energies

Article
Impedance Characterization and Modeling of
Lithium-Ion Batteries Considering the Internal
Temperature Gradient
Haifeng Dai 1,2, *, Bo Jiang 1,2 and Xuezhe Wei 1,2
1 National Fuel Cell Vehicle & Powertrain System Research & Engineering Center, No. 4800, Caoan Road,
Shanghai 201804, China; jiangbo15@tongji.edu.cn (B.J.); weixzh@tongji.edu.cn (X.W.)
2 School of Automotive Studies, Tongji University, No. 4800, Caoan Road, Shanghai 201804, China
* Correspondence: tongjidai@tongji.edu.cn; Tel.: +86-21-6958-3847

Received: 30 December 2017; Accepted: 13 January 2018; Published: 17 January 2018

Abstract: Battery impedance is essential to the management of lithium-ion batteries for electric
vehicles (EVs), and impedance characterization can help to monitor and predict the battery
states. Many studies have been undertaken to investigate impedance characterization and the
factors that influence impedance. However, few studies regarding the influence of the internal
temperature gradient, which is caused by heat generation during operation, have been presented.
We have comprehensively studied the influence of the internal temperature gradient on impedance
characterization and the modeling of battery impedance, and have proposed a discretization model
to capture battery impedance characterization considering the temperature gradient. Several
experiments, including experiments with artificial temperature gradients, are designed and
implemented to study the influence of the internal temperature gradient on battery impedance.
Based on the experimental results, the parameters of the non-linear impedance model are obtained,
and the relationship between the parameters and temperature is further established. The experimental
results show that the temperature gradient will influence battery impedance and the temperature
distribution can be considered to be approximately linear. The verification results indicate that
the proposed discretization model has a good performance and can be used to describe the actual
characterization of the battery with an internal temperature gradient.

Keywords: lithium-ion battery; impedance characterization; temperature gradient; discretization

model

1. Introduction
Currently, the world faces increasingly severe environmental problems, including the greenhouse
effect and industrial pollution [1]. It is also beset by the shortage of resources, especially fossil
fuel energy. To resolve these urgent problems, people consider green cars including battery electric
vehicles (BEVs), fuel cell electric vehicles (FCEVs), hybrid EVs (HEVs), and so on, to be critically
important [2]. As key components of green cars, batteries have attracted great attention in recent
years. Among the current commercial batteries, lithium-ion batteries (LIBs) are considered as the best
choice for automobile application, due to their high power/energy density, long life cycle, safety, and
environmental friendliness [3–5]. However, safe operating conditions are hard to ensure for LIBs, so
the battery management system (BMS) is essential when LIBs are used in vehicles [6,7]. To monitor and
better manage LIBs in the battery pack, the pack voltage, pack current, cell voltage, cell temperature,
cell impedance and so on must be detected.
Battery impedance has been regularly employed to investigate battery parameters and states.
Buller et al. [8] proposed an impedance-based simulation model for supercapacitors and LIBs, and the

Energies 2018, 11, 220; doi:10.3390/en11010220 www.mdpi.com/journal/energies

Energies 2018, 11, 220 2 of 18

results showed that the simulated and measured voltage data were in excellent agreement. Xu et al. [9]
analyzed the impedance spectra of LIBs and derived a simplified impedance model for the estimation
of battery state of charge (SOC). Based on the different value of the simplified equivalent circuit
elements at different SOCs, Westerhoff et al. [10] developed a novel method to estimate the battery
SOC, and this method could be considered as complementary to the ampere-hour integral method.
Moreover, battery impedance has been employed to estimate the battery’s internal temperature and
determine the thermal model parameters [11–14].
Considering the importance of battery impedance, many researchers have studied the impedance
characterization during practical applications. Schönleber et al. [15] derived the impedance of a LIB
electrode from the intercalation reaction of lithium and studied its dependency on SOC, and the
results showed that the electrolyte diffusion impedance is independent of the SOC. Huang et al. [16]
systematically analyzed how different SOCs of 7.5~93.0% can influence battery impedance, and the
results indicated that both charge transfer resistance and diffusion resistance increased dramatically
when SOC is below 26.5%. Jiang et al. [17] investigated the impedance of batteries with different life
cycles (up to 520 cycles) and found that when the frequency is higher than 100 Hz, the impedance
phase of different, aging batteries would be different to each other. Other than the influence of
SOC and battery aging status on battery impedance, battery temperature also has a great impact
on impedance. Andre et al. [18] investigated the influence of temperature and SOC on LIBs and,
through the cell impedance, the non-linear correlation between temperature and impedance was found.
Raijmakers et al. [19] studied the impedance characterization of a pristine nickel cobalt aluminum
oxide battery (NCA) cell at different temperatures and found that ohmic resistance would decrease
as the temperature increases and inductive characteristics barely change. Xiao et al. [20] found that
the battery impedance is sensitive to temperature because the ions’ mobility and permittivity are
dependent on temperature.
During operation, heat generation caused by charge/discharge may contribute to the temperature
rise, and undoubtedly, the temperature rise is inhomogeneous. Usually, the cell internal temperature
will always be higher, and the temperature will decrease from inside to outside, which can be called
the temperature gradient. It is a common phenomenon, but very few studies have investigated the
influence of the temperature gradient. In references [21,22], a lumped-parameter electro-thermal
model was proposed and applied. The parameters of the electrical model were modified according
to the average battery temperature. However, the core temperature was obviously higher than the
surface temperature, and the influence of the temperature gradient was ignored. The influence of
the temperature gradient on an LIB’s impedance characterization has not been extensively studied
either. Troxler et al. [23] designed an artificial temperature gradient for the battery and analyzed the
performance of LIBs. For a cell with similar average temperature, the larger the temperature gradient,
the greater the behavior deviation from a cell with a uniform temperature will be. However, that
study only focused on the charge transfer resistance. In reference [11], the overall resistance of the
battery with inhomogeneous temperature distribution was similar to the resistance of the battery with
homogeneous temperature distribution, and the homogeneous temperature was the mean value of the
inhomogeneous temperature.
The objective of this paper is to investigate battery impedance characterization considering the
internal temperature gradient, and then prove that the model considering the temperature gradient
will perform better. We will propose a novel discretization model and experiments with the design of
artificial temperature gradients for the battery with the help of a heating plate. The remaining part of
this paper is organized as follows: Section 2 will introduce the battery impedance, and a discretization
model, based on the non-linear impedance model, is proposed to study the influence of the battery
internal temperature gradient on impedance. In Section 3, several experiments are conducted to
investigate the impact on battery impedance, and a heating plate is used to construct the artificial
temperature gradient. Section 4 will provide some experimental results and discuss the influencing
factors on battery impedance. The verification results of the proposed discretization model are also
 Energies 2018, 11, 220 3 of 19

Energies 2018, 11, 220

2. Methodology 3 of 18

2.1. Battery Non-Linear Impedance Model

shown in order to verify the model performance. Finally, some conclusions are drawn and summations
Electrochemical impedance spectroscopy (EIS) is the method most used to obtain the
provided in Section 5.
impedance characterization of LIBs, due to its accuracy and non-damaging effects. During EIS
measurement, the electrochemical system is loaded with a specific amplitude but different
2. Methodology
frequency sine current; after measuring the corresponding electrical feedback voltage signal,
2.1. characterization
Battery Non-Linear of the electrochemical
Impedance Model system will be obtained. Figure 1 shows the impedance
spectroscopy of a lithium-ion battery at 50% SOC and ambient temperature if 0 °C. The
Electrochemical
measurement impedance
frequency rangesspectroscopy
from 0.01 Hz (EIS)tois10
thekHz.
method most used
Obviously, the towhole
obtainimpedance
the impedance
characterization of LIBs,ofdue
spectroscopy consists threeto main
its accuracy
regions: and non-damaging
the low-frequency effects.
region, During EIS measurement,
middle-frequency region and the
high-frequency
electrochemical region
system [9]. Thewith
is loaded low-frequency region ranges
a specific amplitude from 0.01
but different Hz to 0.16
frequency sineHz, the after
current;
middle-frequency region ranges from 0.16 Hz to 630 Hz, and the high-frequency region
measuring the corresponding electrical feedback voltage signal, characterization of the electrochemical ranges from
630 Hz
system willtobe
10obtained.
kHz. Figure 1 shows the impedance spectroscopy of a lithium-ion battery at 50%
In the low-frequency region, impedance spectroscopy looks like a straight line with a constant
SOC and ambient temperature if 0 ◦ C. The measurement frequency ranges from 0.01 Hz to 10 kHz.
slope, a typical phenomenon of diffusion [24]. In the middle-frequency region, the impedance
Obviously, the whole impedance spectroscopy consists of three main regions: the low-frequency region,
spectroscopy is a depressed semicircle caused by the charge transfer reaction at the electrode
middle-frequency
surfaces. In theregion and high-frequency
high-frequency region [9]. The
region, the impedance low-frequency
spectroscopy forms aregion
small ranges
curve andfrom 0.01
Hz to 0.16 Hz,
intersects thethe
with middle-frequency
abscissa axis. Theregion ranges from
high-frequency 0.16
region Hz tothe
reflects 630battery’s
Hz, andinductance
the high-frequency
and
region ranges from
ohmic resistance. 630 Hz to 10 kHz.

