion batteries already dates back to the early work.
1980s.1 Interesting reviews dealing with the mathematical modeling The basic electrochemical charge transfer reactions at the posi-
of Li-ion batteries can be found in the literature.2-5 These models are tive and negative electrodes can be represented by
mainly based on the porous electrode theory developed by k1
Newman.6 LiCoO2
Li1−xCoO2 + xLi+ + xe− 共0 艋 x 艋 0.5兲 关1兴
Alternatively, equivalent electronic network models have been k−1
presented for various types of rechargeable batteries.7-11 All these
k2
models are based on the macroscopic descriptions of the fundamen-
tal electrochemical and physical processes occurring inside these Li
Li+ + e− 关2兴
k−2
systems, enabling the quantification of the relevant processes. The
electronic network models were elegantly used to visualize these respectively. The positive electrode generally consists of trivalent
processes. Good agreement between the simulations and experimen- cobaltoxide species, in which the lithium ions are intercalated
tal results was reported.7-11 In addition, the degradation 共aging兲 pro- 共LiCoIIIO2兲 to provide electroneutrality. During charging, the triva-
cess of Li-ion batteries has also been addressed.12,13 However, all lent cobalt is oxidized into four-valent cobalt 共CoIVO2兲 and the ex-
these reports did not address thin-film all-solid-state Li-ion batteries. cess of positive charge is liberated from the electrode in the form of
Solid-state Li-ion batteries represent the state-of-the-art in mod- Li+ ions. The Li+ ions cross the electrolyte and are reduced into
ern battery technology. Further improvement in the solid-state bat- metallic Li at the negative electrode. The reverse reactions take
tery technology requires an in-depth understanding of the electro- place during discharging.
chemical processes involved, and the ability to simulate these
processes is therefore a necessity. The ionically conductive solid- Charge transfer kinetics.— Considering the discrete valence
state electrolytes play an important role in the solid-state battery states for the CoII /CoIV redox couple, the number of electrons 共n兲
design 共see Bates et al.14,15兲. Construction of a consistent math-
transferred is unity. Denoting k1 and k−1 as the forward and back-
ematical model describing the conductivity in the solid-state electro-
ward reaction rate constants, respectively, the partial anodic 共Ia兲 and
lyte therefore forms an essential part of these models. A majority of
all-solid-state Li-ion batteries have a flat thin-film design. An ex- cathodic currents 共Ic兲 at the electrode surface can be represented by
ample of the cross section of an as-deposited solid-state Li-ion bat- s
Ia = FAk1aLiCoO 关3a兴
2
tery is given in Fig. 1a.
The aim of the current paper is to develop a mathematical model s
for all-solid-state Li-ion batteries, which includes all important
s
Ic = FAk−1aCoO a +
2 Li
关3b兴
physical and electrochemical characteristics and is capable of de- where F is the Faraday constant 共96,485 C mol−1兲, A is the elec-
scribing the basic functionality of these devices under a wide variety
trode surface area 共m2兲, and asi is the 共surface兲 activity of species i
of operating conditions.
共mol m−3兲. The reaction rate constants are a function of the elec-
trode potential,16 according to
Theoretical Considerations
k1 = k01e␣LiCoO2共F/共RT兲兲ELiCoO2 关4a兴
Electrochemical description.— A conventional solid-state Li-ion
battery consists of the following elements 共Fig. 1b兲. The negative 0 −共1−␣LiCoO 兲共F/共RT兲兲ELiCoO
k−1 = k−1 e 2 2 关4b兴
electrode comprises metallic lithium. The positive electrode is based
where R is the gas constant 共8.314 J mol−1 K−1兲, T is the absolute
temperature 共K兲, and ␣LiCoO2 is the charge transfer coefficient for
* Electrochemical Society Active Member. reaction Eq. 1. Introducing these equations into Eqs. 3a and 3b
z
E-mail: p.h.l.notten@tue.nl yields

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A216 Journal of The Electrochemical Society, 158 共3兲 A215-A222 共2011兲

If an overpotential ␩LiCoO
ct eq
= ELiCoO2 − ELiCoO is applied to
2 2
drive the charge transfer 共 兲 reaction at the positive electrode, then
ct

Eqs. 5a and 5b can be rewritten as

eq ct
s
Ia = FAaLiCoO k0e␣LiCoO2共F/共RT兲兲ELiCoO2e␣LiCoO2共F/共RT兲兲␩LiCoO2
2 1
关9a兴

eq ct
a +k0 e−共1−␣LiCoO2兲共F/共RT兲兲ELiCoO2e−共1−␣LiCoO2兲共F/共RT兲兲␩LiCoO2
s s
Ic = FAaCoO 2 Li −1
(a) 关9b兴
Combining the partial cathodic and partial anodic current–
potential curves, I = Ia − Ic yields an expression for the kinetics of
the charge transfer reaction at the positive electrode. When, in ad-
dition, the exchange current, as represented by Eq. 8, is introduced,
the following current–potential dependence is obtained

0
ILiCoO2 = ILiCoO 2
冋 s
aLiCoO 2

āLiCoO2
ct
e␣LiCoO2共F/共RT兲兲␩LiCoO2

−
s
aCoO a +
2 Li
s

āCoO2āLi+
e−共1−␣LiCoO2兲共F/共RT兲兲␩LiCoO2
ct
册 关10兴

s
Under fully kinetically controlled conditions, aCoO s
a +/
2 Li
(b) āCoO2āLi+ ⬇ 1 and aLiCoO /āLiCoO2 ⬇ 1 and Eq. 10 can be simplified
s
2
to the Butler–Volmer equation

