Letter

http://pubs.acs.org/journal/aelccp

Massively Distributed Bayesian Analysis of

Electric Aircraft Battery Degradation
Alexander Bills, Leif Fredericks, Valentin Sulzer, and Venkatasubramanian Viswanathan*
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ABSTRACT: Electric vertical takeoff and landing (EVTOL) aircraft have

high power and energy requirements that must be understood throughout
their batteries’ life. Using a fast electrochemical model and high throughput
Downloaded via 103.18.0.19 on February 25, 2024 at 04:37:18 (UTC).

computing, we independently and simultaneously sample the degradation

modes for 21392 cycles of an EVTOL aircraft battery data set, obtaining a
posterior probability distribution for each degradation mode throughout
the life of the aircraft. The model shows a median error of 32.5 mV (or
1.9%) across all cycles. We conduct an identifiability analysis on the
generated mode distributions. We analyze correlations between the modes
and cycling characteristics, finding that depth of discharge, temperature,
and charging current all have significant impacts on degradation. We
introduce a protocol for early identification of active degradation
mechanisms, identifying electrolyte oxidation, active material dissolution,
and growth of a solid−electrolyte interphase as the most likely causes of battery degradation. Finally, we discuss other
applications of large-scale sampling of battery degradation modes.

M aintaining a high cycle life for lithium-ion batteries

reduces their total lifetime cost and environmental
impacts, especially given recent supply chain
disruptions and the scarcity of certain metals required to
build batteries.1 For electric vertical takeoff and landing
(EVTOL) aircraft operators, it is imperative to have a deep
understanding of the remaining useful power of the battery to
ensure safe completion of a mission, meaning both impedance
and capacity must be known.2,3 Battery degradation has many
possible causes, including growth of a solid−electrolyte
interphase (SEI) (potentially enhanced by surface crack-
ing),4−7 loss of active material due to dissolution,8 particle
cracking due to intercalation-induced volume changes,9−11 and
others. These mechanisms can interact, leading to so-called
kneepoints or accelerated aging.12−16
Battery degradation mechanisms result in battery degrada-
tion modes, defined as quantities which change over the life of
the battery and result in degraded performance. Most previous
work on degradation modes primarily considers loss of positive
electrode active material (LAMPE), loss of negative electrode
active material (LAMNE), and loss of lithium inventory
(LLI).15,17 However, for EVTOL aircraft, impedance rise is
as important as capacity fade for the safe completion of the
mission.2,3 Therefore, we choose a more comprehensive set of
modes, including moles of lithium (nLi), positive and negative
electrode active material volume fraction (ϵ+,− s ), positive and
negative electrode porosity (ϵ+,−
e ), and ohmic resistance (ω).
© 2023 The Authors. Published by
American Chemical Society
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Most mechanisms of battery degradation primarily affect one
or more of these parameters, and these parameters could be
directly measured experimentally via a postmortem destructive
physical analysis (though doing so is out of the scope of this
letter).14,16 We note that the methodology developed in this
work could be used for other sets of degradation modes.
These degradation modes can be estimated by specialized
electrochemical tests. LAMPE and LAMNE can be quantified by
analyzing the derivative of voltage with respect to capacity (dV
dQ).17−20 This method requires high quality open circuit
voltage (OCV) measurements collected at low current rates
(though voltage relaxation has also been used21) and is unable
to obtain degradation modes that primarily affect transport and
kinetics. Electrochemical impedance spectroscopy (EIS) can
be used to diagnose impedance-related degradation modes for
cells22−25 and packs,26 and others have combined EIS and
OCV measurements.27,28 However, both of these tests require
specialized hardware and long periods in which the battery
cannot be used. Specifically, measurement of the OCV will
require a minimum of 5 h of inactivity.