Figure1.1.Impedance
Figure Impedance spectroscopy
spectroscopyofof
a battery at 50%,
a battery 0 °C.0 ◦ C.
at 50%,

According to the above battery impedance spectroscopy and the battery equivalent circuit
In the low-frequency
models widely used, we region,
employ impedance spectroscopy
the following model shownlooksinlike a straight
Figure line with
2 to analyze a constant
battery
slope, a typical phenomenon of diffusion [24]. In the middle-frequency region,
impedance. The model consists of four parts to represent the physical and electrochemical reaction the impedance
spectroscopy is a depressed
processes inside semicircle
the battery. caused Lbyand
The inductance theresistance
charge transfer reaction
Ro describe at the electrode
the battery behaviors surfaces.
at
In the
highhigh-frequency
frequency, where region,
the the impedance
resistance spectroscopy
Ro equals the valueforms
of thea small curve of
intersection and
theintersects
impedancewith the
spectroscopy
abscissa axis. The and the abscissa axis.
high-frequency To better
region capture
reflects the non-linear
the battery’s behavior
inductance of ohmic
and the battery, a new
resistance.
equivalent
According to the above battery impedance spectroscopy and the battery equivalent circuitinmodels
circuit element with a constant, frequency-independent phase has been widely applied
lithium-ion
widely used, we equivalent
employcircuit models [23–25].
the following modelThe middle-frequency
shown in Figure 2 toregion is modeled
analyze batterybyimpedance.
a constant The
phase element (CPE) (CPE1) and a resistance (R1) connected in parallel. In the low-frequency region,
model consists of four parts to represent the physical and electrochemical reaction processes inside the
another CPE (CPE2) instead of a Warburg impedance is used to describe the diffusion
battery. The inductance L and resistance Ro describe the battery behaviors at high frequency, where the
characterization, because the Warburg impedance may lead to fitting failure and a CPE can also
resistance
produce Rothe
equals the value of
characterization of the intersection of
an infinite-length the impedance
Warburg spectroscopy and the abscissa axis.
element [25].
To better capture the non-linear behavior of the battery, a new equivalent circuit element with a constant,
frequency-independent phase has been widely applied in lithium-ion equivalent circuit models [23–25].
The middle-frequency region is modeled by a constant phase element (CPE) (CPE1 ) and a resistance
(R1 ) connected in parallel. In the low-frequency region, another CPE (CPE2 ) instead of a Warburg
impedance is used to describe the diffusion characterization, because the Warburg impedance may
lead to fitting failure and a CPE can also produce the characterization of an infinite-length Warburg
element [25].
Energies 2018, 11, 220 4 of 18
Energies 2018, 11, 220 4 of 19

Figure 2. Equivalent circuit of the battery impedance model.

Figure 2. Equivalent circuit of the battery impedance model.
The impedance of a CPE can be expressed in fractional calculus as:
The impedance of a CPE can be expressed in fractional calculus as:
1
Z CPE ( s ) = (1)
Qsα1
ZCPE (s) = (1)
where ZCPE is the impedance of the CPE; s is the Laplace Qsoperator; Q is the fractional coefficient; and
α

α is the fractional order, α ∈ R , 0 ≤ α ≤ 1 . It should be noted that the CPE represents a resistance
ZCPEα is
wherewhen the impedance of the CPE; s is the Laplace operator; Q is the fractional coefficient; and α
= 0, and represents a capacitance when α = 1.
is the fractional order, α ∈ expression
The mathematical R, 0 ≤ α ≤of1.theIt impedance
should be ofnoted that the
the whole CPE represents
equivalent a resistance
circuit model is: when
α = 0, and represents a capacitance when α = 1.
R1 1
The mathematical expression of Z mod
the ) = Ls + Ro + of the
el ( simpedance +
αwholeβ equivalent circuit model is:(2)
1+R1Q1 s Q2 s

where Zmodel denotes the impedance of Ls

the+equivalent R1
circuit model;1L and Ro are the inductance
Zmodel (s) = Ro + + (2)
1 + R1in
resistance in the high-frequency region; R1 is the resistance Q1the
s middle-frequency
α Q2 s β region; Q1 and α
are the fractional coefficient and order of the CPE1; and Q2 and β are the fractional coefficient and
where Zmodel
order CPE2. the impedance of the equivalent circuit model; L and Ro are the inductance
denotes
of the
resistance in the high-frequency region; R1 is the resistance in the middle-frequency region; Q1 and
α are2.2.
theDiscretization
fractional coefficient and order
Model Considering of the CPEGradient
the Temperature 1 ; and Q2 and β are the fractional coefficient and
order of the CPE 2 .
As mentioned above, heat will be generated during charging and discharging, and the heat will
lead to a temperature difference between core and surface. Usually, a battery consists of several
2.2. Discretization Model Considering the Temperature Gradient
electrode layers in which the positive layer and the negative layer are separated by the separator.
Thementioned
As positive andabove,
negativeheat
tabswill
are connected
be generatedin parallel
duringandcharging
then constitute a battery. According
and discharging, and the to heat
this view, we can consider one electrode layer or several electrode layers as a cell
will lead to a temperature difference between core and surface. Usually, a battery consists of several unit, and several
cell units form a battery. The thickness of each cell unit is small so that the temperature of each cell
electrode layers in which the positive layer and the negative layer are separated by the separator. The
unit can be considered as uniform. Every cell unit’s temperature is different if there exists a
positive and negative tabs are connected in parallel and then constitute a battery. According to this
temperature gradient internal to the battery, and every unit’s temperature can be determined if the
view,internal
we can temperature
consider one electrode layer
distribution or several electrode layers as a cell unit, and several cell units
is obtained.
form a battery. The thickness of each cell
In Schmidt’s [11] study, three assumptionsunit is small
aboutso thethat the temperature
battery of eachdistribution
internal temperature cell unit can be
considered as uniform. Every cell unit’s temperature is different if there exists
perpendicular to the electrodes have been made, including the constant distribution, linear a temperature gradient
internal to the battery,
distribution, and everydistribution.
and polynomial unit’s temperature
Constant can be determined
distribution if the
is that the internal temperature
temperature of each
electrodeisisobtained.
distribution a constant equal to the mean value of the temperature of two surfaces. For polynomial
distribution,
In Schmidt’sthe temperature
[11] study, threedistribution
assumptionsinside about
the battery is a polynomial
the battery internalfunction.
temperature distribution
perpendicular to the electrodes have been made, including the constant battery
In our study, we assume the temperature distribution inside the is linear.
distribution, On distribution,
linear the one
hand, considering the battery thickness, the curvature of the temperature distribution line is small,
and polynomial distribution. Constant distribution is that the temperature of each electrode is a
and it can be approximated as linear. On the other hand, the calculation of each cell unit’s
constant equal to the mean value of the temperature of two surfaces. For polynomial distribution, the
temperature will become more complicated if the temperature distribution line is non-linear. The
temperature
assumptiondistribution inside the battery is a polynomial function.
is shown below:
In our study, we assume the temperature distribution inside the battery is linear. On the one
hand,Assumption
considering the temperature
1. The battery thickness, the
distribution curvature
is linear of the temperature
in the direction distribution
vertical to the battery line
tabs if the is small,
battery
and itthickness
can be is far less than theas
approximated battery height.
linear. On the other hand, the calculation of each cell unit’s temperature
will become more complicated if the temperature distribution line is non-linear. The assumption is
shown below:
Assumption 1. The temperature distribution is linear in the direction vertical to the battery tabs if the battery
thickness is far less than the battery height.
Energies 2018, 11, 220 5 of 18
Energies 2018, 11, 220 5 of 19

