Journal of Energy Storage 21 (2019) 272–280

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Journal of Energy Storage

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Investigation of the low frequency Warburg impedance of Li-ion cells by T

frequency domain measurements
⁎
M. Oldenburgera,b, , B. Bedürftigb,c, A. Gruhleb, F. Grimsmannb, E. Richterb, R. Findeisenc,
A. Hintennachb
a
University of Ulm, Department of Electron Microscopy of Materials Science, Albert-Einstein-Allee 11, 89081 Ulm, Germany
b
Daimler AG, Research & Development, Wilhelm-Runge-Str. 11, 89081 Ulm, Germany
c
Otto von Guericke University, Laboratory for Systems Theory and Automatic Control, Universitaetspl. 2, 39106 Magdeburg, Germany

A R T I C LE I N FO A B S T R A C T

Keywords: In this work we investigate the Warburg impedance of Li-ion cells at very low frequencies down to 0.1 mHz.
Low frequency impedance spectroscopy Three different Li-ion cells are used, two 18650-type and one pouch cell of 80 Ah. The measurements are
Warburg impedance hysteresis conducted with electrochemical impedance spectroscopy (EIS). The open circuit voltage is measured separately
Warburg impedance relaxation to enable a correction due to voltage hysteresis effects.
OCV-Hysteresis
It is found that the Warburg impedance does not only dependent on the state of charge (SoC) but also on the
Cell thickness hysteresis
SoC setting current, the rest time after SoC setting, the sinusoidal excitation amplitude and the charge and
discharge history of the cell. It is assumed that the reason for these dependencies are the hysteresis of the open
circuit voltage as well as the hysteresis of the cell thickness.

1. Introduction The criteria of linearity is fulfilled if the current excitation ampli-

For an automotive manufacturer it is very important to predict the
performance of Li-ion cells under all operating conditions. This enables
a prognosis about the possible driving range, power, the cooling system
for the battery, etc. In practice, physically motivated equivalent circuit
models (ECMs) are common to describe the electric behavior of the cell
[1]. These models are a reasonable compromise between calculation
time and model accuracy. However, the parametrization of such models
is not easy because the loss processes in the cell have to be identified
and fitted to an electric circuit model. This requires the identification
and separation of ohmic resistances, the double layer effects and the
diffusion in the electrodes which is usually described by Warburg im-
pedances. Therefore, highly accurate impedance measurements are
required. Especially the low frequency part is prone to measurement
errors [2]. Reasons are noise generated by external signals, temperature
drift, SoC shift and OCV-hysteresis effects which will be discussed in
Section 2. Please note that there are further losses in the cell (e.g. en-
tropy change) which are not covered by the impedance.
The impedance spectrum can be obtained by measurements in the
frequency domain (FD) [1,3] and time domain (TD) [4,5]. To ensure a
high measurement quality, the system under test has to be time-in-
variant and it has to fulfill the criteria of linearity and stationarity [2,6].
tude is sufficiently low. Typically, an excitation amplitude of 10 mV is
used [2,5]. The criteria of stationarity is often violated because of in-
sufficient rest time before the measurement. This violation can lead to
severe deviations between measured cell impedances. The deviation
can be either caused by a measurement effect or by a cell effect. A
measurement effect would be an insufficient voltage drift correction
which superimposes the sinusoidal signal. Cell effects are temperature
gradients or Li-ion concentration gradients within the cell.
For the interpretation of impedance spectra all measurement effects
have to be eliminated and cell effects have to be considered. There are
several compensation methods in the literature to reduce the influence
of voltage drift after SoC-setting [7,6]. Temperature gradients usually
decline within several hours. However, it has been reported that the
equalization processes due to Li-ion concentration inhomogeneities can
take up to several days and they cause a time dependent change of the
charge transfer resistance Rct of the double layer after state of charge
(SoC) setting [8,9]. Nevertheless, a relaxation process of the low fre-
quency diffusion process in the electrodes has not been described so far.
This part of the impedance is typically modeled by Warburg elements.
This paper reports for the first time the change of the Warburg im-
pedance after SoC setting.
A violation of the stationarity criteria can also be caused by a

⁎
Corresponding author at: University of Ulm, Department of Electron Microscopy of Materials Science, Albert-Einstein-Allee 11, 89081 Ulm, Germany.
E-mail address: marc.oldenburger@daimler.com (M. Oldenburger).