Figure 1. An example of an SEM image of an as-produced solid-state Li-ion

0
ILiCoO2 = ILiCoO 2
关e␣LiCoO2共F/共RT兲兲␩LiCoO2 − e−共1−␣LiCoO2兲共F/共RT兲兲␩LiCoO2兴
ct ct

battery 共a兲 and general representation of a planar all-solid-state Li-ion battery 关11兴
共b兲.
In a similar way, the kinetics of the second electrode reaction Eq.
2 can be derived. The general expression for the charge transfer
reaction at the metallic lithium electrode can be represented by

冋 册
s
Ia = FAaLiCoO k0e␣LiCoO2共F/共RT兲兲ELiCoO2
2 1
关5a兴 s
s
aLi ct aLi+ ct
0
ILi = ILi e␣Li共F/共RT兲兲␩Li − e−共1−␣Li兲共F/共RT兲兲␩Li 关12兴
a +k0 e−共1−␣LiCoO2兲共F/共RT兲兲ELiCoO2
s
Ic = s
FAaCoO 2 Li −1
关5b兴 āLi āLi+
0
The exchange current ILiCoO is defined at the equilibrium poten- where asLi and āLi are the surface and bulk activities of the metallic
2
tial where Ia = Ic. Under equilibrium conditions, no concentration Li 共mol m−3兲, ␣Li is the charge transfer coefficient for reaction Eq.
profiles are present and hence all the surface activities are equal to 2, ␩ct
Li is the overpotential of the charge transfer reaction at the
the average bulk activities 共āi兲, i.e., asi = āi. From Eqs. 5a and 5b, it negative electrode, and the exchange current I0Li is given by
0
follows that under this condition, ILiCoO can be represented by
2
eq
0
ILi = FAks2共āLi+兲␣Li共āLi兲共1−␣Li兲 关13兴
0
ILiCoO 2
= FAāLiCoO2k01e␣LiCoO2共F/共RT兲兲ELiCoO2
0 −共1−␣LiCoO 兲共F/共RT兲兲ELiCoO
= FAāCoO2āLi+k−1 e
eq
关6兴 where ks2 is the standard rate constant for reaction Eq. 2. Obviously,
2 2
the activity of metallic lithium is considered unity. Furthermore, it
An expression for the equilibrium potential 共ELiCoO
eq
兲 can then be has been reported that the exchange current density for the metallic
obtained from Eq. 6
2
lithium electrodes17 is much larger than that for LiCoO2 18,19 and
because the electrode areas are exactly the same for planar thin-film
0 0
eq RT k−1 āCoO2āLi+ RT k−1 RT āCoO2āLi+
Li is much smaller than ␩LiCoO2.
batteries it is to be expected that ␩ct ct
ELiCoO = ln 0 = ln 0 + ln
2 F k1āLiCoO2 F k1 F āLiCoO2 For convenience, the charge transfer kinetics of the metallic lithium
reaction will therefore be neglected in this work.
关7兴
which is recognized as the Nernst equation. The first term on the Diffusion and migration in the electrolyte.— The Li3PO4-based
right-hand side represents the standard redox potential and the sec- solid-state electrolyte is a typical ionic conductor in which the con-
ond term takes into account the concentration dependence of the ductivity is caused by the transport of Li+ ions only. Lithium oxide–
eq
electrode potential. Eliminating ELiCoO in Eq. 6, using Eq. 7, leads phosphorus pentoxide 共Li2O–P2O5兲 is a classical glass-forming sys-
2
0
to a general expression for ELiCoO tem. It is known that a quasi-two-dimensional polymeric network of
2
0 ␣LiCoO 0 共1−␣LiCoO 兲 P2O5 is depolymerized in the presence of a modifier, such as
0
ILiCoO 2
= FA共k−1 兲 2共k 1兲 2
Li2O.20,21 This Li2O-induced modification results in converting the
⫻共āCoO2āLi+兲␣LiCoO2共āLiCoO2兲共1−␣LiCoO2兲 bridging oxygen atoms to nonbridging oxygen atoms 共nBO’s兲.22 The
“weak electrolyte” models conclude that Li may reside in the two
= FAks1共āCoO2āLi+兲␣LiCoO2共āLiCoO2兲共1−␣LiCoO2兲 关8兴 types of states in the glass matrix and assume that the ionic conduc-
tion process is dominated by the ions, thermally populating the
in which = ks1 共k01兲共1−␣LiCoO2兲共k−1
0 ␣LiCoO
兲 2 is the standard rate constant higher energy 共mobile兲 sites.23-25 The chemical reaction of the ion-
for reaction Eq. 1. ization reaction