Figure 3 shows
Figure
Energies 2018, 220 the
3 shows
11, thediagram
diagramof ofthe
the battery discretization.InInFigure
battery discretization. Figure 3a,3a,
thethe battery
battery is considered
is considered
5 of 19 as
as a continuous
a continuous battery,battery,
and T and
i is T i is the
the internal
internal temperature
temperature and
and T T
s sis is the
the surface
surface temperature.
temperature. In most
In most case,
the case, the temperature
Figure
temperature 3 shows
of the theofdiagram
two the two of
surfaces surfaces
isthe is similar,
battery
similar, Ti and
is theTimaximum
discretization.
and isInthe maximum
Figure 3a, the battery
battery battery temperature.
is considered
temperature. According
According
as a to
continuous the above
battery, assumption,
and T is the the temperature
internal temperature distribution
and
to the above assumption, the temperature distribution is linear and symmetrical. In Figure
i T s is is
the linear
surface and symmetrical.
temperature. In mostIn3b, we
Figure
case, the3b, we discretize the continuous battery into individual cell units and the battery can be
discretize thetemperature
continuousofbattery
the twointo surfaces is similar,
individual and Tiand
cell units is the themaximum
battery can battery temperature.
be considered as these
considered
According to as the
these several
above cell units
assumption, theconnected
temperature in distribution
parallel. Every cell unit
is linear has a uniform
and symmetrical. In
several cell units connected in parallel. Every cell unit has a uniform temperature.
temperature.
Figure 3b, we discretize the continuous battery into individual cell units and the battery can be
considered as these several cell units connected in parallel. Every cell unit has a uniform
temperature.

Figure
Figure 3.3.Diagram
Diagram of
of battery
battery discretization:
discretization: (a)(a)
continuous battery;
continuous (b) discrete
battery; battery.
(b) discrete battery.

In FigureFigure4, we3. place

Diagrama heating
of batterysource on the left
discretization: (a)side of the battery,
continuous anddiscrete
battery; (b) Ts1 is the temperature of
battery.
Inbattery’s
the Figure 4, leftwe placeand
surface a heating
Ts2 is thesource on theofleft
temperature the side of the
battery’s battery,
right surface. and
If theTs1heating
is the source
temperature
of the battery’s
provides enough
In Figure left surface
heat
4, we and
anda heating
place T
the battery is the
s2 sourcedoestemperature
on not produce
the left of the
side ofheat battery’s
itself, Ts1and
the battery, right
canTs1be surface.
is considered If
the temperature asthe
theheating
of
source
the provides
maximum
battery’s enough
temperature
left surfaceheat theand
ofand the
Tbattery
s2 is thebattery
and does
Ts2 is
temperature nottheproduce
the minimum.
of From
battery’s heat
right to Ts2, Tthe
Ts1itself,
surface. s1Ifcan
thebe
temperatureconsidered
heating inside as the
source
the
maximum battery
provides is in a linear
temperature
enough heatofdistribution.
the the
and battery Every Tcell
anddoes
battery s2 isunit’s
notthe temperature
minimum.
produce heat From can be
itself, determined
Ts1s1 to Tbe
can theif temperature
we obtain
s2 , considered Ts1 inside
as the
the and Ts2. After
battery
maximum inthe determination
is temperature
a linear distribution.of the and
of the battery temperature
Every cell
Ts2 is of eachtemperature
theunit’s
minimum. cell From
unit, the
Ts1 cell
can
to unit’s
Ts2 ,be impedance will
thedetermined
temperature be obtain
ifinside
we
determined.
the battery isFor
in aexample,
linear in Figure
distribution. 4, the
Every impedance
cell unit’s of the
temperature leftmost
can
Ts1 and Ts2 . After the determination of the temperature of each cell unit, the cell unit’s impedance be cell unit
determined performs
if we like
obtain the
Ts1
continuous
and T s2. Afterbattery
the at high temperature,
determination of the and the impedance
temperature of each cell of thethe
unit, rightmost
cell unit’scell unit acts will
impedance as thebe like
will be determined. For example, in Figure 4, the impedance of the leftmost cell unit performs
continuous
determined.battery at low temperature.
For example, in Figure 4, the Theimpedance
continuousofbattery is made
the leftmost cellupunit
of several
performs cell
like units
the
the continuous battery at high temperature, and the impedance of the rightmost cell unit acts as
connected
continuousinbattery
parallel.at high temperature, and the impedance of the rightmost cell unit acts as the
the continuous battery at low temperature. The continuous battery is made up of several cell units
continuous battery at low temperature. The continuous battery is made up of several cell units
connected in parallel.
connected in parallel.

Figure 4. Diagram of battery discretization with a heating source.

Figure4.4.Diagram
Figure Diagram of
of battery
batterydiscretization
discretizationwith a heating
with source.
a heating source.
Energies 2018, 11, 220 6 of 18

Energies 2018, 11, 220 6 of 19

AfterAfter
dividing a battery
dividing with
a battery withananexternal
external heating sourcelike
heating source likeFigure
Figure 4 into
4 into N cell
N cell units,
units, the the
temperature of each cell unit will be as follows:
temperature of each cell unit will be as follows:
i −1
i = T−
Ti =TT − i − 1 (Ts1 − T−
s 2 )T ) (3)
s1 s1 N − 1 ( T s2 (3)
N − 1 s1
where Ti is the temperature of the ith cell unit, and the 1st is the leftmost cell unit.
where Ti is the temperature of the ith cell unit, and the 1st is the leftmost cell unit.
According to the relationship of each cell unit, the impedance of the discretization model can be
According
listed as:
to the relationship of each cell unit, the impedance of the discretization model can be
listed as:
1 1
D-model((ss)
ZD−Zmodel )==N (4)
N
∑Zi (Zs)i (s)
(4)
i =1i =1

wherewhere ZD-model
ZD-model is the
is the impedance
impedance of of
thethe discretizationmodel,
discretization model,and
andZZi iisisthe
theimpedance
impedance of the ith cell
cell unit.
unit.
In the following sections, the influence of temperature on battery impedance will be investigated.
In the following
After the relationship sections,
between Zi andthe influence
Ti in of temperature
ith cell unit is obtained, on
the battery impedance
impedance will be
of the discretization
investigated. After the relationship between Zi and Ti in ith cell unit is obtained, the impedance of
model will be known according to Equations (3) and (4).
the discretization model will be known according to Equations (3) and (4).
According to the above methodology, the flowchart of the discretization modeling of the battery
According to the above methodology, the flowchart of the discretization modeling of the
impedance
batterycan be illustrated
impedance in Figure in
can be illustrated 5. Figure 5.

Figure 5. Flowchart of the discretization modeling of a battery.

Figure 5. Flowchart of the discretization modeling of a battery.
Energies 2018, 11, 220 7 of 18

Energies 2018, 11, 220 7 of 19

3. Experiment
3.
EISExperiment
experiments are undertaken to investigate the battery’s characteristics. A pouch-type LiFePO4
battery with
EIS a nominal capacity
experiments of 40 Ahtois investigate
are undertaken used in thethe experiment, and there are 51
battery’s characteristics. electrode layers
A pouch-type
stacked inside
LiFePO the battery.
4 battery with a The size of
nominal the battery
capacity of 40 isAh133 used×in16.1
is mm the mm × 184 mm.
experiment, and there are 51
Experiments
electrode layerswith temperature
stacked inside the gradients
battery. The orsize
not of
arethedesigned
battery isand133 conducted
mm × 16.1 mm in this
× 184section.
mm. In the
experiment Experiments
without awith temperature
temperature gradients
gradient, or not are
usually littledesigned and conducted
heat is generated in this
in the EIS section.
experiment,In so
the experiment without a temperature gradient, usually little heat
the environmental chamber temperature is considered as the battery temperature. In the experiment is generated in the EIS
withexperiment,
temperature so gradients,
the environmental chamber
a heating plate temperature is considered
is used to construct as the battery
an artificial temperature.
temperature In
gradient in
the experiment with temperature gradients, a heating plate is used to construct an artificial
order to obtain an accurate and qualitative result. One side of the battery is covered with the heating
temperature gradient in order to obtain an accurate and qualitative result. One side of the battery is
plate, and the other side is exposed to the environment. Apparently, due to heat convection, the real
covered with the heating plate, and the other side is exposed to the environment. Apparently, due to
temperature of the side
heat convection, coated
the real with the of
temperature heating
the sideplate may
coated withbethe
lower thanplate
heating the heating platethan
may be lower temperature,
the
and due to heat
heating plateconduction,
temperature,the real
and temperature
due of the side
to heat conduction, the exposed to the environment
real temperature may betohigher
of the side exposed
thanthe
the environment
environmental maytemperature.
be higher than Wethe useenvironmental
thermocouples to obtain the
temperature. Weactual temperature and
use thermocouples to the
temperature
obtain thegradient of the battery.
actual temperature In addition
and the temperatureto this, in order
gradient of the tobattery.
confirmInthe assumption
addition to this, that
in the
order to confirm the assumption that the temperature gradient
temperature gradient is linearly distributed, two thermocouples are placed inside the battery. is linearly distributed, two
thermocouples
Figure 6 shows arethe
placed insideof
position the battery.
the thermocouples inside the battery. T-type thermocouples are
Figure 6 shows the position
used in the experiments, and the diameter of the thermocouples inside the battery.
of the thermocouples is 0.28T-type
mm.thermocouples
One thermocoupleare is
used in the experiments, and the diameter of the thermocouples is 0.28 mm. One thermocouple is
placed in the halfway point within the battery, and another is situated at the quarter point within the
placed in the halfway point within the battery, and another is situated at the quarter point within the
battery. The battery cell under experiment is shown in Figure 7a.
battery. The battery cell under experiment is shown in Figure 7a.

