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Perspective on Commercial Li-ion Battery Testing, Best Practices for Simple

and Effective Protocols

Article  in  Electronics · January 2020

DOI: 10.3390/electronics9010152

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Perspective

Perspective on Commercial Li-ion Battery Testing,

Best Practices for Simple and Effective Protocols
Matthieu Dubarry * and George Baure
Hawaii Natural Energy Institute, University of Hawaii, 1680 East West Road, POST 109, Honolulu, HI 96815,
USA; gbaure@hawaii.edu
* Correspondence: matthieu.dubarry@gmail.com

Received: 14 December 2019; Accepted: 8 January 2020; Published: 14 January 2020

Abstract: Validation is an integral part of any study dealing with modeling or development of new
control algorithms for lithium ion batteries. Without proper validation, the impact of a study could
be drastically reduced. In a perfect world, validation should involve testing in deployed systems,
but it is often unpractical and costly. As a result, validation is more often conducted on single cells
under control laboratory conditions. Laboratory testing is a complex task, and improper
implementation could lead to fallacious results. Although common practice in open literature, the
protocols used are usually too quickly detailed and important details are left out. This work intends
to fully describe, explain, and exemplify a simple step-by-step single apparatus methodology for
commercial battery testing in order to facilitate and standardize validation studies.

Keywords: commercial Li-ion testing; RPT; CtcV; cell-to-cell variations

1. Introduction
Today’s world relies more and more on energy storage technologies and, with several
government incentives for larger integration of zero-emission electricity storage in electromobility
and stationary applications, the demand will keep increasing in the future [1]. To match this demand,
battery technology must improve year after year. To be more than incremental, such improvement
could take the form of disruptive battery technologies [2,3] and, equally as important, the form of
improved battery management systems with innovative control strategies to enable more efficient
and safer battery packs. The latter topic is attracting enormous amount a research and a wide variety
of algorithms have been proposed in recent years [4–8] for state-of-charge (SOC) and state-of-health
(SOH) tracking. For all these studies, there is a dire need for experimental validation so that the
effectiveness of the proposed methodology can be demonstrated. This is often neglected, and some
studies, as promising as they could be, are disregarded because the work was not properly validated
in the laboratory.
Laboratory testing is an expensive and complex task, especially when trying to replicate the
behavior of large deployed battery packs such as the ones in electric vehicles or grid storage systems.
Laboratory results can become non-significant if cells are not handled and characterized properly. In
regard to characterization, laboratory testing at scale is often not possible because of logistical and
cost limitations; most of the testing must then be performed at a much smaller scale and under
slightly different conditions. This raises concerns about the presumptions that the tested cells are
representative of the batch, the duty cycle is relevant to the application, and the pack behaves
similarly to single cells at scale. To address the representativity issue, cell-to-cell variations need to
be studied and quantified. To address the relevance issue, duty cycles must be illustrative of
application data. To address the degradation and state-of-health issue, cells need to be periodically
characterized in a non-intrusive and non-destructive way.

Electronics 2020, 9, 152; doi:10.3390/electronics9010152 www.mdpi.com/journal/electronics

Electronics 2020, 9, 152 2 of 17

The purpose of this publication is to complement [9,10] and describe, in more detail than typical
publications, a testing strategy to address all these issues together. This is meant to provide
newcomers and non-battery specialists some details, definitions, and explanations on how to perform
simple and effective battery testing in order to improve validation studies. This publication does not
aim to compare different approaches to testing protocols nor discuss the complex question of battery
SOH, such discussions can be found in [9,10], respectively, but is intended to describe the Hawaii
Natural Energy Institute (HNEI) methodology. In the past decade and a half, HNEI has been in the
forefront of the development of methodologies to improve non-intrusive characterization of
commercial lithium ion cells to extract maximum relevant information from minimum amount of
testing and instrumentation. In that timeframe, we tested over 1000 commercial cells and published
upwards of 50 highly cited publications on commercial battery testing and modeling.
The HNEI testing strategy consists of five elements, Figure 1. First, a preparation step must be
executed to assure the cells are properly installed, the testers are accurately calibrated, and the
compulsory safety precautions are strictly implemented. Second, a formation protocol must be
performed to verify the cell quality relative to the batch. Third, a reference performance test (RPT)
should be completed at regular intervals to assess the evolution of battery performance over time.
Fourth, a repetitive duty cycle is required to mimic battery usage for a given application. Lastly, an
end-of-test evaluation is undertaken to provide a detailed characterization of cell performance at the
end of life, which includes a final RPT and, if deemed necessary, some post-mortem analyses [11,12].

