Pengujian Performa Baterai

Lithium Ion
Achmad Subhan, S.Si, MT.

Pusat Riset Material Maju - BRIN

achm018@brin.go.id
+62-81315898872
IMPEDANCE

All our dreams can come

true, if we have the
courage to pursue them
(Walt-Disney)
 2. ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY
EIS
Introduction.

Impedance Spectroscopy is also called AC Impedance or just

Impedance Spectroscopy. The usefulness of impedance spectroscopy lies in
the ability to distinguish the dielectric and electric properties of individual
contributions of components under investigation.

Impedance spectroscopy is a non-destructive technique and so can provide time

dependent information about the properties but also about ongoing processes such
as corrosion or the discharge of batteries and e.g. the electrochemical reactions in
fuel cells, batteries or any other electrochemical process.

http://www.gamry.com/App_Notes/EIS_Primer/EIS_Primer.htm
3
4/4/2023
 Basic theory : DC signal
• Resistance : DC signal

• Ohms Law E
R 
I
• For a resistor, R, it follows Ohm’s Law at all current and voltage
levels
• The resistance value is independent of frequency
• AC current and voltage signals through a resistor are in phase
with each other

4/4/2023 4
 Basic theory : AC signal
• Impedance (X) : AC signal
• Impedance applies to AC voltage and current
• Like resistance impedance is a measure of the ability of a
circuit to resist the flow of electrical current
• The excitation potential or AC voltage can be expressed as a
function of time
  2f
Et  E0 sin t  I t  I 0 sin t   
Et  potential at time t I t  response current
E0  the amplitude of the voltage I 0  the amplitude of the current
  the radial frequency   the phase shift

Input signal Cell battery output signal

4/4/2023 5
 Impedance calculation :
• Similar to Ohm’s law

Et E0 sin t  sin t 

Z   Z0
It I 0 sin t    sin t   

• The important point to remember is that when an AC voltage is

applied to a pure capacitor the resulting AC current is shifted in
phase by 90o
• There is no phase shift for a pure resistor

4/4/2023 6
 Serial and Parallel Combinations of Circuit Elements

Very few electrochemical cells can be modeled using a single equivalent circuit element.
Instead, EIS models usually consist of a number of elements in a network. Both serial and
parallel combinations of elements occur.

Impedances in Series: Z eq  Z1  Z 2  Z 3

Impedances in Parallel 1 1 1 1
  
Zeq Z1 Z 2 Z3

Penjelasan Pelatihan 7
 Measure Z(,Vbias)

The result will be Z(,Vo) = V() / I()

8
 - Frequency scan considerations -
What should be the perturbation amplitude?

50 mV

4.59 µA

0.59 µA

10 mV

With 10 mV, current changes are small, system does not change.
Complex writing
E (t ) E0 cos(t ) cos(t )
Z (t )    Z0
I (t ) I 0 cos(t   ) cos(t   )

Using Eulers relationship exp(i )  cos   i sin 

it is possible to express the impedance as a complex function.

The potential is described as,
E (t )  E0 exp( jt )
and the current response as,
I (t )  I 0 exp(it  i )
The impedance is then represented as a complex number,

E
Z   Z 0 exp(i )  Z 0 (cos   i sin  )
I
10
4/4/2023
 Phase shift
Current phase shift due to impedance. Through a
capacitor this phase shift is 90o

Applied
Voltage

Resulting
Current

11
Simple EIS

q1(f)

Data EIS : freq, Zreal, Z im,

phase degree,
Z total,
σ (conductivity)

12
 EIS Nyquist Plots
• A Nyquist plot is made up of a series of vectors representing
the total magnitude of the resistance and capacitance
components

Non Resistive
Component

Phase angle

4/4/2023 13
 Electrochemical Impedance
Spectroscopy
• Bode impedance plot

Impedance Rct
Solution
resistance

Frequency →
4/4/2023 14
 Electrochemical Impedance
Spectroscopy
• Bode Phase plot

Phase angle

Frequency →

4/4/2023 15
 Real Fenomenon = Equivalent circuit

J. Electrochem. Sci. Technol., 2020, 11(1), 1-13

16
Basic Electrical Circuit Elements
EIS data is commonly analyzed by fitting it to an equivalent electrical circuit model. Most of the circuit elements in
the model are common electrical elements such as resistors, capacitors, and inductors. To be useful, the elements
in the model should have a basis in the physical electrochemistry of the system. As an example, most models
contain a resistor that models the cell's solution resistance.
Some knowledge of the impedance of the standard circuit components is therefore quite useful. The Table lists
the common circuit elements, the equation for their current versus voltage relationship, and their impedance:

Component Current Vs.Voltage Impedance

resistor E= IR Z=R
inductor E = L di/dt Z = iL
capacitor i = C dE/dt Z = 1/iC
• Notice that the impedance of a resistor is independent of frequency and has only a real component. Because there is
no imaginary impedance, the current through a resistor is always in phase with the voltage.
• The impedance of an inductor increases as frequency increases. Inductors have only an imaginary impedance
component. As a result, an inductor's current is phase shifted 90 degrees with respect to the voltage.
• The impedance versus frequency behavior of a capacitor is opposite to that of an inductor. A capacitor's impedance
decreases as the frequency is raised. Capacitors also have only an imaginary impedance component. The current
through a capacitor is phase shifted -90 degrees with respect to the voltage.

17
4/4/2023
Serial and Parallel Combinations of Circuit Elements

Suppose we have a 1 and a 4  resistor is series. The impedance of a resistor is the same
as its resistance (see Table 2-1). We thus calculate the total impedance Zeq:

R1 R2
Z eq  Z1  Z 2  R1  R 2  1  4  5

Resistance and impedance both go up when resistors are combined in series.

Now suppose that we connect two 2 µF capacitors in series. The total capacitance of the
combined capacitors is 1 µF

1 1 1
C1 C2  Z1  Z 2  
Z eq iC1 iC2
1 1 1
    1 µF
i (2e ) i (2e ) i (1 )
6 6 e 6

Impedance goes up, but capacitance goes down when capacitors are connected in series.
This is a consequence of the inverse relationship between capacitance and 18
impedance.
4/4/2023
 Basic impedance : R,C,L

4/4/2023 19
 Single time constant

freq Rs X  deg
4
4.5
5.1
…
…
1MHz   S/cm θo
4/4/2023 20
 Equivalent circuit : Randles
• Randles circuit for a simple corroding system

Capacitan
Working ce
electrode
Ref
electrode Charge transfer
resistance = Rtotal - Rs

• Rs = the solution resistance Solution

Resistanc
Resistan
• Rct = the charger transfer ce
e

(polarisation resistance)
• Cdl = the double layer capacitance.
The double layer capacity is in parallel with the
impedance due to the charge transfer reaction
The real axis value at the other (low frequency) intercept is the
sum of the polarization resistance and the solution resistance.
The diameter of the semicircle is therefore equal to the
polarization resistance.

4/4/2023 21
 EIS (Summary)

We start here at the

high frequency

4/4/2023 22
 Teknik mengukur hambatan larutan.

Pada frequensi tinggi arus mengalir pada

Ru melalui Cdl. current interrupt

Step potential
Potensial kecil sehingga tidak ada arus
faradaic => Rct ~ short

23
 Hioki 3522

4.1 k
Autolab

6.95 k

4/4/2023 24
4/4/2023 25
 Same Voc, but impedance ?
800 30,000

25,000
600
2.86 V
20,000
3.16
3.40V
3.42
2.86 V
400 15,000
3.16
3.42
10,000

200

5,000

0 0
0 200 400 600 800 0 5,000 10,000 15,000 20,000 25,000 30,000

JK-20 JK-23

4/4/2023 26
 A Purely Capacitive Coating
A metal covered with an undamaged coating generally has a very high impedance. The
equivalent circuit for such a situation is in the Figure:

R C

The model includes a resistor (due primarily to the electrolyte) and the coating capacitance in series.
A Nyquist plot for this model is shown in the Figure. In making this plot, the following values were assigned:
R = 500  (a bit high but realistic for a poorly conductive solution)
C = 200 pF (realistic for a 1 cm2 sample, a 25 µm coating, and r = 6 )
fi = 0.1 Hz (lowest scan frequency -- a bit higher than typical)
ff = 100 kHz (highest scan frequency)

The value of the capacitance cannot be determined from the Nyquist plot. It can be determined by a curve fit
or from an examination of the data points. Notice that the intercept of the curve with the real axis gives an
estimate of the solution resistance.
The highest impedance on this graph is close to 1010  . This is close to the limit of measurement of most EIS
systems 27
4/4/2023
 Common Equivalent Circuit Models
In the following section we show some common equivalent circuits models.