Figure
Figure 6. Position
6. Position of thermocouples
of the the thermocouples inside
inside the the battery:
battery: (a) quarter
(a) quarter point
point of the
of the battery;
battery; (b) (b)
halfway
halfway within the battery; (c) diagram of the thermocouples inside
within the battery; (c) diagram of the thermocouples inside the battery. the battery.

Figure 7 shows the EIS experimental setup. An electrochemical workstation, as shown in Figure
Figure
7b, 7 shows
including thethe EIS experimental
electrochemical setup.
interface and Anthe electrochemical
frequency response workstation,
analyzer, isas shown
used in Figure 7b,
to generate
including the electrochemical interface and the frequency response analyzer,
the sinusoidal current and then analyze the frequency response of the cell in order to obtain is used to generate
the
the sinusoidal currentAand
battery impedance. then
power analyze
booster the7c)
(Figure frequency
can enlargeresponse of thecurrent
the sinusoidal cell ingenerated
order to byobtain
the the
battery impedance.workstation.
electrochemical A power booster (Figuremeasurement
A temperature 7c) can enlarge the(Figure
station sinusoidal current generated
7d), including the wirelessby the
temperature workstation.
electrochemical unit and the wireless logging station,
A temperature is used to obtain
measurement stationthe temperature
(Figure and log the
7d), including thedata.
wireless
The battery cell is placed in an environment chamber, as shown in Figure 7e.
temperature unit and the wireless logging station, is used to obtain the temperature and log the data.
The battery cell is placed in an environment chamber, as shown in Figure 7e.

3.1. Experiments without the Temperature Gradient

To acquire the characterization of battery impedance and the relationship between the parameters
of the battery’s non-linear impedance model and temperature, the EIS experiment without the
temperature gradient is conducted first. Figure 8 shows the diagram of battery EIS experiment
without the temperature gradient.
 Energies 2018, 11, 220 8 of 19

Energies 2018, 11, 220 8 of 18

Energies 2018, 11, 220 8 of 19

Figure 7. Experimental setup: (a) the battery cell; (b) the electrochemical workstation; (c) the power
booster; (d) the temperature measurement station; (e) the environment chamber.

3.1. Experiments without the Temperature Gradient

To acquire the characterization of battery impedance and the relationship between the
parameters of the battery’s
Figure 7. Experimental setup:non-linear impedance
(a) the battery cell; (b) themodel and temperature,
electrochemical the
workstation; (c) EIS experiment
the power
Figure 7. Experimental
without setup:
the(d)temperature (a) the is
gradient battery cell; (b)
conducted the Figure
first. electrochemical
8 shows workstation;
the diagram (c) of the power
battery EIS
booster; the temperature measurement station; (e) the environment chamber.
booster; (d) the
experiment temperature
without measurement
the temperature station; (e) the environment chamber.
gradient.
3.1. Experiments without the Temperature Gradient
To acquire the characterization of battery impedance and the relationship between the
parameters of the battery’s non-linear impedance model and temperature, the EIS experiment
without the temperature gradient is conducted first. Figure 8 shows the diagram of battery EIS
experiment without the temperature gradient.

8. Diagram
FigureFigure of battery
8. Diagram electrochemical
of battery impedance
electrochemical impedancespectroscopy (EIS)experiment
spectroscopy (EIS) experiment without
without the the
temperature
temperature gradient.
gradient.

Table 1 shows the detailed EIS experiment steps without the temperature gradient. Enough rest
Table
time 1isshows the before
necessary detailedtheEIS
testexperiment
to improve steps without
the accuracy ofthe
the temperature
experiment. Agradient.
sinusoidalEnough
currentrest
time iswith
necessary before the test to improve the accuracy of the experiment. A sinusoidal
2 A amplitude and a frequency ranging from 0.01 Hz to 10 kHz is loaded on the battery. current with
Figure and
2 A amplitude 8. Diagram of battery
a frequency electrochemical
ranging impedance
from 0.01 spectroscopy
Hz to 10 (EIS) experiment
kHz is loaded without the
on the battery.
temperature gradient.

Table 1 shows the detailed EIS experiment steps without the temperature gradient. Enough rest
time is necessary before the test to improve the accuracy of the experiment. A sinusoidal current
with 2 A amplitude and a frequency ranging from 0.01 Hz to 10 kHz is loaded on the battery.
Energies 2018, 11, 220 9 of 18

Table 1. EIS experiments without the temperature gradient. CC-CV: constant current-constant voltage.
Energies 2018, 11, 220 9 of 19

StepTable 1. EIS experiments without the temperature

Experiment Description
gradient. CC-CV: constant current-constant
1 voltage. Rest the battery for 4 h at 25 ◦ C
2
Step Charge the battery to 100% SOC in CC-CV
Experiment mode at 25 ◦ C
Description
3 Rest the battery for 4 h at 30 ◦ C
1 Rest the battery for 4 h at 25 °C
4 EIS Test
2 Charge the battery to 100% SOC in CC-CV◦mode at◦25 °C ◦
Set the chamber temperature to −20 C, −15 C, −10 C, −5 ◦ C, 0 ◦ C, 10 ◦ C and 20 ◦ C,
35 Rest the
andbattery
rest thefor 4 h at for
battery 30 °C
4 h, repeat Step 4
46 EIS Test
Rest the battery for 4 h at 25 ◦ C
Set the chamberthe
Discharge temperature
battery to to
90%−20SOC,
°C, −15
70%°C, −10 50%
SOC, °C, −5 °C, 030%
SOC, °C, SOC,
10 °C and
and 10%
20 °C, andrepeat
SOC, rest
57
the battery
Step 3for 4 h, repeat
to Step 6 Step 4
68 Endbattery for 4 h at 25 °C
Rest the
Discharge the battery to 90% SOC, 70% SOC, 50% SOC, 30% SOC, and 10% SOC, repeat Step 3
7
to Step 6
3.2. Experiments
8
with
End
Artificial Temperature Gradients
As mentioned above, a heating plate is used to construct the temperature gradient. Figure 9
3.2. Experiments with Artificial Temperature Gradients
shows the diagram of the battery EIS experiment with temperature gradients. One side of the
As mentioned above, a heating plate is used to construct the temperature gradient. Figure 9
battery cell is covered with a heating plate. Besides the thermocouples inside the battery, there
shows the diagram of the battery EIS experiment with temperature gradients. One side of the battery
are thermocouples stuckwith
cell is covered to the surface
a heating of the
plate. battery.
Besides Although the
the thermocouples heating
inside plate temperature
the battery, there are and
the chamber temperature
thermocouples stuckcan be surface
to the set to specific values,
of the battery. the actual
Although temperature
the heating of theand
plate temperature battery
the surface
measured chamber
by the temperature
thermocouplescan be will
set tobe
specific
usedvalues, the actual
to analyze thetemperature
temperature of thegradient.
battery surface
The battery
measured by the thermocouples will be used to analyze the temperature gradient. The battery
maintains 50% SOC during the experiment with an artificial temperature gradient in order to focus on
maintains 50% SOC during the experiment with an artificial temperature gradient in order to focus
the correlation
on theof the temperature
correlation gradient.
of the temperature gradient.