Figure 1. Testing sequence within proposed protocols.

2. Methods and Discussion

2.1. Test Preparation

A recent study by Taylor et al. [13] showed that, without careful consideration, slight differences
in the experimental setup could induce up to 4% difference in experimental results on similar cells.
This error has environmental and procedural origins [13]. The environmental errors could stem from
the ambient temperature and humidity; the equipment calibration, accuracy, and resolution; or the
different manufacturing tolerances of the equipment and battery used. Procedural errors are induced
during the testing, and include many circumstances such as moving a sample, loosening a
connection, or not allowing batteries to acclimate to a new temperature properly [13].
Such a high error could drastically influence the conclusions of a study. Thus, steps should be
taken to minimize it. First, battery tester calibrations should be verified. Second, battery holder
contacts must be cleaned to avoid the possible impact of oxidation. Third, the placement of the
connector cables and eventual spacers must be consistent. The measurement cables must be as close
as possible to the battery tabs. In case of 4-point connection (2 for voltage, 2 for current), it is
recommended that the current and voltage cables do not touch each other [13]. Fourth, the torque on
the connections must be carefully controlled and kept constant. Taylor et al. [13] found the optimal
torque to be 12.5 Nm for their connectors. If possible, all cells belonging to one set of experiments
should be tested on the same machine and in the same temperature chamber if temperature is not a
variable. Finally, thermocouples must be added, and their placement should also be consistent (same
position, same amount of tape, etc.). With those steps, the experimental error should be limited to
below 1% [13].
Electronics 2020, 9, 152 3 of 17

Another essential aspect to take into consideration while preparing an experiment is safety. Even
if no abusive testing is performed, failure is always an option. Modern batteries pack a lot of energy
as 55Ah worth of batteries is equivalent to the energy of a hand grenade (150 g of TNT) [14]. When
first received, the batteries should be unpacked under a fume hood to prevent any exposure from
potential electrolyte leakage during transport [14]. They should then be thoroughly checked for any
physical damage, leak, or defect. Defective batteries should be disposed according to local health and
environmental safety office recommendations. For storage, batteries should be discharged a low to
mid SOCs, vacuum sealed in non-metallized plastic bag, and frozen to −27 °C in a commercial freezer.
This is because low temperatures and SOCs were shown effective to prevent impact of calendar aging
for all the major commercial Li-ion chemistries [15]. A plan should also be in place in case batteries
undergo thermal runaway during testing. A discussion on thermal runaway is out of the scope of
this publication and interested readers should refer to [16–19]. To maximize safety, all cells should be
tested in temperature chambers with significant exhaust ventilation to evacuate fumes quickly in case
of failure. Moreover, temperature should always be monitored as it is an excellent indicator of failure
[16–19]. If cell temperature exceeds 80 °C, all testing should be stopped, and the temperature
monitored closely for the next hour. Electrolyte decomposition is an exothermic reaction and if
happening, the temperature of the cell will continue to rise. Therefore, if the cell temperature returns
to room temperature quickly, the risk of dramatic failure is low. Some cooling aid could be applied
to the cells in the form of ice packs [14]. Once cooled, and as precaution, the cell should be transferred
to a sand-filled bucket [14], if possible, made of earthenware. Sand offers the advantage of acting like
a sponge for any leak of boiling electrolyte without the risk of burning or melting. The container must
be kept sealed, outdoor but protected from weather, and temperature monitored for 72 h. If the
temperature keeps increasing, the risk of failure is high. Extreme caution must be exercised as venting
or explosion is possible at any moment without notice. Standard operating procedures and proper
training should be installed to be able to handle such events quickly and safely. These procedures
could include aggressive cooling solutions such as ice packs, dry ice, and CO2 fire extinguishers and
the placement of fire blankets over the overheated cell and on the adjacent cells to prevent
propagation. Personal protective equipment such as heat resistant gloves, a fire-retardant lab-coat,
and a full-face respirator, must be used in all cases. An adapted first aid kit must also be in close
proximity [14].