Received: June 19, 2023
Accepted: July 25, 2023
Published: July 31, 2023
https://doi.org/10.1021/acsenergylett.3c01216
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ACS Energy Letters http://pubs.acs.org/journal/aelccp
Figure 1. (a−e) Voltage vs time for 5 cycles over the life of the aircraft, showing a comparison of the model and data. Each subplot shows
1000 gray (model) trajectories. (f) Cumulative density of the model root mean squared error. (g) Histogram of the model root mean
squared error.
In contrast, Bayesian sampling of electrochemical model
parameters to track degradation modes requires no specialized
hardware and can be used on a standard duty cycle, eliminating
the need for inactivity. Bayesian sampling adds an under-
standing of the identifiability of the model parameters and
estimates of uncertainty, which are crucial given the known
lack of identifiability of electrochemical model parameters.29,30
Such a system is a critical enabling component of a digital twin
of a battery pack.9,31−33
While previous studies have estimated battery degradation
modes,34−38 none have been conducted at the scales required
to undertake analysis of causes and mechanisms of changes in
those modes or to provide real-time updates sufficient to safely
operate electric aircraft. We mitigate the computational cost of
this analysis by employing high throughput computing (HTC),
defined as the parallel execution of many computations in
parallel with minimal or no communication. Each cycle can be
independently sampled in parallel, leveraging the power
provided by large distributed computing networks such as
the open science grid or modern cloud computing systems.39,40
We have automated the method, forging a path toward an
industrial-scale cloud-based digital twin of a battery.9,31,33
Since there is no interaction required between the analyses, the
amount of cycles that can be simultaneously analyzed via this
method is limited only by the number of available computers
and cycles (see Supporting Information Figures S13 and S14).
In a previous work, we collected the largest publicly available
data set of EVTOL aircraft batteries.41 It contains cycling data
for 22 cylindrical cells of 18650 form factor, cycled with a load
profile representative of the conditions an EVTOL aircraft
battery would experience in operation, totaling 21392 cycles.
The cells are Sony VTC-6s, comprised of an NCA (nickel−
cobalt−aluminum oxide) positive electrode and a graphite−
silicon oxide negative electrode.41,42 Each mission cycle
features a takeoff, cruise, and landing phase defined by a
constant power discharge for a specified time. Following a rest
period, the cell is charged at constant current and then
constant voltage (CCCV). Voltage, current, and temperature
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are measured. The mission profile is repeated (with capacity
tests every 50 cycles) until it reaches 2.5 V or 70 °C during any
mission cycle. Power, mission length, ambient temperature,
charge current, and end of charge voltage are each varied one-
at-a-time (see Tables S1 and S2 and ref 41).
Herein, we use Bayesian sampling techniques to sample the
distribution of degradation modes for the EVTOL aircraft
battery data set. We analyze the identifiability of the
degradation modes, finding that resistance and LAM in each
electrode are identifiable. We analyze the correlation of the
mode changes with cycling conditions, finding that the rate of
LAMPE is most strongly correlated with maximum charging
current (ρ = 0.5), the rate of LAMNE is most strongly
correlated with depth of discharge (DOD; ρ = −0.422), and
resistance is most strongly correlated with DOD (ρ = 0.433)
(where ρ is the Pearson correlation coefficient). Finally, we
introduce a protocol for early identification of active
degradation mechanisms and use it to identify electrolyte
oxidation and active material dissolution as the most likely
causes of positive electrode degradation and SEI growth as the
most likely cause of negative electrode degradation. We
conclude with a discussion of potential further applications of
this work.
The model used for parameter inference must be computa-
tionally cheap and contain an adequate representation of the
physics of battery degradation. Electrolytic effects are
important due to the high rates of discharge required for
takeoff and landing.2,3,43,44 The model we use in this work
represents a simplified version of the model developed by
Doyle et al.43−45 The solid diffusion for each particle has been
discretized into two finite volumes: bulk and surface. The
electrolyte has been discretized into three finite volumes:
negative electrode, separator, and positive electrode. This
model can simulate a standard EVTOL flight profile in 385 μs
(see Figures S11 and S12). We impose the temperature as
collected in the data set onto the model (varying it with time at
the same sampling rate as the data). The model is described in
more detail in the Supporting Information (SI).