https://doi.org/10.1016/j.est.2018.11.029
Received 19 June 2018; Received in revised form 28 November 2018; Accepted 28 November 2018
Available online 08 December 2018
2352-152X/ © 2018 Elsevier Ltd. All rights reserved.
M. Oldenburger et al.
change of SoC during the measurement. For high frequencies the
change in SoC is negligible but for very low frequencies the voltage
response is mainly caused by a change in SoC, respectively OCV, and
not by overvoltage.
In addition to the SoC dependent diffusion behavior another more
severe effect influences the measurement in this frequency range. The
most common Lithium insertion materials used in the automotive sector
show a non negligible voltage hysteresis effect (OCV-hysteresis). This
effect describes the different equilibrium potentials for the same state of
charge depending on whether the battery was previously charged or
discharged. An alternating charging and discharging of the cell as done
in EIS measurements leads to a transition between the charge- and
discharge branch of the OCV. These transitions differ for the charge and
discharge process. The result are enclosed areas denoted as OCV hys-
teresis loops which superimpose the voltage signal. Sekushin [10] cal-
culated the theoretical impacts of different OCV hysteresis loops on the
results obtained by EIS. The hysteresis loop leads to a shift in the real
and imaginary part of the impedance. This shift depends on the size and
the direction of the loop as well as on the shape of the hysteresis. In this
paper this effect is studied in detail by changing the amplitude of the
excitation signal.
Additionally, a hysteresis of the Warburg impedance is discovered,
which also depends on the SoC setting current. Beside the widely in-
vestigated OCV hysteresis, Li-ion cells also exhibit a current dependent
mechanical hysteresis [11,12]. We assume that both hysteresis-effects
are the reason for the measured dependence of the impedance on its
history.
2. Theory
In this part we want to focus on the low frequency loss processes
occurring in the cell and how the measurement is affected by the OCV-
hysteresis. The basics of impedance spectroscopy can be found in Ref.
[13].
2.1. Loss processes within the cell
A good overview of all loss processes within a Li-ion cell can be
found in Ref. [14]. They are visualized in Fig. 1. Starting from high to
low frequencies the loss processes are:
Fig. 1. Typical impedance spectrum of a Li-ion cell and common EC to model
the impedance behavior. Four different loss processes can be identified. The low
frequency diffusion behavior is typically modelled by (1) a FSW, (2) a CPE or
(3) a FLW. (For interpretation of the references to color in the text, the reader is
referred to the web version of this article.)
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Journal of Energy Storage 21 (2019) 272–280
1. Inductive losses of metallic elements in the cell and connecting
wires are visualized in green.
2. Ohmic resistance as the sum of several contributions, which are:
electrolyte, separator, current collector and electric conductivity of
the active material.
3. Double layer and charge transfer effects at the interfaces which form
a semi-circle visualized in blue.
4. Mass transport (Li-ion diffusion) within the electrodes. Common
equivalent circuit elements to model the diffusion behavior are the
finite space Warburg (FSW), the finite length Warburg (FLW) and a
constant phase element. They are visualized in red and will be dis-
cussed in the following section.
2.2. Low frequency behavior
The low frequency part in the Nyquist plot consists of two con-
tributions: the diffusion within the electrodes and the capacity of the
cell.
2.2.1. Diffusion
For the modeling of the Li-ion diffusion the three presented
Warburg elements can be used. These elements can be derived directly
from Fick's law by applying different boundary conditions which are:
[13,15].
• FSW: limited diffusion layer and limited electroactive substance
• FLW: limited diffusion layer and ideal reservoir at the boundary
• CPE: semi-infinite diffusion layer
The elements can be used separately or combined. Typical forms are
a single CPE, a serial connection of FLW and FSW [2] and a serial
connection of FLW and capacitor [16].
Here we want to focus on the ideal 1-D finite space element, since
this element is used as simplification to model the lowest frequency part
of the impedance. Buller [17] showed that a transmission line approach
(depicted in Fig. 2(a)) can lead to the same mathematical formula as the
analytically calculated FSW. This allows to model the finite diffusion by
a ladder network with a diffusion resistance ΔRD and a diffusion ca-
pacitance ΔCD. The formulas are:
Fig. 2. (a) Transmission line approach of the Warburg impedance presented by
Buller [17]. (b) Impedance of the FSW element with varying diffusion resistance
ΔRD and varying diffusion capacitance ΔCD. The yellow curves are for
CD = 15 · 105 F, red curves for CD = 10 · 105F and blue curves for CD = 5 ·105 F.
(For interpretation of the references to color in this figure legend, the reader is
referred to the web version of this article.)
M. Oldenburger et al. Journal of Energy Storage 21 (2019) 272–280

∑ ΔRD = RD, ∑ ΔCD = CD, (1)

RD
ZFSW = ·coth( jωRD CD ),
jωCD (2)
where ω is the angular frequency and j the imaginary unit. Fig. 2(b)
shows the analytical FSW calculated for different diffusion resistances
and different diffusion capacities. As can be seen, a varying capacitance
only leads to a change in the imaginary part and a varying resistance
only leads to a change in the real part.
Depending on the electrode material Li-ion cells sometimes exhibit a
non negligible slope in the Warburg branch. It is stated by [18,19] that
this behavior can be caused by the anisotropic diffusion in the particles,
by the particle size distribution and also by the long diffusion process
from the surface of large particles into the center which is not finished
at typical EIS frequencies down to the mHz range. Furthermore, it is
shown in the following sections that the OCV hysteresis also leads to an
increasing real part of the low frequency impedance even for ω ap-
proaching zero.