2.2. Formation
Before the start of any cycle-life evaluation, it is extremely important to identify and quantify
the nature of cell-to-cell variations within a batch of cells [20–25]. A discussion on their origins is out
of the scope of this publication and interested readers should refer to an article by Rumpf et al. [26].
The results of the formation tests are not reported often enough. Several strategies are available in
the literature from C/3 discharge and 50% SOC resistance test [27] to protocols such as HNEI’s initial
conditioning characterization test (ICCT) [28–31]. Lasting less than a week, the ICCT consists only of
C/2 and C/5 cycles, Figure 2, and serves two purposes. The first is to verify that the cells are working
as they should be and that the solid electrolyte interphase layers are properly formed [32]. The second
is to calculate the three parameters that were shown to be critical in determining the manufacturing
variability in a batch of cells [28]. For the ICCT and all the other protocols in this publication, data
collection must be controlled to ensure enough information is gathered while limiting file size. We
recommend some variable time steps aiming for 2000 points per step. For the C/5 step that is
supposed to last around 5 h, 1 point should be recorded every 9 s. For the C/2 cycle, that measurement
rate is accelerated to 1 point every 3.6 s.
Electronics 2020, 9, 152 4 of 17

Figure 2. Initial conditioning characterization test (ICCT) formation test protocol.

Figure 2 details the ICCT protocol. The aim of the first step is capacity stabilization. It is
recommended to start by performing a few charge and discharge cycles (up to 6) to ensure the SEI
layer on the negative electrode is properly formed. Once the capacity is stabilized (less than 0.2%
difference between two consecutive cycles), the second step can be started. The second step consists
of C/2 (discharge in 2 h) and C/5 (discharge in 5 h) discharges with 4-h rests and the manufacturer-
recommended charging protocol.
The capacities and rest cell voltages (RCV), i.e., the voltage measured at the end of a resting
period, measured throughout this test are used to calculate the three attributes that are critical in
determining the manufacturing variability in a batch of cells. In order to fully characterize a batch of
cells, it is important to fully compare the capacity vs. rate relationship for each cell. This relationship
is not straightforward and it can be divided into 3 sections, Figure 3a.

Figure 3. (a) Capacity vs. rate relationship and (b–d) the three attributes that quantify cell-to-cell
variations.
Electronics 2020, 9, 152 5 of 17