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 Journal of The Electrochemical Society, 158 共3兲 A215-A222 共2011兲 A217

kd that at t = 0 no concentration profiles have been developed yet and

Li0
Li+ + n−
kr
describes the transfer process of immobile, oxygen-binded lithium
共indicated by Li0兲 to mobile Li+ ions leaving uncompensated nega-
tive charges 共n−兲 behind, which are chemically associated with the
closest nBO’s.22 In Eq. 14, kd is the dissociation rate constant for the
ionic generation reaction 共s−1兲 and kr is the rate constant for the
inverse recombination reaction 共m3 mol−1 s−1兲. Both constants obey
Arrhenius law. Denoting the activity of mobile Li+ ions by aLi+
共mol m−3兲, the activity of immobile Li ions by aLi0 共mol m−3兲, the
activity of n− by an− 共mol m−3兲, the total activity of Li atoms in the
Li3PO4 matrix by a0 共mol m−3兲, and the fraction of Li, which re-
sides in equilibrium in the mobile state by ␦, the equilibrium activity
eq eq
of the charge carriers can be represented by aLi+ = an− = ␦a0. The
equilibrium activity of immobile lithium is consequently given by
eq
aLi0 = 共1 − ␦兲a0. Under equilibrium conditions, the rates of the for-
eq eq eq
ward and backward reactions are equal 共kdaLi0 = kraLi+an−兲, which
implies that kd = kra0␦ /共1 − ␦兲. The overall rate of the charge car-
2
关14兴 hence that the activities of the charge carriers are equal to their
equilibrium activities. Equations 16c, 16d, 17c, and 17d represent
the flux conditions at the left and right boundaries of the electrolyte
共see also Fig. 1b兲. Assuming that no side reactions take place, the
current flowing through the battery can simply be represented by
I共t兲 = ILiCoO2共t兲 = −ILi共t兲. Equations 16 and 17 accommodate diffu-
sion and migration of both charge carriers. In line with Eq. 15, the
flux of each charge carrier is considered independently. Equations
16 and 17 are solved under the electroneutrality condition a共y,t兲
= an−共y,t兲 = aLi+共y,t兲. The Li+ ions in the electrolyte are generated
from the immobile Li atoms, thus a0 = aLi0共y,t兲 + aLi+共y,t兲
= aLi0共y,t兲 + a共y,t兲. It can be shown27 that Eqs. 16 and 17 can be
reduced to the diffusion equation with respect to a共y,t兲, according to
⳵a 2DLi+Dn− ⳵2a
= +r
⳵t DLi+ + Dn− ⳵y 2
a共y,0兲 = ␦a0

rier generation is given by rd = kdaLi0 − kraLi+an−, and the net rate of ⳵a共0,t兲 I共t兲
=
the inverse reaction is given by the opposite number. ⳵y 2FADLi+
The net current passing the electrode/electrolyte interface in-
duces an ionic mass and charge transport in the electrolyte. In the ⳵a共L,t兲 I共t兲
case of a flat geometry, it is reasonable to assume that the ionic = 关18兴
transport in the electrolyte is also a one-dimensional process, which ⳵y 2FADLi+
can be described by the Nernst–Planck equation26

再
and an analytical expression for the electric field is obtained

Jj = − Dj
⳵a j z jF
⳵y
+
RT
D ja jE 关15兴 E共y,t兲 =
RT 1
F a共y,t兲
−
I共t兲
+
DLi+ − Dn− ⳵a共y,t兲
⳵y
冋
册冎
2FADLi+ DLi+ + Dn−
where J j共y,t兲 is the flux of species j 共mol m s 兲 at a distance y
−2 −1
I共t兲
from the surface of the negative electrode at any moment in time t, − 关19兴
D j is the diffusion coefficient of j 共m2 s−1兲, ⳵a j /⳵y is the concentra- 2FADLi+
tion gradient 共mol m−4兲, E is the potential gradient 共V m−1兲, z j is The total mass-transfer 共mt兲 overpotential across the Li3PO4 electro-
the valence 共dimensionless兲, and a j is the activity 共mol m−3兲 of spe- mt
lyte ␩Li+ can then be given by

冋 册 冕
cies j. The two terms on the right-hand side of Eq. 15 represent the
L
diffusion and migration contributions to the ionic flux. mt RT a共L,t兲
Denoting rd = r and rr = −r where r = kdaLi0 − kraLi+an−, it can ␩Li+共t兲 = ln − E共y,t兲dy 关20兴
F a共0,t兲 0
be shown that the two partial differential equations, describing the
diffusion–migration process combined with the generation/ The first and the second terms in Eq. 20 define the diffusion and
recombination reaction Eq. 14, can be represented by migration components of the total overpotential, respectively.
⳵aLi+ ⳵JLi+ Diffusion in the electrode.— The positive electrode consists of
=− +r 关16a兴 trivalent cobaltoxide species, in which the lithium ions are interca-
⳵t ⳵y
lated 共LiCoIIIO2兲. According to Refs. 28 and 29 Li+ ions in LiCoO2
aLi+共y,0兲 = ␦a0 关16b兴 are screened by the mobile electrons, which accompany Li+ when it
moves from one interstitial site to the other. This screening implies
ILi共t兲 that the migration term can be neglected. Assuming, for simplicity
JLi+共0,t兲 = − 关16c兴 reasons, that the rate of phase transition does not play an important
zLi+FA role and considering the diffusion coefficients in both phases to be
equal, the mass transport of Li ions inside the positive electrode can
ILiCoO2共t兲 be described by the standard diffusion equation
JLi+共L,t兲 = 关16d兴
zLi+FA ⳵aLiCoO2 ⳵2aLiCoO2
= DLi 关21a兴
and ⳵t ⳵y2
⳵ a n− ⳵ J n−
=− +r 关17a兴 aLiCoO2共y,0兲 = aLiCoO
0
关21b兴
⳵t ⳵y
2

⳵aLiCoO2共L,t兲 I共t兲
an−共y,0兲 = ␦a0 关17b兴 DLi = 关21c兴
⳵y FA
Jn−共0,t兲 = 0 关17c兴
⳵aLiCoO2共L + M,t兲
DLi =0 关21d兴
Jn−共L,t兲 = 0 关17d兴 ⳵y
where ILiCoO2共t兲 and ILi共t兲 are the charge transfer currents at the where aLiCoO2共y,t兲 is the Li+ activity 共mol m−3兲 in location y at any
positive and negative electrodes, respectively. Equations 16a and
0
moment of time t, aLiCoO is the activity of Li+ 共mol m−3兲 in the
2
17a represent the mass balances, Eqs. 16b and 17b reflect the fact positive electrode at t = 0 共in equilibrium兲, and DLi is the diffusion

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A218 Journal of The Electrochemical Society, 158 共3兲 A215-A222 共2011兲

Table I. List of symbols.