2.2.2. Capacitive behavior, OCV

The capacitive contribution can be calculated from the slope of the
OCV. This is visualized in Fig. 3(a). The relation between the OCV and
the impedance is given by Zimag =−1/(jωCdiff), where ω is the angular
frequency and Cdiff denotes the differential capacity of the cell at that
SoC. It can be calculated by Cdiff = dQ/dU. Note that this formula only
holds for very low frequencies where the cell behavior can be described
by an ideal capacitor. Otherwise there is a deviation because of the
superimposed Warburg diffusion which also exhibits a capacitive be-
havior (see Fig. 3(a)). Furthermore, if a cell exhibits an OCV-hysteresis
there is a deviation to this formula caused by the transition between the
upper and lower OCV branch during EIS. Depending on the charge
quantity a different slope will be measured. This relation is displayed in
Fig. 3(b).

2.3. Theoretical consideration of the impact of the OCV hysteresis on the

low frequency impedance

During EIS the cell is exposed to a sinusoidal excitation and the cell
response is measured. Consequently, the EIS consists of alternating
charge and discharge currents. As mentioned in the previous chapter,
the alternating charge and discharge currents result in small OCV
hysteresis loops and in a change of the OCV slope. This effect is depicted
in Fig. 4(a) for two different excitation amplitudes which results in a
different amount of charge ΔQ for the charged (orange) and discharged
(blue) state.
The smaller amplitude on the left leads to a smaller change in SoC.
Consequently, the change of the OCV slope is smaller compared to the
Fig. 3. Relation between the low frequency impedance and the differential
capacity Cdiff in case of no hysteresis (a) and in case of a hysteresis (b).
Fig. 4. Theoretical consideration of the influence of the OCV hysteresis on EIS
for a cell (a) and an RC element (b). (c) Impact of the OCV hysteresis on the
impedance of a Li-ion cell. (For interpretation of the references to color in the
text, the reader is referred to the web version of this article.)
larger amplitude on the right side which results in a higher imaginary
part of the impedance for the smaller excitation (see Section 2.2).
The enclosed areas of the loops are equal to the energy lost during
one period. The areas consist of two contributions, one from the dif-
fusion overvoltage and one from the OCV hysteresis. The losses in Ri
and Rct will be neglected for simplicity and we will only look at an ideal
FSW. Since irreversible energy losses are only caused by the real part of
the impedance, any OCV hysteresis will also contribute a real part.
Before the mathematical relation is derived a schematical con-
sideration is presented in Fig. 4. The relation between Re(Z) and the
OCV hysteresis can be shown schematically by looking at a simple RC
element instead of the complete FSW. The current is chosen in a way
that the charge throughput for each frequency is equal. Consequently,
ΔSoC is a constant value. The resulting voltage response with and
without an OCV hysteresis is depicted in Fig. 4(b). In the absence of a
hysteresis the voltage loop becomes very small until it approaches a
straight line for ω → 0. In the case of an OCV hysteresis a small loop
remains which results in a constant voltage response even for very small
frequencies. As a consequence a larger real part impedance is measured
compared to a cell without hysteresis (see inset Nyquist plot of
Fig. 4(b)). For ω → 0 the real part approaches infinity as derived below.
The relation between Re(Z) and an ideal FSW can also be shown

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M. Oldenburger et al. Journal of Energy Storage 21 (2019) 272–280

Table 1
Overview of the investigated cells and information about measurement para-
meters. The denoted voltage response is measured at middle SoC range and may
vary for different SoCs.
Label Cell A Cell B Cell C

Manufacturer SK Panasonic Panasonic

Format Pouch 18650 18650
Chemistry graphite-NMC graphite/silicon- graphite-NCA
NCA
Capacity 80 Ah 3.2 Ah 2.7 Ah
Allowed voltage range 2.5–4.2 V 2.5–4.2 V 2.5–4.2 V
Measurement device HPS CTS CTS
Temperature 25 °C 25 °C 25 °C
FD excit. current 0.35/0.75/ 7.5/20/40 mA 7.5/20/40 mA
(0.1 mHz) 1.5 A
FD volt. response EIS ≈ 6/12/ ≈ 5/13/25 mV ≈ 9/17/31 mV
(0.1 mHz) 21 mV