In the first section at low rates, the capacity is constant because it is only limited by the amount
of lithium that can be exchanged. This corresponds to the cell maximum capacity and it can be
characterized by calculating the capacity ration (Qr, in mAh/% SOC, Figure 3b). The term capacity
ration refers to the capacity (Ah) obtained for each one percent of SOC. RCV measurements at the
beginning of discharge (BOD) and the end of discharge (EOD) are used to derive a SOC range by
interpolation of the maximum and minimum SOCs (e.g., 99.7%–3.2%) from an open circuit voltage
(OCV) vs. SOC curve. The capacity ration is then calculated by dividing the capacity returned during
discharge by the SOC range variation. The maximum capacity corresponds to 100 x Qr, the capacity
for 100% SOC.
In the second section at medium rates, the capacity becomes also limited by diffusion [33] and
starts decreasing with rate following a power law. This section can be characterized either by the
Peukert coefficient [34] or the rate capability (rC, Figure 3c). The Peukert coefficient [34] can be
calculated by fitting the data in the middle section to a C = Int equation where n is the Peukert
coefficient, I the current, and t the nominal discharge time for a specific C-rate. The rate capability
represents a cell’s ability to deliver capacity when the discharge rate increases. It can be calculated by
dividing the capacities at C/2 by the C/5 ones. Both parameters are unitless and, with only two rates
tested in the ICCT, rC if often more appropriate.
In the last section, at high rates, in addition to being limited by the amount of lithium and
diffusion, the capacity starts to be affected by polarization pushing some capacity outside of the
potential window. This can be characterized by measuring the ohmic resistance (R, in Ohms, Figure
3d) [28]. The ohmic resistance represents the contact resistance of the cell in the circuit and the
conductive resistance of the cell (which primarily comes from the electrolyte). Although several
methods could be used to estimate the resistance, such as electrochemical impedance spectroscopy
(EIS), the resistance estimation can be obtained simply by using the initial voltage drop associated
with the C/2 and C/5 discharges. The method is based on the linear regime of the Tafel behavior [35]
which, for small currents, shares some formal similarity with Ohm’s law. Figure 4a presents the
calculation process that was described previously in [36]. If the cells were previously charged to the
exact same SOC prior to the C/5 and C/2 discharges, i.e., that the RCVs were similar, the initial IR
drop can be used to determine the resistance. To calculate the resistance, the measured voltage must
be plotted as a function of rate or current. The slope of the curve is the resistance, normalized or not.
It must be noted that if the data are gathered at different time steps for different rates, priority must
be set on selecting points with similar elapsed time after the application of current. This approach is
also valid to characterize the resistance evolution with temperature and aging.
Once the three attributes are calculated for all the cells in a batch, the statistical analysis of the
cell-to-cell variations can be performed, and the normality of the three attributes examined. A
convenient way to report the data is to represent all three attributes in a 3D space of which an example
is presented in Figure 4b. To help visualize the cell-to-cell variations better, a couple of visual cues
can be added to the plot. First, a full-line rectangle, in which the boundaries correspond to the lower
and upper quartiles (i.e., the 75th and 25th percentiles of the data) for the three attributes of cell-to-
cell variations. Cells located within this rectangle, color-coded in blue, are the closest to batch center
of gravity (the median values for all three attributes) and can be considered the core of the batch. A
second dotted rectangle, three times larger than the first one, was also added. Three times the
interquartile range is often statistically considered as the outliers’ boundaries. Cells located outside
of the outliers’ boundaries were color-coded in red and are excluded from further experimentation.
In the example shown in Figure 4b, most cells were consistent. However, there were three cells that
exhibited resistances higher than normal and, therefore, their use should be discontinued.
Electronics 2020, 9, 152 6 of 17

Figure 4. (a) Initial voltage vs. rate for the resistance calculation and (b) cell-to-cell variation
representation in a 3D space adapted from [29].

2.3. Reference Performance Test

The RPT needs to be performed on a regular interval and at a constant temperature, typically
monthly or every 100 full equivalent cycles and at room temperature, to quantitatively assess battery
performance and SOH. SOH is gauged from the quantification of the degradation modes, the loss of
active material, loss of reactant, and kinetic degradation. A discussion on SOH is out of the scope of
this paper and can be found in [10]. The RPT needs to provide as much information as possible on
SOH without being intrusive [37]. Therefore, the test must be short and not stress the cells, but it
needs to characterize the thermodynamic and kinetic changes. The proposed HNEI RPT protocol is
detailed in Figure 5. It consists of three steps: Conditioning, low-rate cycling, and nominal rate
cycling. The conditioning step ensures that the cells are fully charged before the start of the low-rate
cycle. This is accomplished by performing a standard charge with an additional constant current step
typically at C/50 (discharge in 50 h). The second step is a low-rate cycle, typically C/25 (discharge in
25 h) to assess thermodynamic aspects. The third step is a nominal rate cycle, typically C/2 (discharge
in 2 h) to assess kinetic aspects. Rate for this step can be adapted to the situation. For example, higher
rates can be applied for high-power cells; while lower rates are used for high-energy cells. The caveat
being that this rate must be less aggressive than the rate used in the duty cycling. The RPT protocol
is limited to two cycles to minimize its toll on the cell SOH but additional rates or procedures
(constant power, electrochemical impedance spectroscopy, full OCV vs. SOC test, different
temperatures) [27,38,39] could be added if necessary. This is often done in the literature for the first
RPT only. All regimes are performed at constant current up to the cutoff voltage with the addition of
a residual capacity step at C/50 in between two rests. This residual capacity step is primarily used to
assure that both charges and discharges start from the same SOC independently of the previous rate.
It is also used to calculate the maximum capacity the cell can deliver.
The data gathered during the RPT test allow the execution of several analyses. First, the same
calculation as that of the ICCT test can be undertaken, specifically, the capacity ration, rate capability,
and resistance can be measured. The main difference is that in this case, the capacity ration can be
deciphered directly by adding the capacity measured during the residual capacity measurements at
C/50 to the recorded capacities to obtain the cell maximum capacity to be divided by 100. Values
calculated for the two rates should be similar and close to the one inferred during the ICCT test. With
only two rates tested during the proposed RPT, the rC method is still recommended over the Peukert
method to characterize rate capability. If more rates are tested, the Peukert curve (capacity vs. rate)
could be used as long as the rates are within the section with diffusion limitation (Figure 3a).
Electronics 2020, 9, 152 7 of 17