Notation Dimension Description

L m Thickness of the electrolyte

M m Thickness of the electrode
A m2 Geometrical surface area
as mol m−3 Generic notation for surface activity
ā mol m−3 Generic notation for bulk activity
aLiCoO2 mol m−3 Activity of Li in the positive 共LiCoO2兲 electrode 共generic兲
aLi mol m−3 Activity of Li in the negative 共metallic Li兲 electrode 共generic兲
aLi+ mol m−3 Activity of Li+ in the electrolyte 共generic兲
a n− mol m−3 Activity of n− in the electrolyte 共generic兲
aLi0 mol m−3 Activity of immobile lithium in Li3PO4 matrix
a0 mol m−3 Total activity of Li atoms in Li3PO4 matrix
k1 m s−1 Positive electrode charge transfer anodic reaction rate constant
k−1 m4 mol−4 s−1 Positive electrode charge transfer cathodic reaction rate constant
ks1 m2.8 mol−0.6 s−1 Standard rate constant for positive electrode charge transfer reaction
k2 m s−1 Negative electrode charge transfer anodic reaction rate constant
k−2 m s−1 Negative electrode charge transfer cathodic reaction rate constant
ks2 m s−1 Standard rate constant for negative electrode charge transfer reaction
kr m3 mol−1 s−1 Li+ ion recombination reaction rate constant
kd s−1 Li+ ion generation reaction rate constant
r mol s−1 Net rate of Li+ ion generation/recombination
␦ — Fraction of mobile Li+ ions in the electrolyte in equilibrium
DLi+ m2 s−1 Diffusion coefficient for Li+ ions in the electrolyte
D n− m2 s−1 Diffusion coefficient for n− in the electrolyte
DLi m2 s−1 Diffusion coefficient for Li in the positive electrode
Jj mol m−2 s−1 Flux of species j in the electrolyte
zj — Valence of species j
ILiCoO2, ILi A Main storage reaction currents for the positive and negative electrode correspondingly
I A Current flowing through the battery
0
ILiCoO , I0Li A Exchange currents for the positive and negative electrodes
2
correspondingly
I a, I c A Anodic and cathodic currents for the charge transfer reactions
eq
ELiCoO2, ELiCoO V Voltage and equilibrium voltage of the positive electrode
2
eq
Ebat, Ebat V Voltage and equilibrium voltage of the battery
E V m−1 Electric field 共electric potential gradient兲
␩ V Total overpotential of the battery
␩LiCoO
ct
V The charge transfer overpotential for the positive electrode
mt 2
␩Li+ V The mass-transfer overpotential across the electrolyte
␩LiCoO
d
V The diffusion overpotential for the positive electrode
2
T K Temperature
t s Time

coefficient 共m2 s−1兲 of Li in the electrode. Equation 21a represents ␩t = ␩LiCoO

ct
+ ␩LiCoO
d
+ ␩Li+
mt
关22兴
2 2
how the profile develops as a function of time. Equation 21b reflects
the initial conditions and Eq. 21c describes the supply or consump- according to the three main processes occurring inside the battery:
tion of the Li+ ions at the electrode interface. Equation 21d reveals the charge transfer reaction at the positive electrode, the ionic flow
the insulating condition at the electrode/current collector interface through the solid-state electrolyte, and the diffusion in the interca-
共y = L + M in Fig. 1b兲 through which no Li+ ions can pass. Note lation electrode. Herewith, it is indeed assumed that ␩ctLi at the me-
that the normalized activity of Li in the electrode can be defined as tallic lithium electrode is negligibly low. Table I lists all model
x = aLiCoO2 /aLiCoO
max max
, where aLiCoO is the maximal activity of Li in parameters.
2 2
LiCoO2 共23.3 kmol m 兲. The diffusion overpotential is calculated
−3
Experimental
according to Refs. 28 and 30 as ␩LiCoO d eq
= ELiCoO 共xs兲
2 2 A 10 ␮Ah planar thin-film all-solid-state Li-ion battery was de-
− ELiCoO 共x̄兲 ⬇ 共x − x̄兲共 ⳵ELiCoO /⳵x兲, where x = x共L,t兲 is the nor-
eq s eq s
posited using an in-house built equipment, comprising a radio fre-
2 2
malized surface activity, x̄ is the average bulk activity, and quency sputtering tool with 2 in. targets 共13.56 MHz兲 and thermal/
⳵ELiCoO /⳵x is the derivative of the equilibrium potential of the posi-
eq
E-beam evaporation, both placed in a glove box containing an inert
2
tive electrode at the surface. argon atmosphere. Care was taken that the base pressure before
deposition was always less than 10−6 mbar. Hard masks were used
for the definition of each of the active battery layers. As substrate,
Combined effects.— The equilibrium voltage of the Li-ion bat- silicon covered with a bistack of TiO2 /Pt 共50 nm/250 nm兲 was
tery is the difference between the equilibrium voltage of the positive used. For the cathode 共LiCoO2 target兲, a power of 60 W and a
and negative electrodes, i.e., Eeq eq eq
bat = ELiCoO2 − ELi . The total battery pressure of 8 ⫻ 10−6 bar O2 /Ar 共4:6兲 were used to deposit 320 nm.
overpotential 共␩兲 is the difference between the equilibrium voltages Hereafter, the cathode was thermally annealed at 800°C for 10 min
and the current-driven voltages 共␩ = Ebat − Eeq bat兲. The total battery using rapid thermal anneal at a 60°C/min heating rate in order to
overpotential 共␩t兲 is a sum of three contributions obtain the high-T crystalline phase. Hereafter, a 1.5 ␮m thick