Fig. 5. (a) OCV of cell type A and voltage hysteresis gap between the upper and cell. The system was already presented in a previous publication [7].
lower OCV branch. (b) Small OCV loops measured at 40% SoC. (c) The only modification is an increased step number of 2048 values per
Corresponding differential capacity Cdiff calculated from the envelope OCV and period to reduce the systematic phase error of very low frequencies
from the largest OCV loops. down to a negligible level. The frequency ranges from 100 Hz down to
0.1 mHz with three points per decade and a minimum of four periods
mathematically. The energy loss of one period is: per frequency. This procedure leads to a measurement time of 22 h.
The standard current amplitude of the lowest frequency is 0.02 A,
W= ∮ U dQ (3) (0.35 A for the large pouch cell), which creates a voltage response of
about ≈ 6–15 mV in the middle SoC range. Smaller voltage responses
The power loss is:
lead to a systematic error which results in a phase shift of the im-
2
ω 2 2 ⎛ ω ⎞ pedance. This error is caused by the limited resolution of the BaSyTeC
P = W· = Re(Z )·Ieff = Re(Z )·Qeff ·
2π 2π
⎝ ⎠ (4) A/D converter, which is 0.15 mV. Experiments are conducted in climate
2
chambers to ensure a constant temperature of 25 °C during all mea-
where Ieff is the effective current. Those equations can be transformed
surements.
to:
Before specific tests are conducted all cells are cycled eight times in
2π· ∮ U dQ CCCV mode both during charge and discharge. The current during the
Re(Z ) = 2 CC step was C/2 and the CV mode was stopped at C/20. The cells were
ω·Qeff (5)
considered to have 0% SoC and 100% SoC at these points respectively.
In the case of no hysteresis the integral in the numerator represents Corresponding OCV voltages were ≈ 2.8 V and 4.15 V. The last three
the losses in all diffusion resistances ΔRD and Re(Z) approaches RD for cycles are also used to determine the capacity of the cell. The exact
ω → 0. With an OCV hysteresis the integral in the numerator ap- measurement procedures are described in the next sections.
m
proaches a constant value K which depends on Qeff according to the
degree of saturation of the hysteresis loop. In practice we find m > 1
3.1. OCV
and for our cells at low excitation and 40% SoC m≈ 2.5 as can be
derived from the area within the loops of Fig. 5. The ratio is ≈ 1:4.6
The OCV measurements are used to determine the differential ca-
between curves 2 and 3. The resulting FSW impedance is:
pacity Cdiff and the total anode capacity (as shown in [12]) which is
1 ⎛ K ·2π j ⎞ 1 necessary for the investigation of the C-rate dependency (see Section
Z (ω) = RD + ⎜
2
− ⎟ = RD + (a − jb) 3.5). The OCV of the cell is measured at 25 °C in steps of 2% SoC with
ω ⎝ Qeff Cdiff ⎠ ω (6)
C/20, starting in the discharged state. A pause of 3 h is employed be-
with a, b and A0 as constants to simplify the equation. This represents a tween the charge steps to allow a voltage relaxation. Afterwards, the
straight line with an offset of RD. A straight line in the Nyquist plot same procedure is conducted from the fully charged state down to the
equals a CPE element and the slope depends on characteristics K(Qeff) of discharged state.
the hysteresis as shown in Fig. 4(c). Additionally, very fine OCV-loops are measured at the SoCs where
the EIS is conducted. These measurements are used to calculate the shift
1 A0
Z (ω) = RD + (a − jb) = RD + of the impedance caused by the OCV hysteresis described in Section 2.2.
ω (jω)α (7)
The cell is charged (/discharged) for 10 steps with C/100 followed by a
with A0 as the magnitude and 0 < α < 1 defining the slope of the CPE rest time of 90 min in between. The charge quantity of the 10 steps is
element. Without OCV hysteresis the low frequency impedance would chosen to add up to the same charge amount as used for the lowest EIS-
approach the vertical curve of an ideal capacitor. frequency. Afterwards the cell is discharged (/charged) with the same
procedure until the original SoC is reached. The direction of the loop is
3. Experiment chosen to match the EIS. Because the size of the hysteresis loop is in the
range of the voltage resolution of the BaSyTec device, the voltage is
In this paper three cell chemistries and two cell formats are in- measured with a Keithley DMM7510 multimeter.
vestigated as shown in Table 1.
SoC setting and FD measurements are conducted with a commercial 3.2. Influence of the rest time after SoC setting, Z(t)
BaSyTec CTS and HPS cell test system operated as current source in a
four-wire setup. If not stated differently, the cells are charged or dis- The change of Z with time after an SoC setting is measured in the
charged with 0.8 A for the 18650 cells and 3.5 A for the larger pouch following way: The cells are charged with C/3 from 0% to 10%, 20%,

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M. Oldenburger et al. Journal of Energy Storage 21 (2019) 272–280

40% and 90%. Afterwards, a rest time of 60 min is employed to ensure a

constant temperature within the cell followed by several EIS measure-
ments. The EIS is measured down to 0.1 mHz to analyze the charge
transfer and Warburg impedance. The voltage drift caused by the SoC
setting current can be corrected as shown in Ref. [7].