Figure 5. The reference performance test (RPT) test protocol. EoR stands for end of regime and BoR
stands for beginning of regime.

The second set of information to be gathered from the RPT is the OCV vs. SOC relationship at
the current SOH. A discussion on OCV is out of the scope of this paper and can be found in [9,40].
The OCV vs. SOC relationship can vary a lot with aging and, since gathering a proper OCV vs. SOC
curve can take weeks of testing [9], it is not feasible to repeat the process on every cell at each RPT. A
solution is to calculate a pseudo-OCV curve at each RPT. It has to be stated that, as discussed in [9],
a low-rate charge or discharge cannot be considered as OCV or pseudo-OCV curves as they are not
independent of the regime. The pseudo-OCV curve can be calculated by averaging the low-rate
charge and discharge curves [9,41,42]. This method is usually accurate, but it is highly recommended
to check the validity of the results. First, the residual capacity measurements for the low-rate cycle
must be small, <1% of the maximum capacity. High residual capacity measurement for the low-rate
cycles would suggest that some SOC was not utilized during the low-rate cycles. If so, no data for
this additional capacity were gathered and thus the corresponding OCV voltage cannot be assessed
[31]. In such occurrence, it is recommended to lower the current of the low-rate cycle and of the
residual capacity cycle. The second verification is to compare the SOC obtained by reporting the
RCVs from both cycles on the pseudo-OCV curve with the SOC calculated from the residual capacity
measurements divided by the maximum capacity. The values should be similar.
Using the SOC calculated at end of charge and end of discharge (either from the residual capacity
measurements or the pseudo-OCV curve), the SOC windows used by the different rates can be
compared and tracked [43] so that differences between rates, temperature, or SOH can be compared
and discussed. An increasing difference between low and high rate implies growing kinetic
limitations. A decreasing difference is possible in case of electrochemical milling enhancing the
surface area of the electrode [44]. This allows the comparison of SOC (the percentage of the maximum
lithiation) and the depth-of-discharge (DOD, the percentage of the maximum lithiation under a given
duty cycle) [9]. For the data collected during the RPT protocol, each charge or discharge corresponds
to 100% DOD since the cells were fully charged or discharged prior to the start of the next regime.
More details on the extremely important question of SOC definition can be found in [9].
Electronics 2020, 9, 152 8 of 17

An example of the pseudo-OCV calculation and validation is presented in Figure 6 for a

commercial graphite/nickel aluminum cobalt oxide cell. The residual capacities were below 0.5% of
the maximum capacity, consequently the pseudo-OCV curve was calculated. This pseudo-OCV curve
was then used to infer the SOC from the RCV. For both cycles, the estimated SOCs were within 0.5%
from the residual capacity measurements (highlighted by the vertical bars). In that case, the pseudo-
OCV curve could be deemed accurate enough for use. From the SOC windows, 100% DOD at C/25
corresponds to 99.5% SOC versus 95% SOC in discharge and 90% SOC in charge at C/3. Examples of
results obtainable from these analyses can be found in our previous work including the SOC range
variation with rate [43] and the RCV and OCV evolution upon aging [45], at different temperatures
[46], and for different electrode architectures [44].