Figure 9.Figure 9. Diagram of battery EIS experiment with the temperature gradients.
Diagram of battery EIS experiment with the temperature gradients.
Table 2 shows the detailed EIS experiment steps with a temperature gradient. Enough rest time
Table 2is shows
also necessary before the
the detailed testexperiment
EIS to improve the accuracy
steps withof athe experiment. gradient. Enough rest time is
temperature
also necessary before the test to improve the accuracy of the experiment.

Table 2. EIS experiment with the temperature gradients.

Step Experiment Description

1 Rest the battery for 4 h at 25 ◦ C
2 Charge the battery to 100% SOC in CC-CV mode at 25 ◦ C
3 Rest the battery for 4 h at 25 ◦ C
4 Discharge the battery to 50% SOC in 0.5 C (1 C = 40 A ) at 25 ◦ C
5 Set the heating plate temperature to 30 ◦ C and the chamber temperature to 20 ◦ C
6 Rest the battery for 4 h at 25 ◦ C
7 EIS Test
8 Change the heating plate temperature (every 5 ◦ C), and repeat Step 6 to Step 7
Set the chamber temperature to −20 ◦ C, −15 ◦ C, −10 ◦ C, −5 ◦ C, 0 ◦ C, 10 ◦ C and 15 ◦ C,
9
and rest the battery for 4 h, repeat Step 5 to Step 8
10 End
 4 Discharge the battery to 50% SOC in 0.5 C (1 C = 40 A ) at 25 °C
5 Set the heating plate temperature to 30 °C and the chamber temperature to 20 °C
6 Rest the battery for 4 h at 25 °C
7 EIS Test
8 Change the heating plate temperature (every 5 °C), and repeat Step 6 to Step 7
Energies 2018, 11, 220 10 of 18
Set the chamber temperature to −20 °C, −15 °C, −10 °C, −5 °C, 0 °C, 10 °C and 15 °C, and rest
9
the battery for 4 h, repeat Step 5 to Step 8
10 End
4. Results and Discussion
4. Results and Discussion
4.1. Battery EIS Characterization without the Temperature Gradient
4.1. Battery
Figure EIS Characterization
10 shows without the
the EIS experiment Temperature
results of the Gradient
battery with a uniform temperature. Figure 10a
shows theFigure
EIS of10the battery
shows theat different
EIS temperatures,
experiment and
results of the from this
battery withwe can see temperature.
a uniform that, with theFigure
increase of
temperature, the impedance becomes smaller when the frequency is low. While in
10a shows the EIS of the battery at different temperatures, and from this we can see that, with the the high-frequency
increase
region, the EISof temperature,
curves with the impedance
different becomes smaller
temperatures coincide when
withtheeach
frequency is low.
other and thisWhile in thein the
is clearer
high-frequency
enlarged region,
part of Figure theThis
10a. EIS indicates
curves with different
that temperatures
the temperature coincide
mainly with each
influences theother and diffusion
battery this
and charge transfer reaction processes, while the battery’s inductance and ohmic resistancethe
is clearer in the enlarged part of Figure 10a. This indicates that the temperature mainly influences are not
battery diffusion and charge transfer reaction processes, while the battery’s inductance and ohmic
affected by the temperature. Figure 10b shows the EIS of a battery with the same temperature but
resistance are not affected by the temperature. Figure 10b shows the EIS of a battery with the same
different SOCs. From this picture, we can see that all the curves are close to each other in the middle
temperature but different SOCs. From this picture, we can see that all the curves are close to each
and high frequencies, and in the low-frequency region, the most obvious difference is the slope. With
other in the middle and high frequencies, and in the low-frequency region, the most obvious
the increase
differenceofisthe
theSOC,
slope.the slope
With the of the straight
increase line becomes
of the SOC, the slopelarger. This indicates
of the straight that SOC
line becomes mainly
larger.
impacts the battery diffusion process.
This indicates that SOC mainly impacts the battery diffusion process.

Figure
Figure 10. 10.
EISEISof ofbattery
batterywith
with uniform
uniform temperature:
temperature: (a)(a)
50% state
50% of charge
state (SOC),
of charge different
(SOC), different
temperatures; (b) 10
◦ °C, different
temperatures; (b) 10 C, different SOCs. SOCs.

The EIS results of the battery with uniform temperature are shown in Figure 11 with the
The EIS results
frequency of the battery
as a variable; Figurewith
11a,buniform temperature
shows the impedanceare shown inand
magnitude Figure 11 with
phase of thethe frequency
battery
as a variable; Figuretemperatures,
under different 11a,b shows whilethe impedance
Figure 11c,dmagnitude and phase
is the impedance of the battery
magnitude under
and phase of different
the
battery at while
temperatures, different SOCs.
Figure Figure
11c,d 11aimpedance
is the shows thatmagnitude
the battery and
impedance
phase ofwilltheincrease
battery as the
at different
SOCs.temperature
Figure 11a decreases,
shows thatand the
the battery
battery impedance
impedance at will
−20 °C is almost
increase as 10
thetimes the impedance
temperature at 20 and
decreases,
°C at the frequency of 0.01 Hz
◦ to 0.1 Hz. The impedance phase curves shown
◦ in Figure
the battery impedance at −20 C is almost 10 times the impedance at 20 C at the frequency of 0.01 11b have a Hz
great discrimination between 1 Hz and 10 Hz, and that is why the impedance phase can be used to
to 0.1 Hz. The impedance phase curves shown in Figure 11b have a great discrimination between 1
estimate battery temperature [12]. In a similar way to Figure 10b, the impedance magnitude curves
Hz and 10 Hz, and that is why the impedance phase can be used to estimate battery temperature [12].
In a similar way to Figure 10b, the impedance magnitude curves in Figure 11c and the phase curves in
Figure 11d are close to each other in all frequency ranges, and it can be concluded that the SOC has
little impact on the battery impedance.

4.2. Battery EIS Characterization with Temperature Gradients

Temperature distribution inside the battery is analyzed before obtaining the EIS experiment
results of the battery with the artificial temperature gradients. Figure 12 shows the temperature
distribution inside the battery with the artificial gradients. Due to the battery’s thickness and heat
transfer, the actual temperature gradient may be different to the temperature gradient that is set. Six
groups of data are shown in this figure, including three groups with a smaller set temperature gradient
(10 ◦ C), and three groups with a larger set temperature gradient (35 ◦ C). To get a more intuitive view of
these data, we give them a linear fit, and the fitting results are also shown in the figure. From this, we
can see that the fitting results are excellent, and the R-Square of all fitting results are greater than 0.98.
Energies 2018, 11, 220 11 of 18
Energies 2018, 11, 220 11 of 19

It can beinconcluded thatthe

Figure 11c and thephase
temperature
curves ininside
Figurethe
11dbattery is to
are close linearly distributed,
each other and the
in all frequency assumption
ranges, and
proposed in Section
it can 2 is reasonable.
be concluded that the SOC has little impact on the battery impedance.

Figure 11.Figure
EIS 11. EIS battery
of the of the battery
in Bodein plots
Bode with
plots uniform
with uniform temperature:
temperature: (a,b)(a,b) impedance
impedance magnitude
magnitude and
and phase of battery at 50% SOC, different temperatures; (c,d) impedance magnitude
phase of battery at 50% SOC, different temperatures; (c,d) impedance magnitude and phase of battery and phase of
battery at 10 °C, different SOCs.
at 10 ◦ C,
Energies different
2018, 11, 220 SOCs. 12 of 19

4.2. Battery EIS Characterization with Temperature Gradients

Temperature distribution inside the battery is analyzed before obtaining the EIS experiment
results of the battery with the artificial temperature gradients. Figure 12 shows the temperature
distribution inside the battery with the artificial gradients. Due to the battery’s thickness and heat
transfer, the actual temperature gradient may be different to the temperature gradient that is set. Six
groups of data are shown in this figure, including three groups with a smaller set temperature
gradient (10 °C), and three groups with a larger set temperature gradient (35 °C). To get a more
intuitive view of these data, we give them a linear fit, and the fitting results are also shown in the
figure. From this, we can see that the fitting results are excellent, and the R-Square of all fitting
results are greater than 0.98. It can be concluded that the temperature inside the battery is linearly
distributed, and the assumption proposed in Section 2 is reasonable.

Figure
Figure 12.Temperature
12. Temperature distribution
distribution inside
insidebattery.
battery.