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Figure 2. Two-dimensional hexagonal histograms of the posterior distribution of each parameter as a function of cycle life. From top to
bottom, resistance, negative electrode porosity, positive electrode porosity, fraction of solid in active material, moles of lithium, negative
electrode volume fraction in active material, and positive electrode fraction in active material. For presentation, only bins with a count of 10
or more are shown. The top 5 parameters are used to calculate the bottom 3.
Rather than directly estimating ϵ+,− +,−
s , we sample ϵe and the
fraction of solid which is available for intercalation (f +,−
s ). This
parametrization has the advantage of independence: physical
constraints can easily be placed on the parameters by imposing
uniform priors: f +,−
s and ϵ+,−
e must be greater than 0 and less
than or equal to 1. We calculate LAMPE, LAMNE, and LLI as a
function of each of these parameters (see eqs S16 and S17 in
the SI). The distributions are sampled using the No-U-Turn
sampler (NUTS), an extension of Hamiltonian Monte Carlo
(HMC),46,47 with an acceptance rate of 0.65, and the code is
implemented in the Julia programming language using the
Turing probabilistic programming library.48,49 More details of
the sampler are available in the SI.
Panels a−e of Figure 1 show a comparison of the model and
data for cell VAH01 (VAH abbreviates Vahana and serves as
the prefix to the cell serial number) at 5 cycles over the life of
VAH01. Each pane shows 1000 model trajectories, corre-
sponding to the 1000 samples following the burn-in period of
the sampler. Convergence plots for each of these cycles are
available in Figures S3−S7, along with convergence statistics in
Table S4. Overall, the model demonstrates good agreement
with the data. Figure 1f is a cumulative distribution function of
the root mean squared error (RMSE) for all of the cycles in the
data set, and Figure 1g shows a histogram of the same data,
both plotted with a logarithmic x-axis. Nearly all (>99.9%) of
the cycles have an RMSE of less than 50 mV, and the median
error is 32.5 mV (or 1.9%). More detailed comparisons
between our data and experiments can be found in the SI.
Figure 2 shows two-dimensional histograms of the posterior
distribution of each parameter, with the parameter on the y-
axis and cycle on the x-axis for 6 cells (the remainder are
available in Figure S15). For all cells, ω shows a well-bounded
distribution with an increasing mean, starting around 0.02 Ω
and rising to above 0.04 Ω by the end of life. In a few cells,
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such as VAH30, the rate of change of ω appears to slow at the
end of life, while, in others, such as VAH05 it seems to be
relatively constant.
The negative electrode porosity, ϵ−e is roughly constant, with
a mean of around 0.29. Porosity changes the volume fraction of
the solid (1 − ϵ−e ), requiring an inverse change in f−s to
maintain the same ϵ−s , and changes the effective electrolyte
diffusion coefficient and conductivity due to the Bruggeman
relation (Xeff = X0ϵβ), where X is replaced by the variable of
interest.
The effects of dropping f−s dominate the effects of constant
porosity, resulting in the overall LAMNE (a mechanistic
explanation for this could be electrolyte dry-out, which
would cause loss of active material without changes in
porosity, as some pores would simply be depleted of
electrolyte50). In most cells, the change in ϵ−s appears to
accelerate later in life. Two cells (VAH11 and VAH12) display
a bimodal distribution for ϵ−s . These cells have a low DOD
(Table S2), indicating that a high DOD improves parameter
identifiability.