3.3. Influence of the exciting current amplitude, Z(ΔQ)

A good signal to noise ratio (SNR) is necessary for reliable and re-
producible impedance measurements. Since a sinusoidal current of
large amplitude leads to a change in SoC during the measurements, a
tradeoff between good SNR and small change in SoC is needed. The
impact of the exciting current amplitude on the measurement techni-
ques is tested for all investigated SoCs.
After SoC setting the necessary rest time to reach the stationary state
is maintained before the FD measurements are conducted. The EIS is
started with the lowest possible excitation current which gives a suffi-
cient SNR. Afterwards the current is increased up to the maximum
current and decreased again (see Table 1). The maximum current is
limited by the acceptable change in SoC of ≈ 1.5%.
3.4. Influence of the charge/discharge history, Z(history)
The SoC dependency of the impedance is measured for the charged
and discharged OCV branch. Therefore, the cells are charged to 100%
SoC or discharged to 0% before SoC setting. This ensures that the cell is
completely on the upper or lower OCV branch for the following mea-
surements. The investigated SoCs range from 90% down to 10%. The
necessary rest times for the different cell types, which are derived in
Section 4.2 are maintained before all subsequent EIS measurements.
3.5. Influence of the SoC-setting current, Z(ISoC)
Fig. 6. (a) Measured impedances of cell type A at 10% SoC and different rest
times after SoC setting. (b) Enlarged charge transfer resistance Rct. (c) Enlarged
real part to show the relaxation effect. The red curve shows the Warburg im-
pedance after subtracting the Rct effect. (For interpretation of the references to
color in this figure legend, the reader is referred to the web version of this
article.)
The difference between Cdiff calculated from the OCV (solid lines)
and Cdiff calculated from the hysteresis-loops (dotted lines) is clearly
visible. The transition occurring during EIS leads to an increased slope
of the OCV which results in a smaller Cdiff. Please note that there is not
necessarily a relation between the slope of the transition and the size of
the hysteresis gap.
For the interpretation in Section 4.4 the SoCs with the same Cdiff are
of special interest because the capacitive contribution of the OCV-loops
to the low frequency impedance is the same for the charged and dis-
charged state. Therefore, any differences between the charged and
discharged impedance must either result from a varying diffusion re-
sistance RD or from the hysteresis losses (see Section 2.2 and 2.3).

The impact of different charge and discharge rates is investigated
for several anode SoCs. Grimsmann et al. [12] showed that at 22–27%
and at 45–70% anode SoC the total thickness depends strongly on the
SoC–setting current whereas there is nearly no dependency for 35% or
10% anode SoC. The anode SoC as compared to the cell SoC can be
calculated by identifying the phase transition of LiC6 to LiC12 in the
OCV-SoC curve which corresponds to 50% lithiation of the anode [12].
The investigated cell SoCs are 12.5%, 28.5%, 43.5% and 75.5%, cor-
responding to 10.5%, 24.5%, 37.5 % and 65% anode SoC. The C-rates
range from C/20 to 2 C. The necessary rest times determined in section
4.2 are maintained.
4. Results and discussion
The effects that will be presented in the following sections are
identified for all three cell types and are also completely reproducible.
However, the cells differ in the strength of the effects. For reasons of
clarity, only the results of cell type A are displayed. The results of the
other cells are provided as supplementary information.
4.2. Influence of the rest time after SoC setting, Z(t)
In addition to the reported relaxation process of the charge transfer
resistance Rct, which is caused by an inhomogeneous Li-distribution
along the electrodes [8,9], we discovered a relaxation of the Warburg
impedance after SoC setting (see Fig. 6(a) and (c) at 10% SoC). For
0.1 mHz a change in the real part of 0.07 mΩ is measured from the first
to the fourth measurement. In the same time a relaxation of Rct of about
0.19 mΩ (Fig. 6(b)) is observed and thus leads to an actual Warburg
relaxation of 0.26 mΩ.
The measurement is stopped after four days. After this time the
change of the third to the fourth measurement is in the range of the
measurement accuracy of about 1%. For higher SoCs of cell type A (see
Fig. 7) the Warburg relaxation proceeds significantly faster and after

4.1. OCV measurements

Fig. 5(a) shows the OCV and the corresponding OCV-hysteresis gap
of cell type A. From the OCV the differential capacity Cdiff is calculated
and the results are displayed in part (c) for the upper and lower OCV
branch. Additionally, Cdiff is calculated from the largest hysteresis-loop
which is measured according to the procedure described in section 3.1
leading to pure hysteresis curves without ohmic and dynamic losses.
The resulting loops are displayed in part (b). As expected, a larger
change in SoC during the loops leads to a higher voltage hysteresis. The
dashed trend lines represent the slope of the OCV in that SoC. These Fig. 7. (a) Measured impedances of cell type A at 40% SoC and different rest
measurements will be further used in Section 4.3, where the impact of times after SoC setting. (b) Enlarged charge transfer resistance Rct. (c) Enlarged
the excitation signal amplitude is investigated. real part to show the relaxation effect.

