Moving Boundary and Non Dimensional Modeling and Gitt With Phase Transformations

ECS Transactions, 53 (30) 131-142 (2013)
10.1149/05330.0131ecst The Electrochemical Society
Measurement of the Diffusion Coefficient of Lithium in Tin Thin Films Including

Phase Transformation Effects
Eddie C. W. Fok, and John D. W. Madden
Department of Electrical & Computer Engineering, The University of British Columbia,
Vancouver, British Columbia, Canada
In this work, use of the galvanostatic intermittent titration

technique to extract lithium ion diffusion coefficients in tin thin
films is studied. The measured results are first analyzed under the
traditional solid solution assumptions. The change of phase in the
electrode is then modeled using a moving boundary model, which
more accurately predicts the potential transients during the
galvanostatic pulse.
Introduction
Lithium alloys are promising materials for use in lithium-ion batteries due to their high
lithium storage capacities. Alloys such as lithium-silicon and lithium-tin have capacities
of 4200 mAh/g and 990 mAh/g, respectively. These values are significantly higher than
the 372 mAh/g capacity of the carbon materials that are commonplace in todays lithium
ion batteries.
In order for these and other novel electrode materials to be incorporated in commercial
batteries, many fundamental properties of the materials need to be characterized. The
solute diffusion coefficient is one such property, which has important scientific and
practical implications.
The lithium ion diffusion coefficient is most often measured using the Galvanostatic
Intermittent Titration Technique (GITT) (1-3) or electrochemical impedance
spectroscopy. Traditionally, GITT results are analyzed with the assumption that the
inserted species forms a solid solution with the host. This means any phase change
effects are neglected.
In this paper, measurement of the lithium ion diffusion coefficient in tin thin films is
considered. First, the governing equations for both the single phase and phase
transformation models are discussed. Then, the experimental procedure is presented.
Finally, the results section discusses the use of the single phase model to analyze the
GITT results. Further, the phase transformation model is shown to be better at predicting
the potential transients that are observed during the GITT experiments.
131
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Theory
The charge and discharge process of a tin film electrode can be modeled as a 1D
system, with thickness L. In this section, the single phase model will first be presented,
followed by the phase transformation model.
Single Phase Model
The concentration of lithium ions, C, in the electrode is governed by the diffusion

equation
dC/dt = Dd2C/dx2
[1]
where D is the lithium ion diffusion coefficient, and x is the position in the thickness
direction of the electrode. The boundary conditions specified at the film surface (x=0)
and current collector interface (x=L) are
dC(x = 0, t)/dx = -j/nFD
[2]
dC(x = L, t)/dx = 0
[3]
and
where j is the applied current density, n is the charge number of electroactive species (for
a Li-ion electrode, n = 1), and F is the Faraday constant.
The electrode is assumed to start at equilibrium with concentration C0
C(x, t = 0) = C0
[4]
As shown in (1), for small time t (t << L2/D), the lithium diffusion coefficient can be
approximated using
D = 4/(VMJ/nF)2[(dE/d)/(dE/dt1/2)]2
[5]
where E is the electrode potential (vs. Li/Li+), VM is the electrodes molar volume, and
dE/d is the change in electrode potential due to the stoichiometry change as a result of
the current pulse.
To facilitate comparison between the single phase and phase transformation models,
equations [1]-[4] can be non-dimensionalized using
= x/L
[6]
= Dt/L2
[7]
V = (C-C0)/C0
[8]
J = jL/nFDC0
[9]
132
where , , V, and J are respectively the dimensionless position, time, concentration, and
current density. Equations [1]-[4] becomes
dV/d = d2V/d2
[10]
dV( = 0, )/d = -J
[11]
dV( = 1, )/d = 0
[12]
V(, = 0) = 0
[13]
The surface concentration V( = 0, ) of the system of equations [10]-[13] can be

shown to be given by
n=
V( = 0, ) = 2J [ierfc((2n+)/21/2) + ierfc((n+1-)/1/2)]
n=0
1/2
[14]
where ierfc(x) is the integral of the complement of the error function. The electrode
potential transient, E(), is related to the surface concentration by
E() (E/V)V(=0, )
[15]
So for small changes in concentration, the electrode potential transient is roughly