The positive electrode porosity, ϵ+e , and the variances of ϵ+e
and fs+ remain relatively constant. While ϵe+ increases, fs+
decreases, resulting in decreasing ϵ+s for all cells. LAMNE and
LAMPE each have three primary effects: capacity loss by
decreasing the number of intercalation sites for lithium,
impedance rise from reduced active surface area, and LLI due
to the loss of lithiated active material. While the rate of LAMNE
accelerates, the rate of LAMPE apparently slows in all of the
cycles in Figure 2. In all cells, the data show a drop in nLi,
although VAH11 and VAH12 show the bimodal distribution
discussed above.
It is well-reported in the literature that some parameters of
battery models are unidentifiable.29,30 To analyze the
identifiability of the degradation modes, we show a scatter
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ACS Energy Letters http://pubs.acs.org/journal/aelccp Letter

Figure 3. Degradation parameter and mode identifiability for VAH01 at a cycle in the beginning, middle, and end of life. On the upper right,
posterior distributions for each pair of parameters are plotted against one another. Darker colors indicate a later cycle. The tables on the
bottom left give the correlation coefficient between each pair of variables and the cycle number. On the diagonal are kernel density plots of
the posterior probability distribution of each parameter (note that the y-axis for these should be kernel density or bin count and is not
shown).

Figure 4. (a) Correlation between cycling characteristics and total change in degradation modes and parameters divided by the number of
cycles. (b) Z-scores from the Mann−Kendall test as a function of cycle number for VAH01. (c−e) Computed cosine distances between the
expected and observed degradation mechanisms at (c) 1/3 of life, (d) 2/3 of life, and (e) end of life.

matrix of the pairwise posterior distribution for each pair of
parameters for 3 cycles of VAH01 in Figure 3. We begin by
noting the strong correlation between f−s and ϵ−e , and between
f+s and ϵ+e , all having ρ > 0.9. ω also has a moderate correlation
with ϵ−e , indicative of the aforementioned coupling between
those parameters by the Bruggeman relationship. Interestingly,
ϵ+s shows only a weak correlation with f+s and ϵ+e , indicating that
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ϵ+s is identifiable. Similarly, ϵ−s is very weakly correlated with ϵ−e
and weakly correlated with f−s , indicating that it too is
identifiable in the case of VAH01. Figure S2 shows the same
scatter matrix for VAH12. In contrast to the baseline cycle, for
cycles with low DOD, such as VAH12, the distributions of nLi
and ϵ−s overlap for all cycles. This indicates a low parameter
sensitivity for cycles with lower DOD. For lower DOD cycles,
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ϵ−s and ϵ+s have stronger correlation than those with higher
DOD (ρ ≈ 0.75 for VAH12 and ρ ≈ 0.6 for VAH01). For the
rest of the parameters, the shapes of the distributions remain
relatively constant, indicating no change in structural
identifiability.
Our method facilitates analysis of associations between
specific degradation modes and characteristics of the duty
cycle. Figure 4a shows a correlation heat map between the
cycling characteristics and the average rate of change in each
mode. The average rates of change ω, nLi, ϵ−s , and ϵ+s are all
moderately correlated with DOD. A potential mechanistic
explanation for this is stress gradients induced by volume
changes causing LAMPE and SEI growth on crack surfaces.12
Maximum temperature shows some moderate correlation with
the rate of change of ω and weak correlation with ϵ−s , both
indicative of SEI growth. The maximum current shows a
moderate correlation with LAMPE, again potentially indicative
of particle fracture driven by stress. Applying our method to
larger data sets with more variation in cycling conditions could
help to further improve this analysis.
To gain more mechanistic insight into degradation
mechanisms, we develop a protocol to compare the identified
modes with degradation mechanism models from literature.