As mentioned above, the temperature has a great impact on battery impedance. The next point
As mentioned above, the temperature has a great impact on battery impedance. The next point
to study is the influence of the temperature gradient on the impedance. Figure 13 shows four sets of
to study
data,isincluding
the influence of the temperature
one experiment gradient
at a 10 °C uniform on the impedance.
temperature Figure 13 shows
and three experiments four sets of
with different
data, temperature
including one experiment at a 10 ◦ C uniform temperature and three experiments with different
gradients. In the experiment at a 10 °C uniform temperature, the battery temperature
temperature
gradient gradients.
is considered Inasthe experiment
zero. Although at 10 ◦ Cthree
theaother uniform temperature,
experiments the battery
are implemented temperature
in different
environmental
gradient temperature,
is considered as zero.they have one
Although thething in common,
other the actual heating
three experiments plate temperature
are implemented is
in different
about 10 °Ctemperature,
environmental (10.59 °C, 10.28 °C,have
they 9.76 one
°C), thing
so these
in experiments
common, the areactual
considered
heatingto have
plateatemperature
similar
maximum
is about temperature.
10 ◦ C (10.59 In the
◦ C, 10.28 ◦ C,figure,
9.76 ◦from
C), sothe black
these line to the magenta
experiments line, thetotemperature
are considered have a similar
gradient becomes larger. Figure 13a shows that battery impedance will increase as the temperature
maximum temperature. In the figure, from the black line to the magenta line, the temperature gradient
gradient becomes greater from 0.01 Hz to 10 Hz, and Figure 13b shows that the battery impedance
becomes larger. Figure 13a shows that battery impedance will increase as the temperature gradient
phase will decrease as the temperature gradient becomes greater from 1 Hz to 100 Hz. It may be
becomes greater from 0.01 Hz to 10 Hz, and Figure 13b shows that the battery impedance phase will
concluded that if the maximum battery temperature is fixed, the smaller the minimum temperature,
the greater the battery impedance magnitude.
 to study is the influence of the temperature gradient on the impedance. Figure 13 shows four sets of
data, including one experiment at a 10 °C uniform temperature and three experiments with different
temperature gradients. In the experiment at a 10 °C uniform temperature, the battery temperature
gradient is considered as zero. Although the other three experiments are implemented in different
environmental temperature, they have one thing in common, the actual heating plate temperature is
about 10 °C (10.59 °C, 10.28 °C, 9.76 °C), so these experiments are considered to have a similar
Energies 2018, 11, 220 temperature. In the figure, from the black line to the magenta line, the temperature
maximum 12 of 18
gradient becomes larger. Figure 13a shows that battery impedance will increase as the temperature
gradient becomes greater from 0.01 Hz to 10 Hz, and Figure 13b shows that the battery impedance
decrease asphase
the temperature
will decrease asgradient becomes
the temperature greater
gradient fromgreater
becomes 1 Hz from
to 100 Hz.
1 Hz to It
100may
Hz. be concluded
It may be that
concluded
if the maximum that if the
battery maximum battery
temperature temperature
is fixed, is fixed,
the smaller thetheminimum
smaller the minimum temperature,
temperature, the greater the
the greater the battery impedance magnitude.
battery impedance magnitude.

Figure 13. EIS of battery in Bode plots with different artificial temperature gradients: (a) impedance
Figure 13. EIS of battery in Bode plots with different artificial temperature gradients: (a) impedance
magnitude; (b) impedance phase.
magnitude; (b) impedance phase.
There is another point worth noting in Figure 12: the magenta line and the olive line intersect at
Theretheis half of the point
another battery.worth
According to the
noting inassumption
Figure 12:thatthethemagenta
temperature is linearly
line and thedistributed,
olive linetheintersect at
temperature at the battery’s center can be considered as the average battery temperature. A situation
the half ofwhereby
the battery. According to the assumption that the temperature is linearly distributed, the
several experiments under different temperature gradients but the same battery average
temperature at the battery’s
temperature demonstratecenter canimpedance
similar be considered as the average
characterization should be battery temperature.
verified and discussed. A situation
whereby several We experiments
select some experiments with approximate
under different temperatureaverage temperature,
gradients butincluding
the same thebattery
lower average
average temperature (1 °C) and the higher average temperature (21
temperature demonstrate similar impedance characterization should be verified and discussed.°C). Besides these, we also
supplement the experiments with those of 1 °C and 21 °C uniform temperature. Figure 14 shows the
We select some experiments with approximate average temperature, including the lower average
temperature (1 ◦ C) and the higher average temperature (21 ◦ C). Besides these, we also supplement
Energies 2018, 11, 220 13 of 19
the
experiments with those of 1 ◦ C and 21 ◦ C uniform temperature. Figure 14 shows the experimental EIS
experimental
of a battery with approximateEIS of a battery withtemperature,
average approximate average
and in temperature, and in
Figure 14b,d, Figure
the 14b,d, thephase of a
impedance
impedance phase of a battery with different temperature gradients, but in both cases the similar
battery with different temperature gradients, but in both cases the similar average temperatures almost
average temperatures almost coincide with each other. In Figure 14a,c, the impedance magnitude of
coincide with each other.gradient
each temperature In Figure
differs14a,c, theother
from each impedance
in the low magnitude ofand
frequency range each temperature
is unrelated to the gradient
differs from each other
temperature. in the
It may low frequency
be concluded range
that batteries and
with is unrelated
similar to the temperature.
average temperature possess similar It may be
concludedimpedance
that batteriescharacterizations.
with similar average temperature possess similar impedance characterizations.

Figure 14. Figure

EIS of14.battery
EIS of battery
with with approximateaverage
approximate average temperature:
temperature: (a,b)(a,b)
impedance magnitude
impedance and
magnitude and
phase of battery with approximate
◦ 1 °C average temperature; (c,d) impedance magnitude and phase
phase of battery with approximate 1 C average temperature; (c,d) impedance magnitude and phase of
of battery with approximate 21 °C average temperature.
battery with approximate 21 ◦ C average temperature.
Some summaries and conclusions about the battery impedance characterization can be drawn
according to the above experimental results:
(1) Temperature mainly influences the diffusion and charge transfer reaction processes, while the
battery inductance and the ohmic resistance are not affected. SOC only has an impact on the
battery diffusion process. In general, the temperature has a greater impact on battery
impedance than SOC.
Energies 2018, 11, 220 13 of 18

Some summaries and conclusions about the battery impedance characterization can be drawn
according to the above experimental results:
(1) Temperature mainly influences the diffusion and charge transfer reaction processes, while the
battery inductance and the ohmic resistance are not affected. SOC only has an impact on the
battery diffusion process. In general, the temperature has a greater impact on battery impedance
than SOC.
(2) For batteries with the same maximum temperature, battery impedance will increase as
the temperature gradient becomes greater, especially in the low-frequency region, and the
battery impedance phase will decrease as the temperature gradient become greater in the
middle-frequency region.
(3) In our experiment with artificial temperature gradients, we find that the temperature distribution
can be approximately considered to be linear, so the central temperature is equal to the average
temperature. The experiments with similar average temperature possess similar impedance
characterization, and this is consistent with the idea of lumped parameter model.

4.3. Determination of the Parameters of a Battery Non-Linear Impedance Model

The results of experiments without the temperature gradient are used to fit the equivalent circuit
model, and one2018,
Energies of the fitting results is shown in Figure 15. This indicates that the experimental
11, 220
Energies 2018, 11, 220
14 of 19
14 of 19
data
and the fitting data almost coincide at all the experimental frequencies, and Figure 15a shows that in
experimental data
experimental data and
and the
the fitting
fitting data
data almost
almost coincide
coincide atat all
all the
the experimental
experimental frequencies,
frequencies, and
and
the high-frequency
Figure 15a region
15a shows
shows the
that in EIS is not a straight
the high-frequency
high-frequency regionline
theperpendicular
EIS is
is not toline
not aa straight
straight theperpendicular
abscissa axis; so, maybe a
to the
the
Figure that in the region the EIS line perpendicular to
resistance abscissa
parallelaxis;
abscissa with
axis; so,inductance
so, maybe
L canparallel
maybe aa resistance
resistance improve
parallel withthe
with
fitting.LLOverall,
inductance
inductance can improve
can
thethe
improve fitting
the results
fitting.
fitting.
are
Overall,
Overall, theacceptable
the
fitting
and can befitting results
usedresults are
in theare acceptable
discretization and can be
model. used in the discretization
acceptable and can be used in the discretization model. model.