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 Journal of The Electrochemical Society, 158 共3兲 A215-A222 共2011兲 A219

4.2 4.2

Voltage [V]
4.0
Voltage [V]

4.1

3.8 4.0

3.6 3.9

3.4
3.8

3.2
3.7

3.0
-40 -30 -20 -10 0 10
Time [min]
Figure 2. 共Color online兲 Experimentally measured voltage profiles during
CCCV charging 共CC = C-rate; Vmax = 4.2 V兲, relaxation and discharging at
various C-rates 共3.2, 6.4, 12.8, 25.6, and 51.2 C-rate兲.
Li3PO4 layer was deposited using a power of 30 W using a Li3PO4
target 共at a pressure of 15 ⫻ 10−6 bar Ar兲. Finally, 150 nm cobalt
was deposited as the current collector at ⬃5 Å/s via E-beam evapo-
ration. The as-prepared battery was charged and discharged accord-
ing to the following regime: constant current constant voltage
共CCCV兲 charging with a 1.6 C-rate till the maximum voltage level
of 4.2 V was reached, followed by a 30 min relaxation period and a
current constant 共CC兲 discharge. The following discharge rates were
successively applied: 1.6, 3.2, 6.4, 12.8, 25.6, and 51.2 C. Cycling
was performed on an 8-channel Biologic VMP3 battery tester
equipped with a low current and impedance boards. The experimen-
tal data are obtained at room temperature, i.e., 25°C, the same tem-
perature as used for the simulations.
Results and Discussion
Figure 2 shows the charge and discharge voltage curves as a
function of time where, for convenience reasons, t = 0 corresponds
to the start of each discharge cycle. It is remarkable to see that these
thin-film batteries can be discharged with extremely high currents up
to 51.2 C-rate.
20 3.6
0 20 40 60 80 100 120
I [ µA cm -2]
Figure 4. 共Color online兲 The blue symbols are measured voltages at various
values of Qout; The red line is the regression interpolation; The red dots
represent the extrapolated equilibrium voltage. The curves were obtained at
Qout = 0, 2, 4, 8, 9.25, and 9.50 ␮Ah cm−2.
Figure 3 shows the same discharge curves but now plotted as a
function of the amount of extracted charge 共Qout兲, i.e., capacity den-
sity, together with the extrapolated equilibrium voltage curve 共green
line兲. Note that the equilibrium voltage of the battery is equal to that
of the positive electrode as the voltage of the metallic Li electrode is
0 V vs Li/Li+, i.e., Eeq eq
bat = ELiCoO2. The equilibrium voltage has been
determined by regression extrapolation 共see Chap. 4 in Ref. 31兲. The
regression extrapolation was applied separately on the flat and steep
parts of the equilibrium voltage curve. Figure 4 shows, as an ex-
ample, the dependence of the voltage on the applied discharge cur-
rent for six different values of Qout. A linear relationship between the
current density and voltage is found for the low Qout values up to
8 ␮Ah cm−2. At low state-of-charges, a nonlinear dependence is
found, which can be well approximated by a quadratic regression
model. The steep part of the equilibrium voltage curve has been
obtained by applying a regression model to the set of Qout and cur-
rent densities. By extrapolating the currents to zero, the equilibrium
voltage can be determined. Figure 5 shows the dependence of Qout
[ µAh cm-2]

4.2
10.0

4.0
Voltage [V]

9.8
out
Q

3.8
9.6
3.6

9.4
3.4

9.2
3.2

9.0
3.0 0 20 40 60 80 100 120
0 2 4 6 8 10 I [ µA cm -2]
-2
Q [ µAh cm ]
out
Figure 5. 共Color online兲 The blue symbols are measured Qout values as a
Figure 3. 共Color online兲 Equilibrium voltage 共green兲 obtained from extrapo- function of discharge current; The red line is the regression interpolation;
lation and experimentally measured discharge curves 共1.6, 3.2, 6.4, 12.8, The red symbols represent the extrapolated Qout values. The curves are ob-
25.6, and 51.2 C-rate兲. tained at V = 3.0, 3.2, 3.4, 3.6, and 3.8 V.