proportional to the concentration at the surface of the electrode.
Phase Transformation Model
In the phase-change model, equations [1]-[4] are modified to include the presence of
two phases, and a phase boundary between them. The moving boundary model that will
be used in this work was first proposed by Wagner in (4). The phase boundary location
splits the electrode thickness into regions I (0 x ) and II ( x L). The diffusion
equation applies individually to both phases
dC/dt = DId2C/dx2
(0 x )
[16]
dC/dt = DIId2C/dx2
( x L)
[17]
where DI and DII are the lithium ion diffusion coefficients in phases I and II, respectively.
The phase boundary movement satisfies the conservation of lithium ions at the
interface, which can be written as
Cdd/dt = DI(dC/dx|x=-) DII(dC/dx|x=+)
[18]
where Cdd is the lithium ion per unit cross section generated or consumed by a
displacement of d in the phase boundary.
133
As before, the boundary conditions are

dC(x = 0, t)/dx = -j/nFD
[18]
dC(x = L, t)/dx = 0.
[19]
and the initial conditions have become

C(, = 0) = C0
(0 x )
[20]
C(, = 0) = Cd
( x L)
[21]
As in the single phase model, equations [16]-[21] can be made dimensionless using
equations [6]-[9], and introducing
= /L
[22]
= D2/D1
[23]
cd = Cd/C0
[24]
where is the dimensionless phase boundary position, is the ratio of lithium ion
diffusion coefficient of phase 2 to that of phase 1, and cd is the dimensionless form of Cd.
The dimensionless equations become
dV/d = d2V/d2
(0 )
[25]
dV/d = d2V/d2
( 1)
[26]
dV( = 0, )/d = -J
[27]
dV( = 1, )/d = 0
[28]
cdd/d = (dV/d| =-) (dV/d|=+)
[29]
V(, = 0) = 0
(0 )
[30]
V(, = 0) = cd
( 1)
[31]
Unlike the set of equations [10]-[13], there is no closed-form solution for equations
[25]-[31]. In this work, the finite-element solver COMSOL Multiphysics is used to
numerically calculate the solution to this set of equations.
Experimental
Copper foil (lithium-ion battery grade, MTIXTL) was degreased by sonication for 15
minutes in acetone. The oxide was removed by placing the foil in 10% (v/v) H2SO4 for 5
minutes. The foil was sealed onto a PVC plate with electroplating tape (3M) so that tin is
134
coated on one side. The tin deposition bath consisted of 137 g/L potassium
pyrophosphate, 36 g/L tin pyrophosphate, and 0.3 g/L gelatin. The electrodeposition was
performed at a constant current density of 2.5 mA/cm2 for 5 minutes at room temperature
with stirring. This deposition procedure was taken from (5). The tin thickness was about
1 m.
The tin electrode was a disc of 1 cm diameter cut from the tin-coated copper foil. A
custom designed setup was built to hold the electrodes inside a stainless steel coin cell
case (MTIXTL). The reference and counter electrodes were lithium films (SigmaAldrich). Glass microfiber filters were used as separators between the working and
reference electrodes, as well as between the reference and counter electrodes. The
electrolyte solution was 1 M LiClO4 in propylene carbonate (BASF). Approximately 200
L of electrolyte solution was used to wet the separators.
Before the GITT test, the electrode was cycled between the potential limits of 0.8 V
and 0.05 V vs. Li/Li+ for 5 cycles at descending current densities of 100 A/cm2, 80
A/cm2, 60 A/cm2, 40 A/cm2, and 20 A/cm2. The GITT procedure consisted of
pulses of 40 A/cm2 for 6 minutes, followed by a rest period of 40 minutes. The anodic
direction test was performed until the electrode potential reached below 0.01 V. The
cathodic direction test was performed until the electrode potential went above 1.2 V.
Electrochemical tests were performed using an Autolab PGSTAT101 (Metrohm AG),
controlled using the NOVA software. Cell assembly and testing were performed in an
argon-filled glovebox.
Scanning electron microscopy and Auger microscopy was performed using a Thermo
VG Microlab scanning Auger microscope.
Results
A scanning electron microscope image of the tin surface is shown in figure 1. The
film appears to be relatively flat and without significant features. Scanning Auger
microscopy before and after a series of Ar+ sputtering proved that the deposited tin was
chemically pure.
135
Figure 1. Scanning electron microscope image of the tin surface.