Figure 15. Fitting result: (a) EIS; (b) impedance magnitude; (c) impedance phase.
Figure
Figure 15. 15. Fitting
Fitting result:
result: (a) (a) EIS;
EIS; (b)(b)impedance
impedance magnitude;
magnitude;(c) impedance phase. phase.
(c) impedance
Figure 16
Figure 16 shows
shows the
the fitting
fitting parameters
parameters of
of the
the battery
battery model,
model, and
and R
Roo and
and R
R11 decrease
decrease
exponentially
Figureexponentially
16 shows thewith temperature
fitting
with increase,
parameters
temperature while
of the
increase, Q1,1, and
battery
while Q and Q22 increase
model,
Q increase exponentially
and Roexponentially when exponentially
and R1 decrease
when the
the
temperature increases.
increases.
with temperature increase, while Q1, and Q2 increase exponentially when the temperature increases.
temperature

Figure 16. Parameters of battery non-linear impedance model: (a) inductance L; (b) resistance Ro; (c)
Figure 16.Figure 16. Parameters of battery non-linear impedance model: (a) inductance L; (b) resistance Ro; (c)
Parameters
resistance R1; (d)of battery
fractional non-linear
coefficient impedance
of CPE model: (a) inductance L; (b) resistance Ro ;
1, Q1; (e) fractional coefficient of CPE2, Q2; (f) fractional
resistance R1; (d) fractional coefficient of CPE1, Q1; (e) fractional coefficient of CPE2, Q2; (f) fractional
(c) resistance R of; (d)
order CPEfractional
1 and CPE2, coefficient
α and β.
order 1of CPE1 and CPE2, α and β.
of CPE1 , Q1 ; (e) fractional coefficient of CPE2 , Q2 ; (f) fractional
order of CPE1 and CPE2 , α and β.
We employ
We employ aa polynomial
polynomial fit
fit to
to get
get the
the relationship
relationship between
between the
the battery
battery impedance
impedance model
model
parameters and
parameters and temperature,
temperature, and
and the
the formula
formula can
can be
be listed
listed as:
as:

L
-11
L == 4.66
4.66 ××10
10-11 tt ++ 4.58 10-8-8
4.58××10
 R = -1.95 × 10-9-9 t33 + 1.27 × 10-7-7 t 22 − 4.10 ×10-6-6 t + 1.3 × 10-3-3
Roo = -1.95 × 10 t + 1.27 × 10 t − 4.10 ×10 t + 1.3 × 10
RR1 = -1.01× 10-6-6 t33 + 5.66 × 10-5-5tt 22 −−1.1 10-3-3tt+8.9
1.1××10 10-3-3
+8.9 ××10
 1 = -1.01× 10-4 t3 + 5.66 × 10
Q = 3.89 × 10-4 t3 + 7.8 × 10-3-3t 22 + 0.29t + 11.22 (5)
Energies 2018, 11, 220 14 of 18

We employ a polynomial fit to get the relationship between the battery impedance model
parameters and temperature, and the formula can be listed as:

L = 4.66 × 10−11 t + 4.58 × 10−8



Ro = −1.95 × 10−9 t3 + 1.27 × 10−7 t2 − 4.10 × 10−6 t + 1.3 × 10−3





−6 3 −5 2 −3 −3
 R1 = −1.01 × 10 t + 5.66 × 10 t − 1.1 × 10 t + 8.9 × 10



Q1 = 3.89 × 10−4 t3 + 7.8 × 10−3 t2 + 0.29t + 11.22 (5)
 Q2 = 1.9 × 10−3 t3 + 0.62t2 + 25.19t + 354.13



α = 0.82 − 4.2 × 10−3 t





β = 1.6 × 10−3 t + 0.48


where t is the temperature in centigrade, and L, Ro , R1 , Q1 , Q2 , α and β are the model parameters.
Energies 2018, 11, 220 15 of 19
The above work has enabled the relationship between the battery impedance model
parameters Theandabovethework
temperature
has enabledtothe
berelationship
obtained, between
and thethe
relationship will bemodel
battery impedance usedparameters
in the battery
discretization model.
and the temperature to be obtained, and the relationship will be used in the battery discretization
model.
4.4. Verification of Battery Impedance Model Considering the Temperature Gradient
4.4. Verification of Battery Impedance Model Considering the Temperature Gradient
In most cases, the battery’s surface temperature or average temperature is used to modify the
In most cases,However,
battery’s impedance. the battery’s
thesurface
abovetemperature or average
analysis makes temperature
it obvious is used
that the to modify
internal the
temperature
battery’s impedance. However, the above analysis makes it obvious that the internal temperature
gradient has a great influence on battery impedance. Figure 17 shows the comparison of the
gradient has a great influence on battery impedance. Figure 17 shows the comparison of the
experimental results and lumped model impedance modified by the surface temperature. The
experimental results and lumped model impedance modified by the surface temperature. The
parameters of the
parameters lumped
of the lumpedmodel
modelare areobtained
obtained according
according totoEquation
Equation(5)(5)andand battery
battery surface
surface
temperature. Plainly, there are large deviations between the experimental results and
temperature. Plainly, there are large deviations between the experimental results and the lumped the lumped
model impedance
model impedancemodified
modifiedbybythethesurface
surfacetemperature, nomatter
temperature, no matterwhat
whatthethe maximum
maximum surface
surface or or
minimum surface
minimum temperatures
surface temperaturesare.
are.

Figure
Figure 17. Comparison
17. Comparison of the
of the experimentalresults
experimental results and
and lumped
lumpedmodel
modelimpedance modified
impedance by the
modified by the
surface temperature: (a) EIS; (b) impedance magnitude; (c) impedance phase.
surface temperature: (a) EIS; (b) impedance magnitude; (c) impedance phase.

According to the discretization model shown in Equation (4) and the relationship between the
According
impedance modelto the parameters
discretization model shown
and temperature in Equation
in Equation (4) impedance
(5), the and the relationship between
of a battery with
the impedance model parameters
artificial temperature gradientsandcan temperature
be obtained. in Equation
Three (5), thewith
experiments impedance
a higher of a battery with
temperature
gradient
artificial (the actual
temperature temperature
gradients can bedifference
obtained. between battery surfaces
Three experiments with aishigher
greatertemperature
than 20 °C) gradient
are
chosen to verify the battery discretization model. Figure 18 shows the verification
◦
(the actual temperature difference between battery surfaces is greater than 20 C) are chosen to verify of the battery
discretization model. The discretization model considering the temperature gradient and the
the battery discretization model. Figure 18 shows the verification of the battery discretization model.
lumped model considering only the average temperature are also compared.
The discretization model considering the temperature gradient and the lumped model considering
Overall, the proposed battery discretization model is closer to the actual experimental data than
only the average temperature are also compared.
the lumped model. From Figure 18b,e,h, we can see that both the proposed model and the lumped
Overall, the proposed
model deviate battery
from the actual discretization
experimental datamodel is closer
from 0.01 Hz to 10toHz.
theThis
actual
may experimental
be because that data
the than
the lumped model.
relationship Fromtemperature
between Figure 18b,e,h,
and thewe can seeorder
fractional that both
of CPEthe proposed
1 and CPE2 may model
not beand theFrom
linear. lumped
modelFigure
deviate frominthe
18c,f,i, actual
most cases,experimental
the proposeddata fromimpedance
model’s 0.01 Hz tophase
10 Hz. This may
is closer beexperimental
to the because that the
data, which
relationship proves
between the accuracyand
temperature of the proposed
the model.
fractional order of CPE1 and CPE2 may not be linear. From
Figure 18c,f,i, in most cases, the proposed model’s impedance phase is closer to the experimental data,
which proves the accuracy of the proposed model.
Energies 2018, 11, 220 15 of 18
Energies 2018, 11, 220 16 of 19