We use the Mann−Kendall test to determine whether any
parameter has a significant trend over life of the battery.51−53
Figure 4b shows the Z-score as a function of the cycle life. For
the parameters that vary significantly, all trends are identified
in the first 100 cycles. To compare the observed trends to the
expected trends, we define a vector for each mechanism and
cell, assigning −1 for an expected or observed decrease, 0 for
no effect, and 1 for an expected or observed increase. Finally,
we take the cosine distance between the observed vector and
the expected vector for each cell and mechanism. The expected
effects of each mechanism are shown in Table S3. Panels c−e
of Figure 4 show the cosine distances for all cells and all
mechanisms at 3 points over the battery life. More detailed
results, including cycle-by-cycle Z-score plots and diagnoses,
are available in the SI. Our algorithm infers SEI growth as the
most likely degradation mechanism affecting the negative
electrode, and dissolution, electrolyte oxidation, and stress-
based LAM as the most likely mechanisms affecting the
positive electrode. The scores are notably low for positive
electrode SEI formation as well as positive electrode pore
clogging.
The degradation modes as identified via this method have
uses beyond the protocol we developed herein and
applications beyond electric aviation. One use-case for
electrochemical modeling is the development of model-based
fast charging protocols.54−61 These protocols aim to reduce
charging time while constraining internal quantities related to
safety and degradation.62 They assume that the model
parameters are known. Our method allows engineers who
develop these methods to adopt their protocols to the
degraded state of the battery, and having probability
distributions for the modes will let them quantify uncertainty
in the degradation caused by the protocol.
Another use-case is forecasting future degradation. The
identified degradation mode distributions will allow engineers
and operators to initialize and update their models with the
current state of the battery.31,33 They can also be used to train
machine-learning models on more specific degradation modes,
which currently focus primarily on impedance and ca-
pacity63−65 or to develop machine-learning diagnostic
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methods.66 Finally, they could be used to further help identify
degradation mechanisms via techniques such as symbolic
regression.67,68 These models could additionally help to
facilitate a second life usage for aircraft batteries69,70 by
allowing engineers to forecast batteries’ future capabilities.
Having parameter distributions rather than point estimates will
allow engineers to quantify uncertainty stemming from the
state of battery degradation for all of these applications.71
There are also immediate applications for this method and
these data. For example, it is unclear what battery state
information will be displayed to aircraft operators. Given that
aircraft have to maintain a minimum power to remain aloft,
pilots will likely need to be informed of the current state of
available power (SOAP).72,73 These estimated modes will
allow operators to have a wide range of information to display
to the pilot, including available power, range, and thermal
consequences of any given trajectory.2 They can also use these
correlations to modify the operating profiles of their aircraft.
For example, it is obvious based on these data that a slightly
lower DOD can lead to a much longer lifetime, meaning that it
is likely economically beneficial for operators to minimize
DOD. By having extrapolative physical models for battery
degradation, aircraft operators and designers can conduct trade
studies on battery degradation, for example, studying the
economic effects of increased degradation from DOD.
One disadvantage of the proposed methodology is its high
computational cost. However, in practice, the computational
cost could be reduced in several ways. First, in some
applications (specifically lower power applications), there is
likely no need to simulate an electrolyte. This will reduce the
computational cost by decreasing the time needed to simulate
a model as well as by decreasing the cost of a gradient
evaluation by decreasing both the model size and number of
parameters (the computational expense of forward sensitivity
analysis is O(np) and adjoint sensitivity analysis is O(n + p),
where n is the number of equations and p is the number of
parameters74), at the cost of losing information regarding
degradation modes that primarily affect the electrolyte. While
even lower order models could be used, we caution that
empirical models, such as equivalent circuit models, cannot
provide the same level of insight as physics-based models.
Another option that could help decrease the computational
cost is to use the previous cycle’s posterior distribution as the
prior for any given cycle (except for the first cycle), which
would likely speed convergence by starting the sampler near
the posterior, given that battery degradation typically changes
on a time scale much longer than one cycle. Finally, in practice,
it is unlikely that every cycle needs to be sampled; though
decreasing the sampling rate will decrease the temporal
resolution of the identified degradation modes.
There are several ways in which this work could be
improved upon in the future. The first is to modify the model.