Potential of the tin film electrode during the 60 A/cm2 discharge and charge is shown
in figure 2. The curve shows plateaus during both discharge and charge. These indicate
the occurrence of phase transformation reactions in the electrode. By comparing the
potentials of these plateaus to those in (6), specific reactions can be assigned to each
plateau. During discharge, the first three plateaus are associated, respectively, to the
reactions
Sn + Li+ + e- Li2Sn5
[32]
Li2Sn5 + Li+ + e- LiSn
[33]
LiSn + Li+ + e- Li7Sn3
[34]
Below ca. 0.4 V, the extended slope is due to the closely spaced transformations between
the phases Li7Sn3, Li5Sn2, Li13Sn5, Li7Sn2, and Li22Sn5.
136
Figure 2. Potential of the electrode during discharge and charge at 60 A/cm2.

The discharge GITT results are shown in figure 3. Current pulses lead to the
downward potential peaks in the plot. The subsequent potential reversal is due to the
relaxation in the experimental procedure. At the ends of these relaxation periods, the
rates of potential changes are approximately 10 V/s. This illustrate that the 40 minutes
relaxation period allows the electrode to sufficiently relax before the subsequent
discharge pulse. If the relaxation period is increased significantly, the leakage current
becomes an issue. The electrode potential at the end of each relaxation period gives an
approximate open circuit voltage of the electrode at that state. Three plateaus in the open
circuit voltage can be identified at ca. 0.74 V, 0.66 V, and 0.50 V. These three plateaus
correspond to the reactions in equations [32]-[34].
Figure 3. Results from the GITT experiment in the discharge direction.
137
Figure 4 shows the GITT results for the charging direction. As in the discharge case,
examination of the potential at the end of each relaxation periods shows three plateaus
that are associated with phase change reactions.
Figure 4. Results from the GITT experiment in the charge direction.

Using the single phase approximation, the lithium ion diffusion coefficients in the
electrode can be calculated using equation [5]. The results for the discharging and
charging directions are shown in figures 5 and 6, respectively. The range of diffusion
coefficients found here is consistent with those reported in (3). Large dips in the
diffusion coefficients can be seen at potentials close to the phase change potentials. This
is due to the small change in potential after a current pulse when the electrode potential is
in the vicinity of a plateau. This can be explained by the large quantity of charge that is
needed to complete the transformation of the electrode from one phase to another. Since
the single phase approximation does not take this phase transformation into account, the
lithium diffusion coefficients are inaccurate close to the plateaus in the open circuit
potential.
138
Figure 5. Lithium ion diffusion coefficient in the tin film, extracted from the GITT
experiment in the discharge direction.
Figure 6. Lithium ion diffusion coefficient in the tin film, extracted from the GITT
experiment in the charge direction.
To examine more closely the effects of phase change on the GITT results, the
charging GITT data for the 0.54V plateau was investigated further. Figure 7 shows the
potential transients during four consecutive galvanostatic pulses. The figure shows that
each pulse results in a significant overpotential, before the potential begins to flatten.
Also, each subsequent pulse produces a higher overpotential than the last.
139
Figure 7. Potential transients during four consecutive charging pulses of the GITT
experiment (1st: cross, 2nd: star, 3rd: circle, 4th: dot) near the 0.54 V open circuit potential
plateau.
The single phase and phase transformation models were used to try to reproduce these
features in the GITT data. The value of the dimensionless parameter J that was used for
the single phase model computation is shown in table I. The single phase model results
are shown in figure 8, which were computed using equation [14].
The phase transformation model system of equations [25]-[31] was solved using
COMSOL Multiphysics. The arbitrary Lagrange Eulerian method was used to calculate
and monitor the position of the phase boundary. The parameters used in the calculations
are shown in table I. 0 is the initial dimensionless phase boundary position. A larger 0
means the phase boundary is located further away from the electrode surface.
TABLE I. Values of Model Parameters Used in the Calculations
Model Parameter
Single Phase Model
J
0.1
0
cd
Phase Transformation Model