Figure 6. The C/25 charge and discharge curves and associated pseudo-open circuit voltage (OCV)
curve. Black squares and blue circles indicate the state-of-charge (SOC) estimated from C/3 and C/25
rest cell voltages, respectively. Vertical lines indicate the amount of additional capacity added by the
residual capacity steps.

The third set of information that can be gathered from the RPT is the voltage vs. capacity curves
of the low and high-rate cycles. The low-rate cycle provides thermodynamic information; while the
high-rate cycle reveals kinetic information. Since voltage variations are minute, derivatives are
recommended, either incremental capacity (IC, dQ/dV = f(V)) [9,42,45,47–49] or differential voltage
(DV, dV/dQ = f(Q)) [50–52]. Interested readers should refer to [9] for a complete discussion of the
advantages and disadvantages of both these electrochemical voltage spectroscopies (EVS).
As mentioned in [9], there are two levels of analysis for the EVS curves. The qualitative way is
the easiest and involves comparing the curves. Different features of interest (FOI) [53] (Figure 7a) can
be discussed and characterized without a complete understanding of the underlying electrochemical
process. To properly discuss changes, it is extremely important to describe the peaks properly (Figure
7b). By convention, for IC, discharge peaks are negative and charge peaks are positive. The peak
potential is measured at the base of the peak and not at maximum intensity. Each peak corresponds
to a thermodynamic property, a redox reaction, and thus the potential of the reaction is the same in
charge and discharge. The voltage of the maximum of intensity could be affected by hysteresis [54],
polarization, and kinetics [55]. For example, if a peak is broadening, the position of the intensity
maximum changes, whereas the underlying reaction is still the same and thus starts at the same
potential, Figure 7b. In that case, the slope of the front of the peak would be an interesting FOI to
characterize kinetic changes. Another example is the shifting of all the peaks towards lower potential
during discharge, which is usually a clear indication that the resistance is increasing (not observable
on DV curves [9]). The resolution needed for IC and DV curves depends on the chemistry. Following
common practices from X-ray diffraction studies, having 5 or 6 points above the half-width of the
thinner peak would be considered sufficient resolution to trust peak intensity and position.
Furthermore, 1 mV or 2 mV voltage steps usually provide good enough resolution for single cells,
but this depends on chemistry and on the quality of the data. If noise filtering techniques are applied
to clean the curves, particular attention must be set on possible peak displacements.
Electronics 2020, 9, 152 9 of 17

Figure 7. (a) Feature of interest (adapted from [53]) and (b) incremental capacity (IC) peak
description.

In addition to the traditional IC and DV analysis, with the same dataset, other voltage derivative
techniques can be useful in the study of relaxation curves and the temperature variations. Analysis
of dV/dt = f(t) plots have shown the potential to identify lithium plating from relaxation curves [56].
Differential temperature curves with respect to voltage (dT/dV = f(V)) can also provide additional
information on degradation mechanisms [57].
The quantitative analysis is much more complex, but it determines the magnitudes of the
degradation modes such as loss of active material, loss of reactant, and kinetic degradation [55,58,59].
The methodology concerning the interpretation of the incremental capacity curves is out of the scope
of this paper and was extensively described in previous publications [9,58,59] with the introduction
of the clepsydra analogy that visualized the problem as communicating vessels with the liquid
representing the lithium in the system and the shapes of the vessels defined by the derivative of the
voltage responses for both electrodes (Figure 8a). This step can be bypassed by using one of the
publicly available mechanistic models [59–61] that relies on electrode half-cell data to build a virtual
replicate and emulate the impact of all degradation mechanisms based on simple parameters such as
the loading ratio (LR) between the capacities of the positive and negative electrodes and their offset
(OFS), Figure 8b. Every degradation induces changes to LR and OFS, Figure 8c, and those changes
can be related to the degradation modes via a simple set of equations [59].
The typical way of performing the analysis of IC or DV curves is to first select some FOIs [53,62],
then compare their experimental evolution to predicted ones for individual degradation modes, and
finally validate by simulating the full degradation to match the entire voltage response of the cell.
The full match might only be possible with the exact same positive and negative electrodes as the
ones used in the considered cells. For this reason, we recommend harvesting electrodes from one cell
and test them versus a reference electrode to later be used in the mechanistic model. Discussion on
how to open commercial cells and perform half-cell testing is out of the scope of this paper and more
details can be found in [29,63–69]. Individual electrodes in half-cell should be tested with an RPT
protocol similar to the one presented in Figure 5 but with more rates ranging from twice as low to
twice as fast to enable simulation of loss of active material and kinetic changes [55]. Since only one
RPT is performed on the half-cells and the capacity at each rate is normalized from the RCVs, the
residual capacity measurements and the OCV curve, degradation between cycles is not an issue.
Thus, increasing the number of rates tested improves the accuracy of the simulations. However, some
attention needs to be spent on the procedure to minimize cell-to-cell variations and improve the
agreement of the data from the half-cells and the full cell [66]. With one RPT for the full cell and one
RPT for each electrode, enough information is available to build a virtual cell and use the mechanistic
modeling tools. If one of the electrodes is a blend of several active materials, the best results will be
obtained if half-cell data are available for each individual electrode component. If the cells cannot be
opened, or if individual components of blended electrodes cannot be gathered, the same analysis can
be done using reference materials [70]. However, in that case, only trends can be used to compare the
mechanistic simulations to the experimental data.
Electronics 2020, 9, 152 10 of 17