As solution times for electrochemical simulations improve via
better tools and numerical methods,75,76 higher order models
ranging from three-dimensional electrochemical models to
multiphase porous electrode theory77 to higher dimensional
models78 could be used to conduct these kinds of analyses.
The second is to use more and different data sets including
different cycling conditions and different chemistries and cells,
which will help to ensure generalization and to provide data to
researchers in applications other than electric aviation. Finally,
future researchers can conduct postmortem destructive
physical analyses in order to verify the discovered parameters.
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■ ASSOCIATED CONTENT
Data Availability Statement
The data generated in this work are available from the authors
upon request. The code used in this work is available on
github.
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsenergylett.3c01216.
Modeling and sampler details, convergence plots and
statistics, and more detailed additional results including
statistical and diagnostic results for each cell and further
comparison between experiment and data (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Venkatasubramanian Viswanathan − Department of
Mechanical Engineering, Carnegie Mellon University,
Pittsburgh, Pennsylvania 15213, United States; orcid.org/
0000-0003-1060-5495; Email: venkvis@cmu.edu
Authors
Alexander Bills − Department of Mechanical Engineering,
Carnegie Mellon University, Pittsburgh, Pennsylvania 15213,
United States; orcid.org/0000-0001-7992-8837
Leif Fredericks − Department of Mechanical Engineering,
Carnegie Mellon University, Pittsburgh, Pennsylvania 15213,
United States; orcid.org/0000-0002-5069-4915
Valentin Sulzer − Department of Mechanical Engineering,
Carnegie Mellon University, Pittsburgh, Pennsylvania 15213,
United States
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsenergylett.3c01216
Author Contributions
Conceptualization: A.B. and V.V. Software: A.B. and L.F.
Modeling: A.B. and V.S. Analysis: A.B. and L.F. Writing: initial
draft, A.B.; final draft, all authors.
Notes
The authors declare the following competing financial
interest(s): The authors have filed a patent application related
to digital twins for battery packs in aviation.
■ ACKNOWLEDGMENTS
We acknowledge support from Airbus A3 and Ampaire and
discussions with Evan Frank, Devin Charles, Nate Wynn,
Shashank Sripad, and Matthew Guttenberg, as well as
experimental support from Airbus Defense and Space and
Romain Tellier. This research was done using services
provided by the OSG Consortium, which is supported by
the National Science Foundation Award Nos. 2030508 and
1836650. This work used the Extreme Science and Engineering
Discovery Environment (XSEDE), which is supported by
National Science Foundation (NSF) Grant No. ACI-1548562.
Specifically, it used the Bridges-2 system, which is supported
by NSF Award No. ACI-1928147, at the Pittsburgh Super-
computing Center (PSC).
■ REFERENCES
(1) Ciez, R. E.; Whitacre, J. F. Examining different recycling
processes for lithium-ion batteries. Nature Sustainability 2019 2:2
2019, 2, 148−156.
3583
Letter
(2) Fredericks, W. L.; Sripad, S.; Bower, G. C.; Viswanathan, V.
Performance Metrics Re- quired of Next-Generation Batteries to
Electrify Vertical Takeoff and Landing (VTOL) Aircraft. ACS Energy
Letters 2018, 3, 2989−2997.
(3) Yang, X. G.; Liu, T.; Ge, S.; Rountree, E.; Wang, C. Y.
Challenges and key requirements of batteries for electric vertical
takeoff and landing aircraft. Joule 2021, 5, 1644−1659.
(4) Darling, R.; Newman, J. Modeling Side Reactions in Composite
Li y Mn2 O 4 Elec- trodes. J. Electrochem. Soc. 1998, 145, 990−998.
(5) Ramadass, P.; Haran, B.; Gomadam, P. M.; White, R.; Popov, B.
N. Development of First Principles Capacity Fade Model for Li-Ion
Cells. J. Electrochem. Soc. 2004, 151, A196.