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M. Oldenburger et al.
24 h changes are negligible. Therefore, a rest time of 24 h is considered
sufficient for SoCs above 10% and was employed before each FD
measurement. For 10% a rest time of 72 h is employed.
When comparing cell types A, B and C it is clearly visible that cell
type B exhibits much stronger Warburg relaxation behavior than the
other two cell types (see Figs. 11 and 15 in the appendix). The relative
change of the real part of the impedance is about 15% of cell type B
compared to ≈ 4% for type A and C. A possible reason for this behavior
might be the silicon-graphite composite used as anode material of cell
type B which also shows very long voltage relaxation behavior.
Additionally, both 18650 cell types show a very long relaxation of
the Rct. Therefore, the rest time of cell type B and C was chosen to be
100 h. Furthermore, the charge throughput by the EIS does not affect
the relaxation process. This can be seen in Fig. 11(c) where a new
spectrum is recorded after a rest time of 120 h after SoC setting for cell
type B. No difference to the last EIS of the first measurement series
could be identified.
4.3. Influence of the exciting current amplitude, Z(ΔQ)
The size of the exciting current amplitude has a severe impact on the
measured impedance. Considering the signal to noise ratio (SNR), a
large excitation and system response is favorable to reduce measure-
ment errors. The disadvantage is the larger change in SoC during the
half-periods. Additionally, the change in SoC causes a distortion of the
sinusoidal voltage response by small OCV hysteresis loops.
Fig. 8(a) shows the impedance of cell type A at 40% SoC, measured
for three different current amplitudes. The curves are almost identical
down to 1 mHz. For lower frequencies there is a distinct deviation be-
tween the three different EIS excitation amplitudes. To exclude an effect
caused by SoC dependent Warburg impedance, several measurements
at slightly increased SoCs (0.3 Ah, 0.6 Ah and 0.9 Ah) are conducted. As
can be seen, a change in SoC leads to very small changes of the im-
pedance and hence the SoC dependency of the Warburg impedance
cannot be the reason for the remaining deviation. Note that an effect
from temperature due to the higher excitation can be excluded since
this would lead to a smaller cell impedance.
Therefore, the measured deviations of the impedance have to be
Fig. 8. (a) Measured impedance of cell type A at 40% in the charged state. The three different excitation currents lead to a change of 0.37%, 0.83% and 1.65% Δ SoC.
The influence of the SoC dependency of the Warburg diffusion is tested by EIS measurements at slightly increased SoC. (b) Applied OCV loop correction of 0.1 mHz.
(c) Schematic OCV loops in the charged state for three excitations. (d) Decreased imaginary part of the smaller excitation currents after a large current excitation.
Please note that the axis are not symmetric to better show the shift of the real part.
277
Journal of Energy Storage 21 (2019) 272–280
caused by the OCV hysteresis. As mentioned in Section 1 for very low
frequencies a non negligible part of the overvoltage is caused by a
change in SoC. The alternating charge and discharge currents of EIS
lead to OCV loops which superimpose the voltage signal. A theoretical
consideration of the influence on the impedance was presented in
Section 2.3. The additional voltage of the hysteresis can be subtracted
from the voltage response by separately measuring the small OCV loops
(see Section 3.1). The corrected impedances at 0.1 mHz for the three
different excitations are displayed in Fig. 8 (b). As expected, only the
real part of the impedance is affected by the correction. Considering the
measurement error, it seems that the real part approaches the same
value for all excitations after subtracting the contribution from the
hysteresis. The existing deviation in the imaginary part of around
1.8 mΩ between Zimag(EIS 1) and Zimag(EIS 3) can be fully explained by
the different slopes of the small OCV loops, depicted schematically in
Fig. 5 (c). The capacitive contribution to the impedance changes from
7.2 mOhm for EIS 1 to 5.3 mOhm for EIS 3.
Fig. 8 (d) shows additional EIS measurements, which are conducted
after EIS 3 of part (a), with decreasing current amplitudes. There is no
difference in the real part of EIS 2 and 4 and also of EIS 1 and 5 but the
imaginary part decreases to the value of EIS 3. It seems that the large
current excitation has led to a persisting slope of the OCV loops which
does not change during lower current excitations.
These measurements show that the excitation current of EIS has to
be chosen carefully. In addition to the criteria of linearity
(UEIS < 25 mV), which forms an upper limit for the current excitation,
and the change in SoC during EIS, a tradeoff between good SNR and a
possible shift due to the OCV hysteresis has to be considered. A small
excitation is recommended because this will reduce the number of
points which have to be corrected. In our case we used 5-7 mV to
maintain a sufficient precision of the voltage measurement.
4.4. Influence of the charge/discharge history, Z(history)
To investigate the influence of the charge and discharge history the
impedance is measured with different amplitudes on the charged and
discharged OCV branch. The results of cell type A are displayed in
Fig. 9. The red curves indicate the charged branch and the blue curves