Figure
Figure 18. Verification
18. Verification of battery
of battery discretizationmodel:
discretization model: (a–c)
(a–c)EIS,
EIS,impedance
impedancemagnitude andand
magnitude phase of of
phase
battery with heating plate temperature set at 25◦°C and −15 °C
◦ environmental temperature;
battery with heating plate temperature set at 25 C and −15 C environmental temperature; (d–f) EIS, (d–f) EIS,
impedance magnitude and phase of battery with heating plate temperature set at 30 °C and −10 °C
impedance magnitude and phase of battery with heating plate temperature set at 30 ◦ C and −10 ◦ C
environmental temperature; (g–i) EIS, impedance magnitude and phase of battery with heating plate
environmental temperature; (g–i) EIS, impedance magnitude and phase of battery with heating plate
temperature set at 35 °C and −5 °C environmental temperature.
temperature set at 35 ◦ C and −5 ◦ C environmental temperature.
Figure 19 shows the errors of the discretization model and the lumped model. Obviously, the
magnitude
Figure error ofthe
19 shows the errors
discretization
of the model is smallermodel
discretization in the whole frequency
and the lumped range, whileObviously,
model. the phase the
errors in Figure 19d–f show that the lumped model performs a little better than
magnitude error of the discretization model is smaller in the whole frequency range, while the phase the discretization
errorsmodel in the
in Figure low-frequency
19d–f show that region.
the lumpedApparently,
model the lower athe
performs temperature,
little better thanthe thegreater the
discretization
magnitude error. In Figure 19a–c, the experiment with the lower average temperature has a greater
model in the low-frequency region. Apparently, the lower the temperature, the greater the magnitude
error in the low frequency range. In the high-frequency region, the relationship between the phase
error. In Figure 19a–c, the experiment with the lower average temperature has a greater error in the
error and the frequency is approximately linear and independent of temperature. This may be due to
low frequency
the batteryrange. In themodel’s
impedance high-frequency region,
inherent defect thea relationship
that single inductor between
may not therepresent
phase error and the
the real
frequency is approximately linear and independent of temperature. This may be
characterization of battery impedance in the high-frequency region. In the whole frequency range, due to the battery
impedance model’s
the maximum inherent magnitude
impedance defect thaterror
a single
of theinductor may not represent
battery discretization model isthe
1.46real characterization
mOhm, and the
of battery
maximumimpedance
impedance in the
phasehigh-frequency
error is 6.96°. region. In the whole frequency range, the maximum
impedance Table 3 compares
magnitude the of
error statistical data of
the battery the discretization
discretization modelmodel and mOhm,
is 1.46 the averageandtemperature
the maximum
model. Obviously, the
impedance phase error is 6.96 . accuracy
◦ of the discretization model is higher, especially the impedance
magnitude
Table of the proposed
3 compares model.
the statistical dataAmong
of thethe three experiments
discretization model with different
and the average temperature
temperature
gradients, the root mean squared error (RMSE) of the proposed model is at least 15% smaller than
model. Obviously, the accuracy of the discretization model is higher, especially the impedance
that of the average temperature model. For the model impedance phase, the proposed model is
magnitude of the proposed model. Among the three experiments with different temperature gradients,
slightly superior.
the root mean squared error (RMSE) of the proposed model is at least 15% smaller than that of the
average temperature model. For the model impedance phase, the proposed model is slightly superior.
Through the above analysis, the performance of the proposed model is proved to be accurate and
effective. Compared with the lumped model with the average temperature, the proposed model is
identical to the actual battery impedance. With the help of the discretization model, we can obtain a
more accurate characterization of the battery.
Energies 2018, 11, 220 16 of 18
Energies 2018, 11, 220 17 of 19

Figure
Figure 19. Errors
19. Errors of the
of the discretizationmodel
discretization modeland
and the
the lumped
lumped model:
model:(a–c) impedance
(a–c) magnitude
impedance magnitude
errors; (d–f) impedance phase errors.
errors; (d–f) impedance phase errors.
Table 3. Statistical data of the discretization model and the average temperature model.
Table 3. Statistical data of the discretization model and the average temperature model.
Magnitude Error (mOhm) Phase Error (°)
Root Mean Squared
Discretization Average Temperature Discretization Average Temperature
Error (RMSE) Magnitude
Model Error (mOhm)
Model Model Phase Error (◦ )
Model
Root Mean
Set:Error
Squared 25~−15 °C 0.67 0.77
Average 2.20 2.54
Average
Set: 30~−10 °C Discretization
0.16 0.32 Discretization
1.77 1.84
(RMSE) Temperature Temperature
Set: 35~−5 °C Model0.15 0.23 Model
2.22 2.34
Model Model
Set: 25~ ◦C
−15 the above analysis,
0.67 the performance
0.77of the proposed 2.20 2.54
Through model is proved to be accurate
Set: 30~ − 10 ◦C 0.16 0.32 1.77 1.84 model
and effective.◦ Compared with the lumped model with the average temperature, the proposed
Set: 35~−5 C 0.15 0.23 2.22 2.34
is identical to the actual battery impedance. With the help of the discretization model, we can obtain
a more accurate characterization of the battery.
4.5. Limitations and Future Work
4.5. Limitations and Future Work
In the proposed discretization model, the temperature distribution in the direction parallel to the
battery taps In the proposedIndiscretization
is ignored. model, the distribution
fact, the temperature temperature distribution in the direction
is inhomogeneous in this parallel
direction.to The
the battery taps is ignored. In fact, the temperature distribution is inhomogeneous in this direction.
temperature of the part close to the battery taps is higher. Moreover, this model may not be suitable for
The temperature of the part close to the battery taps is higher. Moreover, this model may not be
cylindrical-type batteries because the volume of inner and outer layers is different and the calculation
suitable for cylindrical-type batteries because the volume of inner and outer layers is different and
of eachthe calculation of eachwill
layer impedance layerbecome
impedancecomplex.
will become complex.
The proposed
The proposed discretization
discretizationmodel
modelisisbased
based onon the batterynon-linear
the battery non-linear impedance
impedance model.
model. It is It is
worthworth
notingnoting
that this
thatmodel is generic
this model for batteries
is generic with similar
for batteries characterizations
with similar like thelike
characterizations impedance
the
impedance
spectroscopy spectroscopy
shown in Figureshown
1. Forinother
Figure 1. For other
lithium-ion lithium-ion
batteries withbatteries
differentwith different
battery battery the
chemistries,
batterychemistries,
non-linear theimpedance
battery non-linear
model impedance model may
may be different and be different
should and should be
be determined determined
first. In that case,
the discretization method can be applied to batteries with various chemical materials.chemical
first. In that case, the discretization method can be applied to batteries with various Verification
materials. Verification of the adaptability of this discretization method to other battery chemistries
of the adaptability of this discretization method to other battery chemistries shall be conducted in
shall be conducted in future work.
future work.
Considering the thickness of the battery used in this paper, the temperature distribution is
Considering the thickness of the battery used in this paper, the temperature distribution is
assumed to be linear. Unlike the artificial temperature gradient in this paper, the core and surface
assumed to be linear.
temperatures Unlike the
will construct artificial temperature
the temperature gradient
gradient in actual in this paper,
applications the core
of batteries. Futureand surface
work
temperatures
will focus on the temperature distribution of the battery with a larger size. Based on anwork
will construct the temperature gradient in actual applications of batteries. Future
will focus on the temperature
electrothermal distribution
model, the core of the
temperature willbattery with aonline,
be estimated largerandsize.
thenBased on anparameters
the model electrothermal
model, will
thebecore
modified according
temperature willto be
theestimated
proposed online,
discretization
and thenmodel. The modified
the model modelwill
parameters parameters
be modified
will eventually
according improve the
to the proposed precision of the
discretization batteryThe
model. electrothermal
modified modelmodel. parameters will eventually
improve the precision of the battery electrothermal model.
Energies 2018, 11, 220 17 of 18

5. Conclusions
This paper proposed a battery discretization model and designed some experiments to investigate
the impedance characterization of a battery with internal temperature gradients. Some conclusions
and summations are drawn below:
(1) Temperature has a more significant impact on battery impedance than SOC. In the low-frequency
region, the temperature gradient will influence the impedance magnitude, and in the
middle-frequency region, the temperature gradient will influence the impedance phase. For
batteries with the same maximum temperature, battery impedance will increase as the
temperature gradient gets greater, especially in the low-frequency region.
(2) The temperature distribution inside the battery can be approximately considered to be linear, and
batteries with the similar average temperature have a similar impedance characterization.
(3) A discretization model was proposed to investigative the impedance of a battery with temperature
gradients, and experimental results show that the model performs well. The maximum impedance
magnitude error is 1.46 mOhm. Compared to the lumped model with average temperature, the
impedance produced by the proposed model is identical to the actual battery impedance, and the
RMSE of the proposed model is at least 15% smaller than that of the average temperature model.

Acknowledgments: This work is financially supported by the National Natural Science Foundation of China
(NSFC, Grant No. 51677136) and the National Key Research and Development Program of China (Program No.
2017YFB0103105).
Author Contributions: Haifeng Dai designed the experiments and wrote the paper; Bo Jiang performed the
experiments and analyzed the results; Xuezhe Wei reviewed and revised the paper. All authors read and approved
the manuscript
Conflicts of Interest: The authors declare no conflict of interest.

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