(6) Safari, M.; Morcrette, M.; Teyssot, A.; Delacourt, C. Multimodal
Physics-Based Aging Model for Life Prediction of Li-Ion Batteries. J.
Electrochem. Soc. 2009, 156, A145.
(7) Ning, G.; Popov, B. N. Cycle Life Modeling of Lithium-Ion
Batteries. J. Electrochem. Soc. 2004, 151, A1584.
(8) Lin, X.; Park, J.; Liu, L.; Lee, Y.; Sastry, A. M.; Lu, W. A
Comprehensive Capacity Fade Model and Analysis for Li-Ion
Batteries. J. Electrochem. Soc. 2013, 160, A1701−A1710.
(9) Li, H.; Liu, A.; Zhang, N.; Wang, Y.; Yin, S.; Wu, H.; Dahn, J. R.
An Unavoidable Challenge for Ni-Rich Positive Electrode Materials
for Lithium-Ion Batteries. Chem. Mater. 2019, 31, 7574−7583.
(10) Ai, W.; Kraft, L.; Sturm, J.; Jossen, A.; Wu, B. Electrochemical
Thermal-Mechanical Modelling of Stress Inhomogeneity in Lithium-
Ion Pouch Cells. Journal of The Elec- trochemical Society 2020, 167,
013512.
(11) Gauthier, R.; Luscombe, A.; Bond, T.; Bauer, M.; Johnson, M.;
Harlow, J.; Louli, A. J.; Dahn, J. R. How do Depth of Discharge, C-
rate and Calendar Age Affect Capacity Retention, Impedance Growth,
the Electrodes, and the Electrolyte in Li-Ion Cells? J. Electrochem. Soc.
2022, 169, 020518.
(12) Laresgoiti, I.; Kabitz, S.; Ecker, M.; Sauer, D. U. Modeling
mechanical degradation in lithium ion batteries during cycling: Solid
electrolyte interphase fracture. J. Power Sources 2015, 300, 112−122.
(13) Yang, X. G.; Leng, Y.; Zhang, G.; Ge, S.; Wang, C. Y. Modeling
of lithium plating in- duced aging of lithium-ion batteries: Transition
from linear to nonlinear aging. J. Power Sources 2017, 360, 28−40.
(14) Reniers, J. M.; Mulder, G.; Howey, D. A. Review and
Performance Comparison of Mechanical-Chemical Degradation
Models for Lithium-Ion Batteries. J. Electrochem. Soc. 2019, 166,
A3189−A3200.
(15) Attia, P. M.; et al. Review�“Knees” in Lithium-Ion Battery
Aging Trajectories. J. Electrochem. Soc. 2022, 169, 060517.
(16) O’Kane, S. E.; Ai, W.; Madabattula, G.; Alonso-Alvarez, D.;
Timms, R.; Sulzer, V.; Edge, J. S.; Wu, B.; Offer, G. J.; Marinescu, M.
Lithium-ion battery degradation: how to model it. Phys. Chem. Chem.
Phys. 2022, 24, 7909−7922.
(17) Dubarry, M.; Truchot, C.; Liaw, B. Y. Synthesize battery
degradation modes via a diagnostic and prognostic model. J. Power
Sources 2012, 219, 204−216.
(18) Han, X.; Ouyang, M.; Lu, L.; Li, J.; Zheng, Y.; Li, Z. A
comparative study of commer- cial lithium ion battery cycle life in
electrical vehicle: Aging mechanism identification. J. Power Sources
2014, 251, 38−54.
(19) Birkl, C. R.; Roberts, M. R.; McTurk, E.; Bruce, P. G.; Howey,
D. A. Degradation diagnostics for lithium ion cells. J. Power Sources
2017, 341, 373−386.
(20) Bloom, I.; Jansen, A. N.; Abraham, D. P.; Knuth, J.; Jones, S. A.;
Battaglia, V. S.; Hen- riksen, G. L. Differential voltage analyses of
high-power, lithium-ion cells: 1. Technique and application. J. Power
Sources 2005, 139, 295−303.