M. Oldenburger et al.
Fig. 9. Impedance hysteresis of cell type A from 90% to 10% SoC. The impedance is measured with different current amplitudes for each SoC in the charged and
discharged state. (For interpretation of the references to color in the text, the reader is referred to the web version of this article.)
indicate the discharged branch.
As expected, there is a difference in the imaginary part of the im-
pedance between the charged and discharged state. This deviation can
be explained by the varying slopes of the OCV-loops (see Fig. 5 (c)). The
differences become visible for frequencies below 2 mHz.
However, even after applying the introduced OCV loop correction
(which is not displayed here for reasons of clarity) there is a non neg-
ligible deviation in the real part between the charged and discharged
state for several SoCs. This deviation does not vanish even after several
weeks of rest time. In the case of 70% SoC the OCV loops for the
charged and discharged state are nearly the same. Thus, an OCV loop
correction does not change the difference in the real part of Z which is
depicted in Fig. 9. Consequently, the remaining deviation in the real
part has to be caused by a varying diffusion resistance RD (see Section
2.2.1) in the charged and discharged state. The result is an non negli-
gible impedance hysteresis.
The same measurements are also conducted for the other two cell
types (please see appendix Figs. 13 and 16). The results show very si-
milar behavior of type C as observed for the pouch cell. For high SoC
the impedance in the charged and discharged state are nearly the same
and for 70% SoC the cell shows the same impedance hysteresis-effect.
The differences of the imaginary part can be explained by the slopes of
measured OCV loops. This is not a surprising result assuming that the
OCV-loops are mainly affected by the graphite OCV-hysteresis and that
there is a varying diffusion coefficient for the different graphite stages.
The results of cell type B which has a mixed graphite/silicon anode also
shows similar behavior for higher SoC. For lower SoCs the silicon has a
stronger impact especially on the imaginary part which complicates
further interpretation.
4.5. Influence of the SoC-setting current, Z(ISoC)
As described in [12], the thickness of graphite electrodes depends
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Journal of Energy Storage 21 (2019) 272–280
on the C-rate of the charge and discharge current. This means that there
is a different structural composition of the graphite electrode (LiC6,
LiC12, LiC18, …) which could be visible in impedance measurements.
Fig. 10(a) shows the current dependency of the cell thickness already
presented in [12] and part (b) shows the impedance of cell type A for
different discharge currents in the range from −2 C to −0.05 C. The
OCV loop correction is not displayed because it does not change the
observed trend of the curves.
As observed for the cell thickness, there is nearly no dependency of
the impedance at 12.5% and 43.5% SoC. For the other two SoCs there is
a clear dependency of the Warburg impedance on the C-rate used for
SoC setting. A lower C-rates lead to lower impedance and an increased
C-rate leads to an increased impedance. The effect is visible for fre-
quencies below 2 mHz and it is most significant for 28.5% SoC. This
finding correlates very well with the cell thickness. At 28.5% the cell
thickness exhibits the strongest dependency on the SoC setting current.
Note that a smaller cell thickness does not necessarily result in a
higher impedance due to smaller lattice constants as observed for
72.5% SoC. The different C-rates lead to different structural composi-
tions within the graphite electrode. Consequently there are varying
diffusion constants and varying Li-ion concentrations along the cross-
section of the particles which might explain the observed impedances.
The same behavior described above for cell type A is also found for
type C (see Fig. 17 in the appendix). However, the cell shows a smaller
dependency on the SoC setting current. Since both cells have a graphite
anode but different cathode materials the results support the assump-
tion that the effect is caused by the graphite anode. Due to the fact that
it is not possible to identify the anode SoC of cell type B no measure-
ments are conducted here. The reason is the unknown amount of silicon
in the anode.
M. Oldenburger et al.
Fig. 10. (a) Cell thickness curves for different C-rates of a 20 Ah pouch cell. Graphic edited from [12]. (b) Impact of the SoC setting discharge current on impedance
measurements. The EIS is measured with 0.3 Ah for all SoCs and excitation currents. OCV loop correction is not displayed for reasons of clarity.
5. Summary and conclusion
The low frequency impedance of Li-ion cells depends on the SoC
setting current, the rest time after SoC setting, excitation amplitude and
the charge and discharge history of the cell which reults in an im-
pedance hysteresis.
In this work, each factor has been investigated in detail for three
different cells and the impact on the measured impedance was de-
termined at 25 °C. It was concluded that a rest time of at least 100 h is
necessary for the 18650 cells and 24 h for the pouch cell. The influence
of the OCV hysteresis on EIS measurements can be reduced by choosing
a small excitation with a sufficient SNR. However, the correct im-
pedance can only be determined by separately measuring the OCV