0.1
0.2, 0.4, 0.6, 0.8
1
1
The computed results for the phase change model are shown in figure 9. For all four
initial phase boundary positions, there is a rapid increase in potential, followed by
flattening of the potential. Also, subsequent galvanostatic pulses results in increasing
overpotentials. These features were observed in the experimental results in figure 7.
This can be explained by the effects of the phase boundary position on the early potential
transient. The further the boundary is away from the electrode surface, the later the effect
of the phase boundary and phase changes are reflected in the surface lithium ion
concentration. Therefore, subsequent pulses of a moving boundary reaches a higher
potential before flattening.
140
On the other hand, from the single phase model, a small overpotential is seen at the
beginning, followed by a sloping potential transient at later times. Therefore, the phase
change model predicts the GITT results more accurately than the single phase model.
Figure 8. Calculated concentration transients during the charging phase of the GITT
experiment using the single phase model.
Figure 9. Calculated concentration transient during the charging phase of the GITT
experiment using the phase transformation model. The four curves correspond to
different starting phase boundary locations 0: 0.2 (solid), 0.4 (dot), 0.6 (dash), and 0.8
(dash-dot).
141
Conclusions
In this work, tin thin films were characterized using the galvanostatic intermittent
titration technique. The lithium ion diffusion coefficient was first extracted from the
resulting data under single phase assumptions. Large drops in diffusion coefficients were
observed at potentials close to the phase transformation potentials of tin. This can be
explained by the phase change that occurs at these potentials. A moving boundary model
was numerically computed to explain the shape of the potential transients during the
galvanostatic pulses. This model can be used to more accurately model the galvanostatic
intermittent titration experiments.
Acknowledgments
The authors gratefully acknowledge financial support from the Natural Sciences and
Engineering Research Council of Canada.
References
1. W. Weppner and R.A. Huggins, J. Electrochem. Soc., 124, 1569 (1977).
2. K.I. Pidatko, Russian J. of Electrochem., 42, 63 (2006).
3. J. Xie, N. Imanishi, A. Hirano, Y. Takeda, O. Yamamoto, X.B. Zhao, and G.S.
Cao, Solid State Ionics, 181, 1611 (2010).
4. W. Jost, Diffusion in Solids, Liquids, Gases, Academic, New York (1960).
5. J. Yang, M. Winter, and J.O. Besenhard, Solid State Ionics, 90, 281 (1996).
6. M. Winter and J. O. Besenhard, Electochimica Acta, 45, 31 (1999).
142

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ECS Transactions, 53 (30) 131-142 (2013)

10.1149/05330.0131ecst The Electrochemical Society

Measurement of the Diffusion Coefficient of Lithium in Tin Thin Films Including

In this work, use of the galvanostatic intermittent titration

ECS Transactions, 53 (30) 131-142 (2013)

The concentration of lithium ions, C, in the electrode is governed by the diffusion

ECS Transactions, 53 (30) 131-142 (2013)

The surface concentration V( = 0, ) of the system of equations [10]-[13] can be

So for small changes in concentration, the electrode potential transient is roughly

ECS Transactions, 53 (30) 131-142 (2013)

As before, the boundary conditions are

and the initial conditions have become

cdd/d = (dV/d| =-) (dV/d|=+)

ECS Transactions, 53 (30) 131-142 (2013)

ECS Transactions, 53 (30) 131-142 (2013)

Figure 1. Scanning electron microscope image of the tin surface.

Li2Sn5 + Li+ + e- LiSn

LiSn + Li+ + e- Li7Sn3

ECS Transactions, 53 (30) 131-142 (2013)

Figure 2. Potential of the electrode during discharge and charge at 60 A/cm2.

Figure 3. Results from the GITT experiment in the discharge direction.

ECS Transactions, 53 (30) 131-142 (2013)

Figure 4. Results from the GITT experiment in the charge direction.

ECS Transactions, 53 (30) 131-142 (2013)

ECS Transactions, 53 (30) 131-142 (2013)

Phase Transformation Model

ECS Transactions, 53 (30) 131-142 (2013)

ECS Transactions, 53 (30) 131-142 (2013)

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