Figure 8. (a) Clepsydra analogy, (b) parameterization for mechanistic modeling, and (c) the effect of
changes of loading ratio and electrode offset.

For analysis, the FOI selection must only be made after an exhaustive sensibility analysis [10,53].
It is highly recommended to first simulate a degradation map with the voltage changes and capacity
loss associated with all the individual modes to gain an understanding of which FOI is more sensible
to a degradation mode. Logical deductions from this degradation map usually allow the direct
estimation of at least one of the degradation modes. With one quantified, another is then usually
unambiguously decipherable and so on until only one is remaining. Quantifying the last degradation
mode directly is usually not possible because of combined effects with the others. This quantification
usually necessitates a full fit match. This could be achieved through an automated calculation. Some
algorithms were proposed in the literature based on FOIs but most of them neglected the proper
sensibility analysis and hence should not be trusted to be universal. A detailed discussion on the
necessity for sensibility analysis is presented in [53]. Among the others, examples of degradation
maps can be found in [71] for graphite//nickel cobalt aluminum oxide cells, in [53,59] for
graphite//lithium iron phosphate cells, and in [53,72] for lithium titanate oxide//manganese nickel
cobalt oxide. Example of studies with blended electrodes can be found in [70,73]. In our past IC
studies [44,53,59,65,70–75], we often used different FOIs and entry points for the IC analysis
depending on the chemistry and the experimental trends. This highlights that a step-by-step
instruction list on how to perform the analysis is not possible and that it should always be guided by
a sensibility analysis to be repeated for every new study. It must be noted that IC or DV analysis are
usually chemistry specific and, as such, results should never be extrapolated to other chemistries
without careful considerations and verifications.

2.4. Duty Cycle

The definition of the duty cycle test is the most important part of any degradation or validation
study. Battery degradation is path dependent [10,74,76–80] meaning that different conditions are
degrading battery differently, not just increasing or decreasing the rate. Therefore, to be
representative of a given application, the duty cycle to be applied needs to be as close as possible to
the real use, which is most likely stochastic [74,76–80]. Depending on the cells, some cycling profiles
could be surprisingly harsh. For example, our fast charging studies showed no impact of 4C constant-
current discharges compared to 1C but fast degradation under EV type pulsing discharges in which
the average current was around C/3 and the maximum current 4C [10,65,75]. This stresses that
significant time needs to be allocated to properly define the duty cycle based on the targeted
application. If datasets are available, fuzzy logic [81] and statistical analysis [82] are good options to
Electronics 2020, 9, 152 11 of 17

