Battery task (Lab 2)
By: Carta Danilo
We have the EIS data after every 50 cycles for two Li-ion batteries, with NMC cathode. One of them
has a slightly calendared cathode of 40 % porosity, and the other is calendared more to 30% porosity.
Q1: - Identify which EIS spectra belong to which samples.
In the plots below, the data for sample 1 and sample 2 are consistently plotted for cycles 0, 100, and
200. I have opted to perform this analysis at these specific cycles. Upon examining the plots,
particularly the Nyquist plot, it is evident that sample 1 consistently begins with a higher impedance
than sample 2. This indicates that sample 2 possesses a lower impedance than sample 1.
Furthermore, sample 2 consistently exhibits lower impedance magnitudes across all frequencies in
the Bode plot, characteristic of enhanced ion accessibility in structures with higher porosity.
The phase angles at lower frequencies for sample 2 further affirm the hypothesis of increased
porosity, implying altered kinetic processes associated with a larger electroactive surface area. Based
on the Electrochemical Impedance Spectroscopy (EIS) spectra during cycle 0, it is reasonable to assert
that sample 2 corresponds to the battery with a cathode featuring 40% porosity, while sample 1
corresponds to the cathode with 30% porosity.
As the cycling progresses, the discernibility of differences becomes increasingly pronounced. Sample
2 consistently exhibits a heightened slope in the Nyquist diagram, coupled with consistently lower
impedance values and increasing phase angles at lower frequencies.
The decrease in impedance values and the evolution of the Nyquist diagram for Sample 2 suggest
potential structural alterations within the cathode throughout the cycling process, aligning with the
anticipated behavior of electrodes with higher porosity. Therefore, the identification of Sample 2 as
the battery with the cathode featuring 40% porosity is substantiated by the Electrochemical
Impedance Spectroscopy (EIS) spectra at cycle 100.
The latest plots for cycle 200 of both samples further illuminate our initial hypotheses. In summary,
the discernible characteristics observed in the Nyquist and Bode plots, during cycles 0, 100, and 200,
provide a robust foundation for identifying Sample 2 as the Li-ion battery with the cathode featuring
40% porosity, while Sample 1 corresponds to the cathode with 30% porosity.
Q2: - Identify which part of spectra belong to ohmic resistance,
contact resistance, charge transfer resistance and diffusion resistance.
Part 1: Ohmic Resistance (R_s): Ohmic
resistance represents the resistance
associated with the electrolyte and any
conductive elements outside the
electrochemical cell. In EIS spectra, it is
typically observed at high frequencies (to
the left on the Nyquist plot) and appears as
a near-vertical line.
Part 2: Contact Resistance (R_ct): Contact
resistance arises from imperfect electrical
contact at the interfaces within the cell,
such as electrode/electrolyte interfaces. It
is often represented by a semicircle in the
mid-frequency range on the Nyquist plot.
Part 3: Charge Transfer Resistance (R_ct): Charge transfer resistance is associated with the kinetics of
electrochemical reactions occurring at the electrode surfaces. It is associated with the movement of
ions between the electrode and electrolyte during the charging and discharging processes.
(also represented by a semicircle on the Nyquist plot, typically at intermediate frequencies)
Part 4: Diffusion Resistance (Warburg Element): Diffusion resistance is related to mass transport
limitations, and it is often observed as a sloping line at lower frequencies on the Nyquist plot. It can
be represented by a Warburg element, which is a diagonal line with a 45-degree slope.
Q3: Degradation of Li-ion battery cathode follows different path: surface degradation of cathode
materials, electrolyte dry out, fracture of active material, electrode delamination, pore clogging,
carbon-binder contact loss with active material, etc. Fit the impedance spectra evolution during the
Charge transfer and 𝜎𝑤). Plot them vs cycle number and discuss the results considering possible
200 cycles to an equivalent circuit model and find the different resistances (R ohmic, R contact, R
graph. Do the same for R contact, R Charge transfer and 𝜎𝑤 ….in total there should be 4 graphs)
degradation phenomenon. (e.g. plot R ohmic vs cycle number for both S1 and S2 samples in one
Sample 1 Sample 2
18
16
14
12
Rohmic [Ω]
10
8
6
4
2
0
0 50 100 150 200
Cycle number
Sample 1: shows a slight decrease in ohmic resistance over the first 100 cycles, followed by a smalle
increase at 150 cycles.
Sample 2: Shows an consistent increase in ohmic resistance with every cycling step
Conclusion: Sample 1 maintain lower ohmic resistance then sample 2.
The consistent increase in ohmic resistance for Sample 2 indicates a degradation trend. Over cycling,
some increase in resistance is normal due to factors like electrode/electrolyte interface changes and
material degradation. However, excessive or rapid increases may indicate accelerated degradation.
Sample 1 Sample 2
25
20
15
Rcontact [Ω]
10
0
0 50 100 150 200
Cycle number
The graph above illustrates R contact (Contact Resistance) as a function of cycle number for both
samples.
For both samples, there is a clear increasing trend in contact resistance over the provided data points.
The increase in contact resistance over the provided data points for both samples suggests that there
may be issues with the interfaces or contacts within the battery. This could be due to factors such as
degradation of materials, formation of resistive layers, or other interface-related issues.
Sample 2 consistently having lower contact resistance than Sample 1 might indicate that Sample 2
has better-performing interfaces or more stable contacts.
Sample 1 Sample 2
120
100
Rcharge transfer [Ω]
80
60
40
20
0
0 50 100 150 200
Cycle number
Graph three focuses on R Charge transfer (Charge Transfer Resistance) against cycle number for both
S1 and S2 samples.
For both Sample 1 and Sample 2, there is variability in the ohmic charge transfer resistance values.
It's essential to assess trends and patterns over the provided data points. Sample 2 generally has
lower ohmic charge transfer resistance compared to Sample 1 at each data point.
Lower ohmic charge transfer resistance values suggest better charge transfer efficiency at the
electrode-electrolyte interface. Sample 2 appears to have more efficient charge transfer compared to
Sample 1. Variability over cycles may indicate changes in the electrochemical interfaces.
Ohmic charge transfer resistance is influenced by the characteristics of the electrode-electrolyte
interface. Changes in this resistance can be linked to degradation at the interface.
Sample 1 Sample 2
10
9
σw [Ω/√s]
6
0 50 100 150 200
Cycle number
The fourth graph shows 𝜎𝑤 (Warburg Impedance) in function of cycle number, providing insights
into the diffusion-controlled processes within the battery.
Warburg impedance values typically reflect the diffusion characteristics of ions in the electrolyte.
Higher Warburg impedance values may indicate slower diffusion processes. Lower values may suggest
more efficient ion diffusion in Sample 2 compared to Sample 1.
The Warburg impedance is influenced by the properties of the electrolyte. Changes in electrolyte
composition or characteristics can affect these values. Temperature can influence ion diffusion.
Ensure that the measurements are conducted under consistent temperature conditions.