To elements used in the following equivalent circuits are presented in the Table. Equations
for both the admittance and impedance are given for each element.

Equivalent Admittance Impedance

element
R 1/R R

C iC 1/1/iC

L 1/iL iL

W (infinite Y0(i)1/2 1/Y0(i)1/2

Warburg)
O (finite Warburg) Y0 i coth( B i ) tanh( B i ) / Y0 i 

Q (CPE) Y0(i) 1/Y0(i)

 EIS
• Diffusion or Mass Transfer controlled process
• Nyquist plot - Warburg Impedance

←Frequency

Bode Impedance plot Bode Phase plot

4/4/2023 29
4/4/2023 30
 Charge Transfer Resistance
A similar resistance is formed by a single kinetically controlled electrochemical reaction. In this case
we do not have a mixed potential, but rather a single reaction at equilibrium.
Consider a metal substrate in contact with an electrolyte. The metal molecules can electrolytically
dissolve into the electrolyte, according to:

or more generally:

In the forward reaction in the first equation, electrons enter the metal and metal ions diffuse into the
electrolyte. Charge is being transferred.
This charge transfer reaction has a certain speed. The speed depends on the kind of reaction, the
temperature, the concentration of the reaction products and the potential.
The general relation between the potential and the current holds:

F = Faradays constant
io = exchange current density T = temperature
Co = concentration of oxidant at the electrode R = gas constant
surface a = reaction order
Co* = concentration of oxidant in the bulk n = number of electrons involved
CR = concentration of reductant at the electrode h = overpotential ( E - E0 )
surface 31
Diffusion: Warburg impedance with infinite thickness
Diffusion can create an impedance known as the Warburg impedance. This impedance depends on
the frequency of the potential perturbation. At high frequencies the Warburg impedance is small
since diffusing reactants don't have to move very far. At low frequencies the reactants have to
diffuse farther, thereby increasing the Warburg impedance.
The equation for the "infinite" Warburg impedance

On a Nyquist plot the infinite Warburg impedance appears as a diagonal line with a slope of 0.5. On a
Bode plot, the Warburg impedance exhibits a phase shift of 45°.
In the above equation, s is the Warburg coefficient defined as:

 = radial frequency
DO = diffusion coefficient of the oxidant
DR = diffusion coefficient of the reductant
A = surface area of the electrode
n = number of electrons transferred
C* = bulk concentration of the diffusing species (moles/cm3)
32
4/4/2023
Constant Phase Element (for double layer capacity in real
electrochemical cells)
Capacitors in EIS experiments often do not behave ideally. Instead, they act like a constant phase element (CPE)
as defined below.
Z  A(i ) 

When this equation describes a capacitor, the constant A = 1/C (the inverse of the capacitance) and the
exponent  = 1. For a constant phase element, the exponent a is less than one.

The "double layer capacitor" on real cells often behaves like a CPE instead of like a capacitor. Several theories
have been proposed to account for the non-ideal behavior of the double layer but none has been universally
accepted. In most cases, you can safely treat  as an empirical constant and not worry about its physical basis.

33
4/4/2023
 Cole-Cole Plots: Impedance Plots in the Complex Plane

When we plot the real and imaginary components of impedance in the complex plane
(Argand diagram), we obtain a semicircle or partial semicircle for each parallel RC Voigt
network:

The diameter corresponds to the resistance R.

The frequency at the 90° position corresponds to 1/t = 1/RC

34
4/4/2023
 Analyzing Circuits
By using the various Cole-Cole plots we can calculate values of the elements of the equivalent
circuit for any applied bias voltage

By doing this over a range of bias voltages, we can obtain:

the field distribution in the layers of the device (potential divider) and the relative widths
of the layers, since C ~ 1/d
35
4/4/2023
 Bode Plot oft Randalls cell
This Figure is the Bode plot for the same cell. The solution resistance and the sum of the solution resistance and the
polarization resistance can be read from the magnitude plot. The phase angle does not reach 90° as it would for a pure
capacitive impedance. If the values for Rs and Rp were more widely separated the phase would approach 90°.
Bode Plot for 1 mm/year Corrosion Rate

36
4/4/2023
Simple simulation using excel :

37
4/4/2023
Example: a full cell
Adding to the previous example a double layer with capacitance and a charge transfer impedance, we get the
equivalent circuit:
This circuit models a cell where polarization is due to a combination of kinetic and
diffusion processes. The Nyquist plot for this circuit is shown in the Figure. As in
the above example, the Warbug coefficient is assumed to be about 150 W sec-1/2.
Other assumptions: Rs = 20  , Rct = 250  , and Cdl = 40 µF.