loops occurring during EIS and applying a voltage correction.
Furthermore, a variation of the measurement parameters Z(ISoC) and Z
(history) can lead to a deviation of the real part of two impedance
measurements at the same SoC of up to 20%.
279
Journal of Energy Storage 21 (2019) 272–280
The assumption that the effects are caused by the graphite electrode
is supported by the varying cell chemistries used. All three cells have
different electrode compositions with graphite being the only common
material. In addition, the correlation of the current dependent im-
pedance and the cell thickness of the pouch cell is another indicator for
this assumption.
Future work will focus on a time domain investigation of the pre-
sented effects. This enables the separate examination of the charge and
discharge process, which is not possible with EIS. Thereby, the occur-
ring OCV hysteresis losses can be investigated in more detail.
Acknowledgement
The authors would like to thank Felix Brauchle for his support in
editing the manuscript and the graphics it contains.
M. Oldenburger et al.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at https://doi.org/10.1016/j.est.2018.11.029.
References
[1] D. Andre, M. Meiler, K. Steiner, H. Walz, T. Soczka-Guth, D.U. Sauer,
Characterization of high-power lithium-ion batteries by electrochemical impedance
spectroscopy. II: Modelling, J. Power Sources 196 (12) (2011) 5349–5356, https://
doi.org/10.1016/j.jpowsour.2010.12.102.
[2] B.A. Boukamp, Impedance spectroscopy, strength and limitations, Technisches
Messen 71 (2004) 454–459, https://doi.org/10.1524/teme.71.9.454.42758.
[3] P.L. Moss, G. Au, E.J. Plichta, J.P. Zheng, An electrical circuit for modeling the
dynamic response of Li-ion polymer batteries, J. Electrochem. Soc. 155 (12) (2008)
A986–A994, https://doi.org/10.1149/1.2999375.
[4] D. Klotz, M. Schönleber, J.P. Schmidt, E. Ivers-Tiffée, New approach for the cal-
culation of impedance spectra out of time domain data, Electrochim. Acta 56 (24)
(2011) 8763–8769, https://doi.org/10.1016/j.electacta.2011.07.096.
[5] N. Lohmann, P. Weßkamp, P. Haußmann, J. Melbert, T. Musch, Electrochemical
impedance spectroscopy for lithium-ion cells: test equipment and procedures for
aging and fast characterization in time and frequency domain, J. Power Sources 273
(2015) 613–623, https://doi.org/10.1016/j.jpowsour.2014.09.132.
[6] E. Karden, S. Buller, R.W. De, Doncker, A method for measurement and inter-
pretation of impedance spectra for industrial batteries, J. Power Sources 85 (1)
(2000) 72–78, https://doi.org/10.1016/S0378-7753(99)00385-7.
[7] M. Oldenburger, B. Bedürftig, A. Gruhle, E. Richter, A new approach to measure the
non-linear butler-volmer behavior of electrochemical systems in the time domain, J.
Energy Storage 14 (Part 1) (2017) 16–21, https://doi.org/10.1016/j.est.2017.09.
002.
[8] F.M. Kindermann, A. Noel, S.V. Erhard, A. Jossen, Long-term equalization effects in
Li-ion batteries due to local state of charge inhomogeneities and their impact on
impedance measurements, Electrochim. Acta 185 (Supplement C) (2015) 107–116,
280
Journal of Energy Storage 21 (2019) 272–280
https://doi.org/10.1016/j.electacta.2015.10.108.
[9] A. Barai, G.H. Chouchelamane, Y. Guo, A. McGordon, P. Jennings, A study on the
impact of lithium-ion cell relaxation on electrochemical impedance spectroscopy, J.
Power Sources 280 (Supplement C) (2015) 74–80, https://doi.org/10.1016/j.
jpowsour.2015.01.097.
[10] N.A. Sekushin, Impedance of electrochemical cell with hysteresis effects in vol-
tammetric characteristics, Russ. J. Electrochem. 47 (12) (2011) 1374–1380,
https://doi.org/10.1134/S102319351112010X.
[11] B. Bitzer, A. Gruhle, A new method for detecting lithium plating by measuring the
cell thickness, J. Power Sources 262 (Supplement C) (2014) 297–302, https://doi.
org/10.1016/j.jpowsour.2014.03.1.
[12] F. Grimsmann, F. Brauchle, T. Gerbert, A. Gruhle, M. Knipper, J. Parisi, Hysteresis
and current dependence of the thickness change of lithium-ion cells with graphite
anode, J. Energy Storage 12 (Supplement C) (2017) 132–137, https://doi.org/10.
1016/j.est.2017.04.006.
[13] E. Barsoukov, J.R. Macdonald, Impedance Spectroscopy – Theory, Experiment, and
Applications, WILEY-INTERSCIENCE, 2005, https://doi.org/10.1002/0471716243.
[14] A. Jossen, Fundamentals of battery dynamics, J. Power Sources 154 (2) (2006)
530–538, https://doi.org/10.1016/j.jpowsour.2005.10.041.
[15] T. Jacobsen, K. West, Diffusion impedance in planar, cylindrical and spherical
symmetry, Electrochim. Acta 40 (2) (1995) 255–262, https://doi.org/10.1016/
0013-4686(94)E0192-3.
[16] J. Illig, Physically based Impedance Modelling of Lithium-Ion Cells. PhD thesis,
Department of Electrical Engineering and Information Technology, Karlsruhe
Institute of Technology (KIT), 2014.
[17] S. Buller, Impedance-Based Simulation Model for Energy Storage Devices in
Advanced Automotive Power Systems. PhD thesis, Institute for Power Electronics
and Electrical Drives, RWTH Aachen University, 2003.
[18] Juhyun Song, Z. Martin, Bazant, Electrochemical impedance of a battery electrode
with anisotropic active particles, Electrochim. Acta 131 (2014) 214–227, https://
doi.org/10.1016/j.electacta.2014.03.013 Electrochemical Impedance
Spectroscopy.
[19] J. Song, M.Z. Bazant, Effects of nanoparticle geometry and size distribution on
diffusion impedance of battery electrodes, J. Electrochem. Soc. 160 (1) (2013)
A15–A24, https://doi.org/10.1149/2.023301jes.