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A220 Journal of The Electrochemical Society, 158 共3兲 A215-A222 共2011兲

0.0 on the applied discharge current at five different voltages. For all
voltages, nonlinear dependencies between Qout and the applied cur-
η [V]

rent are found, which have been approximated by a quadratic regres-

-0.1
sion. Qout can then be found by extrapolating toward zero current.
The difference between the equilibrium voltage and the discharge
-0.2 voltage is the overpotential. The dependence of the total experimen-
tal overpotential as a function of Qout at various discharge rates is
shown in Fig. 6. For all currents, a wide flat plateau is followed by
-0.3 a sharp decrease at the end of the discharge process.
Figure 7 shows the optimized simulations obtained with the ap-
-0.4
plied model. Good agreement is obtained between the experimental
results 共blue dots兲 and the theoretical prediction 共red lines兲 for all
共dis兲charge currents. The optimized parameters are listed in Table II.
-0.5 Figure 8a shows the contributions of the various overpotential
components during discharging at 3.2 C-rate. It is evident that the
diffusion overpotential at the LiCoO2 electrode 共␩LiCoO d
兲 provides
-0.6 2
0 2 4 6 8 10 the largest contribution at the beginning of discharging, but reduces
Q [ µAh cm -2] toward zero, except at the very end of the discharge process where it
out increases sharply due to the steep concentration gradient of Li ions
mt
Figure 6. 共Color online兲 Experimental overpotentials as a function of Qout at in the cathode. The mass-transfer overpotential 共␩Li+兲 of the electro-
various C-rates 共from 1.6 to 51.2 C-rate兲. lyte is the second in magnitude at the beginning of discharging, but
dominates in the end. The charge transfer overpotential 共␩LiCoO ct
兲 is
2
initially small but is growing significantly toward the end of the
4.2 discharge process.
Similarly, a high discharge rate of 51.2 C 共Fig. 8b兲 induces a
mt
4.0 high mass-transfer overpotential 共␩Li+兲, which is slowly increasing
Voltage [V]

upon discharging. This overpotential across the electrolyte is respon-

sible for at least half of the total overpotential starting from the
3.8
second half of the discharge process. The diffusion overpotential at
the cathode 共␩LiCoO
d
兲 contributes significantly in the beginning and
3.6 2
at the very end of the discharge process. This behavior is in-line
with the definition of the diffusion overpotential which is propor-
3.4 tional to the derivative of the equilibrium voltage 共see Diffusion in
the electrode兲. Consequently, the overpotential is small in the second
3.2 half of the discharge process, where the corresponding equilibrium
voltage curve is rather flat and explodes sharply at the very end of
the discharge process, where the equilibrium voltage drops rapidly.
3.0 The simulated total overpotential agrees well with the experimen-
-40 -30 -20 -10 0 10 20
Time [min] tally determined overpotentials plotted in Fig. 5: in the case of a
51.2 C-rate discharge simulation, a wide overpotential plateau at
Figure 7. 共Color online兲 Overall performance of the model during dis- about −0.2 V is calculated which is in good agreement with the
charges with various C-rates. The blue symbols are measurements and, the experimentally determined overpotential in Fig. 6 共black line兲. By
red lines are the model predictions. carefully checking the various overpotential contributions at the end

Table II. Model parameters.

Estimated
Parameter Dimension value Description

L nm 1500 Thickness of the electrolytea

M nm 320 Thickness of the electrodea
A cm2 1 Geometrical surface areaa
a0 mol m−3 6.01 ⫻ 104 Total activity of Li atoms in Li3PO4 matrixb
kr m3 mol−1 s−1 0.90 ⫻ 10−8 Li+-ion recombination reaction rate
␦ — 0.18 Fraction of free Li+ ions in equilibrium
DLi+ m2 s−1 0.90 ⫻ 10−15 Diffusion coefficient for Li+ ions in the electrolyte
D n− m2 s−1 5.10 ⫻ 10−15 Diffusion coefficient for n− in the electrolyte
max
aLiCoO mol m−3 2.33 ⫻ 104 Maximal activity of Li in the positive electrodec
2
DLi m2 s−1 1.76 ⫻ 10−15 Diffusion coefficient for Li in the positive electrode
␣LiCoO2 — 0.6 Charge transfer coefficient for the positive electrode
ks1 m2.8 mol−0.6 s−1 5.1 ⫻ 10−6 Standard rate constant for positive electrode charge
transfer reaction
a
Design parameters.
b
Outcome of NDP analysis.
c
Estimated from the design parameters and maximal capacity of the battery. All the remaining parameters
are obtained from model optimization.

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 Journal of The Electrochemical Society, 158 共3兲 A215-A222 共2011兲 A221

0
η [mV]

aLiCoO [kmol m ]
-3
25

1.0
-25

x
2
20 0.9

0.8
-50
15 0.7

0.6

-75 0.5
300
200 2
1.5
1
100 0.5
(a) -100
0 -0.5
0
0 5 10 15 20 Electrode [nm] Time [min]
Time [min]
Figure 9. 共Color online兲 Development of the Li-concentration profile inside
the positive electrode during 51.2 C discharge.
0.0
η [V]