38
4/4/2023
 Bode plot
The Bode plot for the same data is shown here. The lower frequency limit was moved down to 1mHz to better
illustrate the differences in the slope of the magnitude and in the phase between the capacitor and the Warburg
impedance. Note that the phase approaches 45° at low frequency.

39
4/4/2023
 Simple simulation using excel : Recycle spent Graphite (halfcell).

600

400

200

0
0 500 1000 1500 2000 2500

-200

-400

-600

2500

2000

1500

1000

500

0
0.01 0.1 1 10 100 1000 10000 100000

4/4/2023 40
 Cell Impedance : EIS !!! Sample Names : !!!
P52 16A-3 eis1
P52 16A-1 cdfast

4/4/2023 41
4/4/2023 42
4/4/2023 43
4/4/2023 44
 Evaluation of Li anode material
for LIB
(Counter electrode is LCO)
1500 300

200

-Z" ()
Information:
1000 100
-Z'' ()

 Semi-circles in the high- and middle-frequency region reflect the

0
0 100 200 300

Z' () interfacial characteristics of the electrode

500 Before cycle
Pristine Li  Straight line in the low-frequency region represents the Warburg
Li-SiOC
Li@SiOC
0 diffusion of lithium ions in the electrochemical cells
0 500 1000 1500
Z' ()

Parameters:
 Amplitude: 7.1 mV
 Frequency: 1 mHz – 1 MHz

4/4/2023 45
 Impedance spectra

500 QSEI QDL

Pristine Si (PAA)
RE
TNM-Si-B (PAA)
400 RSEI RCT ZW TNM-Si-C (PAA)
TNM-Si-C@C (PAA)

-Z" ()
300 70

60

50

200

-Z" ()
40

30

20
100 10

0
0 10 20 30 40 50 60 70
Z' ()
0
0 100 200 300 400 500
Z' (
• RE : Resistance of the bulk electrolyte
• RSEI : the resistance for Li+ conduction in the SEI layer
• RCT : charge transfer resistance

Resistance Pristine Si TNM-Si-B TNM-Si-C TNM-Si-C@C

RE (Ω) 3.096 3.489 2.214 2.823
RSEI (Ω) 53.83 30.55 20.87 13.37
RCT (Ω) 15.71 1.712 1.517 0.41

4/4/2023 46
 6000
500 Fe2O3@Carbon
QSEI QDL
S0 (PAA) Re C(sf+ct) Cint
Porous Fe2O3
RE BSNR-1 (PAA)
R(sf+ct) Ws
400 RSEI RCT ZW BSNR-2 (PAA) 4500
BSNR-2@C(PAA)
1000

300 70

-Z" ()
Element Freedom Value Error Error %

-Z'' ()
60 750
3000 Re Free(+) 0 N/A N/A
50

200 C(sf+ct) Fixed(X) 0 N/A N/A

-Z" ()
-Z" ()
40 500
30
R(sf+ct) Fixed(X) 0 N/A N/A
20
Cint Free(+) 0 N/A N/A
250
100 10
1500 Ws-R Fixed(X) 0 N/A N/A
0
Ws-T Fixed(X) 0 N/A N/A
0
0 10 20 30 40 50 60 70
0 Ws-P
250 Fixed(X)
500 0.5
750 N/A
1000 N/A
Z' ()
0
Z' ()
0 100 200 300 400 500
0 Data File:
Z' ( 0 1500 3000 Circuit Model Fil4500
e: D:\Backup-drive\00000000\Col
6000 laboration\Gachon University collaboration\An\Impedance\Equivalent sircuit model.mdl
Mode: Run Simulation / Freq. Range (0.001 - 1000000)
Z' () Maximum Iterations: 100
Optimization Iterations: 0
Type of Fitting: Complex
Type of Weighting: Calc-Modulus

Different material has a different equivalent circuit model (ECM).

You can do a trial and error to find the best (ECM).
But, the simplest way is to find an ECM from existing paper on subject material.

4/4/2023 47
 Kesimpulan
• Kapasitas maksimum tidak menjadi penentu utama performa baterai. Crates, impedansi , life cycle
menentukan performa secara keseluruhan.