define a representative usage cycle. Alternatively, literature might suggest adapted duty cycles,
although they might not be fully representative [74].
Even if a representative usage is determined, real-life conditions can fluctuate significantly.
Therefore, it might be valuable to test conditions around the representative usage to look for optimal
or detrimental conditions for performance or durability. Testing every possible condition is not
possible. Fortunately, some statistical tools allow the sampling of a wide range of values for
meaningful parameters with an optimal number of experiments. This is called design of experiments
and it is effective in battery testing. Interested readers are referred to [83–86] for more details on how
to set them up and how to interpret the results. Such a methodology was already proposed and
successfully applied to battery testing in recent years [30,87–92].
The duty cycle is the center part of any study. The RPT will help diagnosis and enable prognosis
on the cells but these results need to be relevant to different duty cycles. With a well-defined testing
plan, some statistical analyses, such as the analysis of variance (ANOVA), can be executed to establish
the significance of the different factors in the duty cycle (e.g., current, depth of discharge, and
temperature). An example of significance analysis from [70] is presented in Figure 9. It shows the
relative significance of the different factors: The SOC swings, the rate, and the temperature on the
different degradation modes. Such results can then be used to derive the optimal conditions to limit
capacity loss or the effectiveness of a given control algorithm.

Figure 9. Example of a significance analysis taken from [70].

For studies focused on long-term ramifications, it is important to quantify the intrinsic variability
in cycle aging and calendar aging, in other words, how much difference is observed between several
cells performing the exact same duty cycle. Several studies reported a noticeable spread in cycle-lives
[20,23,31,93,94] that could be detrimental to the durability of battery packs. Moreover, as discussed
in [10], for the deployment of algorithms, validation on one duty cycle is not enough. The entirety of
the degradation paths should be tested. If this is not possible experimentally, modeling solutions
should be considered [10,95,96]. In some cases, the capacity is shown to be increased after performing
an RPT compared to the last cycles before the RPT. This could be associated with negative electrode
overhang [97,98] and its impact will usually fade away after a few cycles.

2.5. Post-Mortem
If necessary, and to validate the diagnosis gathered from the analysis of the RPT, some post-
mortem tests can be carried out. This will require multiple apparatus and thus details are out of the
scope of this publication. The range of post-mortem tests proposed in the literature is wide [11,12,99]
and some techniques might require a lot of resources. They are typically performed by opening the
aged cells to test individual electrodes but some can be performed on full cells [11]. Electrochemical
tests on aged electrodes can verify changes in OFS and LR and validate the loss of reactant and loss
of active material quantifications [64] and other tests can be used to discover the origin of the losses.
Electronics 2020, 9, 152 12 of 17

3. Conclusions
In summary, laboratory battery testing is a much more complex task than it appears. Properly
defined and executed plans expedites a deeper understanding of the performance and SOH of
commercial batteries. Inadequate validation can delegitimize a good study. This paper presents best
practices for simple and effective testing of batteries. For the most part, execution only requires a
multichannel potentiostat/galvanostat without the need for other complex instrumentation. This will
allow characterization of not only the cell-to-cell variations, but also evolution of SOH throughout
the lifetime of the cells. Although this publication was centered on single cell testing, the same
approach can also be used for modules or packs if safety controls are in place so that no single cell
can be overcharged or overdischarged.

Author Contributions: Conceptualization, M.D.; methodology, M.D.; software, M.D.; validation, M.D. and G.B.;
formal analysis, M.D. and G.B.; resources, M.D.; data curation, M.D.; writing—original draft preparation, M.D.;
writing—review and editing, M.D. and G.B.; visualization, M.D.; supervision, M.D.; project administration,
M.D.; funding acquisition, M.D. All authors have read and agreed to the published version of the manuscript.

Funding: This work was funded by ONR Asia Pacific Research Initiative for Sustainable Energy Systems
(APRISES), award number N00014-18-1-2127. M.D. is also supported by the State of Hawaii.

Acknowledgments: The authors are thankful to all the past staff that helped define and affine these protocols,
most notably Bor Yann Liaw, Cyril Truchot, and Arnaud Devie. M.D. would also like to thank the University of
Hawaii Material Science Consortium for Research and Education for advanced material characterizations.

Conflicts of Interest: The authors declare no conflict of interest.

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