discharge current is switched off after 1 min, the concentration pro-

-0.1
files rapidly relax to their equilibrium value of 11 kmol m−3.
Figure 11 shows the development of the total overpotential 共pink
-0.2
line兲 and the individual contributions of diffusion 共red line兲 and
migration 共blue line兲 at 51.2 C-rate discharging. The equilibrium
situation 共t ⬍ 0兲 corresponds to a zero overpotential. When the cur-
-0.3 rent is switched on, a 40 mV voltage drop is instantaneously
formed, which is fully carried by the electric field as no concentra-
tion gradient has been built up yet. This rapid initial increase is
-0.4 followed by a more steady increase of both migration and diffusion,
in total amounting to 110 mV at the end of discharging. The thick-
nesses of the electrode 共M兲 and the electrolyte 共L兲 have been deter-
(b) -0.5 mined by scanning electron microscopy 共SEM兲. The total number of
0 0.25 0.50 0.75 1.00
Li in the Li3PO4 electrolyte has been analyzed by neutron depth
Time [min]
profiling 共NDP兲 to be a0 = 6.01 ⫻ 104 mol m−3. The simulations
show that, in equilibrium, only about 18% of the Li atoms are mo-
Figure 8. 共Color online兲 Development of the overpotentials as a function of
bile and that the Li-ion recombination reaction rate is moderately
time during low-current 共a兲 and high-current 共51.2 C兲 discharging 共b兲. The
red lines represent simulated Butler–Volmer overvoltage 共␩LiCoOct
兲, the pink
large 共kr = 0.9 ⫻ 10−8 m3 mol−1 s−1兲. Both diffusion coefficients
mt
2
are estimated to be of the order of 10−15 m2 s−1.
lines represent mass-transfer overpotential in the electrolyte 共␩Li +兲, and the
Figure 12 reviews the concentration profiles across the entire
green lines represent diffusion overpotential in the solid-state electrode
共␩LiCoO
d
兲. The black lines are the total simulated overvoltage, i.e., the sum-
battery stack at three moments in time: directly preceding constant
2
mation of the three individual components 共␩t兲.
current-discharging 共blue line兲, 20 s after 51.2 C-rate discharging
has been commenced 共red line兲, and after 50 s 共pink line兲 just before
discharging will be terminated. It can be concluded that before dis-
charging no concentration profiles are present in both the electrode
of the discharge process, it becomes clear that diffusion inside the
LiCoO2 electrode is the leading process, inducing the current inter-
ruption at the battery cutoff voltage of 3.0 V.
Figure 9 shows in more detail the development of the Li-ion
aLi+ [kmol m ]
-3

concentration profile in the LiCoO2 electrode upon discharging at a 16

high 51.2 C-rate. Starting at t = 0, the system is at equilibrium and
14
no concentration gradient has been built up yet. As soon as a dis-
charge current is applied, a concentration profile is built up across 12
the LiCoO2 electrode, increasing more rapidly at the electrode/
electrolyte interface. This is in good agreement with the Li- 10
intercalation reaction Eq. 1, which indeed reveals an influx of Li
8
ions into the positive electrode during discharging. The diffusion
coefficient for Li in the electrode has been analyzed to be 1.76 6
⫻ 10−15 m2 s−1, which also agrees well with the reported experi-
1.5
mental results.32,33 After about 1 min, the current is switched off and
the concentration profile quickly relaxes toward the equilibrium. 1 3
The evolution of the concentration profile of Li+ ions across the 2
0.5 1
electrolyte upon high current discharging is shown in Fig. 10. Start- 0
ing from a flat concentration profile at equilibrium, a steep increase Electrolyte [µm] 0
Time [min]
of the Li+-concentration is found at the metallic Li/electrolyte inter-
face 共at y = 0, see also Fig. 1b兲, while at the LiCoO2/electrolyte Figure 10. 共Color online兲 Development of the Li-concentration profile inside
interface 共y = L兲 the concentration becomes rather low. When the the electrolyte layer during 51.2 C discharge.

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A222 Journal of The Electrochemical Society, 158 共3兲 A215-A222 共2011兲

Conclusions
0.00
A one-dimensional model has been applied to simulate the per-
Diffusion formance of all-solid-state Li-ion batteries. The model describes the
η [V]

-0.02 electrode, electrolyte, and the interface between those elements. The
proposed model provides a detailed information about the various
-0.04 diffusion and migration fluxes, concentration profiles, and the cor-
Migration
responding overpotential contributions, occurring across the elec-
trode and electrolyte. The model provides good fits with the mea-
-0.06 surements, including discharge curves with high C-rates.