• Katoda yang bagus memiliki plateau pada rentang volt tinggi.

• Anoda yang bagus memiliki plateau pada rentang volt rendah (nearly zero is desirable)

• Koeficient difusi Lithium-ion bisa dihitung dari CV and EIS.

• CV dapat digunakan untuk menentukan tipe material elektroda.

• Puncak tajam Cv menunjukkan tipe baterai redoks (faradaic )
• Parallelogram (tanpa puncak menunjukkan material tipe capacitor (non faradaic)

• Karakteristik Equivalent circuit untuk tiap material dapat berbeda.

• Improving material diperlukan utk mendapatkan performa elektroda terbaik.

48
Terima kasih

All our dreams can come

true, if we have the
courage to pursue them
(Walt-Disney)
 Software WBCS
CV Parameter : CD Parameter : Cycle Parameter :
Design uji
Conditions rest rest
CV voltage
Current / Crates Current
Scan rates
Ch/ds High Voltage High Voltage
Switching
voltage Low voltage Low voltage
Crates
Low voltage Cycles Cycles

Cycles Rest time Rest time Rest time

50
Penjelasan Pelatihan 51
 CV Parameter : Baca *initial voltage
Implementasi :
Conditions Rancangan CV :
voltage Buka file schedule baru :
Control condition :
Scan rates Add step seperlunya.
Scan rates: 100 uV/S
Switching 1. Rest : 10 detik
voltage Voltage between : 2.5 – 4 V 2. Cndv : initial voltage
3. Vscan ( value V disamakan dg cndv, scan rates (mV/s)
Low voltage Repeat : 3 time 4. Lastvsan ( scanrates : nilai negative, value : low V)

Rest time Selesai 5. Control condition : loop type : cycle, count :3

6. Rest : 15 menit

Penjelasan Pelatihan 52
Penjelasan Pelatihan 53
 CD Parameter : Baca *initial voltage
Implementasi :
Conditions Rancangan CV :
voltage Buka file schedule baru :
Control condition :
current load Add step seperlunya.
Current : +-50, 20, 10 uA
High voltage 1. Rest : 10 detik
Voltage between : 1.7– 4 V 2. Current : -50 uA, stop at V < 1.7
Low voltage 3. Rest 10 detik
Repeat : 5 time 4. Current : 50 uA, stop at V> 4.0
Rest time 5. Control condition : loop type : cycle, count :5
Selesai 6. Ulang step 2 dengan nilai i 20 dan 10 uA.
7. Rest : 15 menit

Penjelasan Pelatihan 54
Penjelasan Pelatihan 55
 Latihan :
• Sebuah material katoda NMC akan dilakukan CV dg Batasan sbb :
• Tipe half cell.

Baca : inisial voltage

• CV menanjak dahulu kemudian menurun . Dengan laju 100 uV/s
• Batasan voltage between : 3.0 – 4.4 V
• Pengulangan 3 cycles.

Penjelasan Pelatihan 56
 Latihan …
• Sebuah material Anoda artificial graphite akan dilakukan CV dg
Batasan sbb :
• Tipe half cell.

Baca : inisial voltage

• CV menurun lalu menanjak. Dengan laju 100 uV/s
• Batasan voltage between : 0.1 – 2.2 V
• Pengulangan 3 cycles.

Penjelasan Pelatihan 57
 Latihan …
• Sebuah sel dg Anoda artificial graphite dan NMC akan dilakukan CV
dg Batasan sbb :
• Tipe full cell

Baca : inisial voltage (rendah … mV)

• CV menanjak lalu menurun. Dengan laju tiga macam: 200 (2x),120,60
uV/s
• Batasan voltage between : 2.8 – 4.15 V
• Pengulangan 1 cycles.

Penjelasan Pelatihan 58
 Latihan …
• Sebuah sel dg Anoda artificial graphite dan NMC akan dilakukan CD
dg Batasan sbb :
• Tipe full cell

Baca : inisial voltage (rendah … mV)

• Charing dahulu. Current : 500 uA, 1mA, 2mA, 5mA, 10 mA. Each 5x.
• Batasan voltage between : 2.8 – 4.15 V
• Selesai pada kondisi SoC 100%.

Penjelasan Pelatihan 59
 Latihan EIS
• Diberikan data eis sbb : buatlah equivalent circuitnya.

Ada 4 data . Masing2 perkelompok.

Penjelasan Pelatihan 60