-0.08 Total
Acknowledgments

-0.10
The authors thank Dr. H.T. Hintzen 共Eindhoven University of
Technology兲 and Dr. I. Kokal for their valuable discussions. The
work has been supported by the European Union 共FP7兲 within the
-0.12 framework of the Superlion project.
0 1 2 3
Eindhoven University of Technology assisted in meeting the publication
Time [min]
costs of this article.
Figure 11. 共Color online兲 Development of the overpotentials across the elec- References
trolyte layer during 51.2 C discharge: diffusion 共red line兲, migration 共blue
1. M. Doyle, T. F. Fuller, and J. Newman, J. Electrochem. Soc., 140, 1526 共1993兲.
line兲, and summation of those two, total 共pink line兲. 2. C. R. Pals and J. Newman, J. Electrochem. Soc., 142, 3274 共1995兲.
3. L. Song and J. W. Evans, J. Electrochem. Soc., 147, 2086 共2000兲.
4. G. G. Botte, V. R. Subramanian, and R. E. White, Electrochim. Acta, 45, 2595
共2000兲.
and the electrolyte, indeed implying that the battery is in the equi- 5. P. M. Gomadam, J. W. Weidner, R. A. Dougal, and R. E. White, J. Power Sources,
librium state. However, as soon as the current is switched on, sig- 110, 267 共2002兲.
nificant concentration gradients in both the electrode and the elec- 6. J. S. Newman, Electrochemical Systems, Prentice-Hall, Englewood Cliffs, NJ
trolyte are established, with significant accumulation at the metallic 共1991兲.
7. W. S. Kruijt, P. H. L. Notten, and H. J. Bergveld, J. Electrochem. Soc., 145, 3764
lithium electrode 共y = 0兲 and depletion at the electrolyte/cathode 共1998兲.
interface 共y = L兲. The lithium concentration in the positive elec- 8. P. H. L. Notten, W. S. Kruijt, and H. J. Bergveld, J. Electrochem. Soc., 145, 3774
trode, conversely, is growing with time, in agreement with the main 共1998兲.
9. H. J. Bergveld, W. S. Kruijt, and P. H. L. Notten, J. Power Sources, 77, 143
storage reaction Eq. 1. The simulated total overpotential corresponds 共1999兲.
to charge transfer resistances of the order of 50–100 ⍀ at the volt- 10. W. S. Kruijt, E. de Beer, P. H. L. Notten, and H. J. Bergveld, Abstract 104, The
age plateau but obviously increases at the end of discharging. This is Electrochemical Society Meeting Abstracts Vol. 97-1, Paris, France, p. 114 共1997兲.
also in good agreement with the reported experimental results.18,19 11. H. J. Bergveld, W. S. Kruijt, and P. H. L. Notten, Battery Management Systems—
Design by Modelling, Philips Research Book Series, Vol. 1, Kluwer Academic
Publishers, Boston 共2002兲.
12. D. Danilov and P. H. L. Notten, Abstract 390, in Proceedings of the 12th IMLB
Conference, Nara, Japan, 2004.
13. D. Danilov and P. H. L. Notten, in Proceedings of the 5th IEEE Vehicle Power and
Propulsion Conference, IEEE, Dearborn, p. 317 共2009兲.
20 20 14. J. B. Bates, N. J. Dudney, G. R. Gruzalski, R. A. Zuhr, A. Choudhury, C. F. Luck,
aLiCoO [kmol m ]

and J. D. Robertson, J. Power Sources, 43, 103 共1993兲.

aLi+ [kmol m ]

-3
-3

15. J. B. Bates, N. J. Dudney, D. C. Lubben, G. R. Gruzalski, B. S. Kwak, Y. Xiaohua,

and R. A. Zuhr, J. Power Sources, 54, 58 共1995兲.
16. P. H. L. Notten, in Interstitial Intermetallic Alloys, F. Grandjean, G. J. Long, and K.
H. J. Buschow, Editors, Chap. 7, p. 151 Kluwer, Dordrecht 共1995兲.
15 15 17. N. Munichandraiah, L. G. Scanlon, and R. A. Mars, J. Power Sources, 72, 203
2

共1998兲.
18. Y. Iriyama, T. Kako, C. Yada, T. Abe, and Z. Ogumi, J. Power Sources, 146, 745
共2005兲.
19. I. Yamada, Y. Iriyama, T. Abe, and Z. Ogumi, J. Power Sources, 172, 933 共2007兲.
20. J. R. van Wazer, Phosphorus and its Compounds, Vol. 1, Interscience, New York
10 10 共1958兲.
21. S. W. Martin, Eur. J. Solid State Inorg. Chem., 28, 163 共1991兲.
22. H. Kahnt, J. Non-Cryst. Solids, 203, 225 共1996兲.
23. M. D. Ingram, C. T. Moynihan, and A. V. Lesikar, J. Non-Cryst. Solids, 38-39, 371
共1980兲.
24. D. Ravaine and J. L. Souquet, Phys. Chem. Glasses, 18, 27 共1977兲.
5 5 25. S. W. Martin and C. A. Angell, J. Non-Cryst. Solids, 83, 185 共1986兲.
26. A. J. Bard and L. R. Faulkner, Electrochemical Methods, Fundamentals and Ap-
plications, John Wiley & Sons, New York 共1980兲.
27. D. Danilov and P. H. L. Notten, Electrochim. Acta, 53, 5569 共2008兲.
28. W. R. McKinnon and R. R. Haering, in Modern Aspects of Electrochemistry, Vol.
0 0 15, R. E. White, J. O. M. Bockris, and B. E. Conway, Editors, Chap. 4, p. 235,
0 0.5 1 1.5 1.82 Plenum, New York 共1983兲.
29. K. Kang and G. Ceder, Phys. Rev. B, 74, 094105 共2006兲.
y [ µm] 30. S. Atlung, K. West, and T. Jacobsen, J. Electrochem. Soc., 126, 1311 共1979兲.
31. V. Pop, H. J. Bergveld, D. Danilov, P. P. L. Regtien, and P. H. L. Notten, Battery
Management Systems: Accurate State-of-Charge Indication for Battery-Powered
Figure 12. 共Color online兲 Concentration profiles in the complete battery
Applications, Philips Research Book Series, Vol. 9, Springer, New York 共2008兲.
stack before discharging 共51.2 C-rate兲 has been commenced 共blue兲, in the 32. J. Xie, N. Imanishi, A. Hirano, M. Matsumura, Y. Takeda, and O. Yamamoto, Solid
middle of the discharge process 共red兲, and just before the discharge current State Ionics, 178, 1218 共2007兲.
will be terminated 共pink兲. The electrolyte is at the left, the LiCoO2 electrode 33. H. Sato, D. Takahashi, T. Nishina, and I. Uchida, J. Power Sources, 68, 540
is indicated by the shaded area. 共1997兲.

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