(21) Chen, B. R.; Walker, C. M.; Kim, S.; Kunz, M. R.; Tanim, T. R.;
Dufek, E. J. Battery aging mode identification across NMC
compositions and designs using machine learning. Joule 2022, 6,
2776−2793.
(22) Troltzsch, U.; Kanoun, O.; Trankler, H.-R. Characterizing aging
effects of lithium ion batteries by impedance spectroscopy. Electro-
chim. Acta 2006, 51, 1664−1672.
https://doi.org/10.1021/acsenergylett.3c01216
ACS Energy Lett. 2023, 8, 3578−3585
ACS Energy Letters http://pubs.acs.org/journal/aelccp
(23) Zhang, Y.; Wang, C.-Y. Cycle-Life Characterization of
Automotive Lithium-Ion Bat- teries with LiNiO[sub 2] Cathode. J.
Electrochem. Soc. 2009, 156, A527.
(24) Pastor-Ferńandez, C.; Yu, T. F.; Widanage, W. D.; Marco, J.
Critical review of non- invasive diagnosis techniques for quantification
of degradation modes in lithium-ion batteries. Renewable and
Sustainable Energy Reviews 2019, 109, 138−159.
(25) Huang, Q. A.; Shen, Y.; Huang, Y.; Zhang, L.; Zhang, J.
Impedance Characteristics and Diagnoses of Automotive Lithium-Ion
Batteries at 7.5% to 93.0% State of Charge. Electrochim. Acta 2016,
219, 751−765.
(26) Huhman, B. M.; Heinzel, J. M.; Mili, L.; Love, C. T.; Wetz, D.
A. Investigation into State-of-Health Impedance Diagnostic for 26650
4P1S Battery Packs. J. Electrochem. Soc. 2017, 164, A6401−A6411.
(27) Schindler, S.; Danzer, M. A. A novel mechanistic modeling
framework for analysis of electrode balancing and degradation modes
in commercial lithium-ion cells. J. Power Sources 2017, 343, 226−236.
(28) Pastor-Ferńandez, C.; Uddin, K.; Chouchelamane, G. H.;
Widanage, W. D.; Marco, J. A Comparison between Electrochemical
Impedance Spectroscopy and Incremental Capacity-Differential
Voltage as Li-ion Diagnostic Techniques to Identify and Quan- tify
the Effects of Degradation Modes within Battery Management
Systems. J. Power Sources 2017, 360, 301−318.
(29) Berliner, M. D.; Zhao, H.; Das, S.; Forsuelo, M.; Jiang, B.;
Chueh, W. H.; Bazant, M. Z.; Braatz, R. D. Nonlinear Identifiability
Analysis of the Porous Electrode Theory Model of Lithium-Ion
Batteries. J. Electrochem. Soc. 2021, 168, 090546.
(30) Forman, J. C.; Moura, S. J.; Stein, J. L.; Fathy, H. K. Genetic
identification and fisher identifiability analysis of the Doyle-Fuller-
Newman model from experimental cycling of a LiFePO4 cell. J. Power
Sources 2012, 210, 263−275.
(31) Kapteyn, M. G.; Pretorius, J. V.; Willcox, K. E. A probabilistic
graphical model foun- dation for enabling predictive digital twins at
scale. Nature Computational Science 2021 1:5 2021, 1, 337−347.
(32) Ruan, H.; Chen, J.; Ai, W.; Wu, B. Generalised diagnostic
framework for rapid battery degradation quantification with deep
learning. Energy and AI 2022, 9, 100158.
(33) Dubarry, M.; Howey, D.; Wu, B. Enabling battery digital twins
at the industrial scale. Joule 2023, 7, 1134−1144.
(34) Ramadesigan, V.; Chen, K.; Burns, N. A.; Boovaragavan, V.;
Braatz, R. D.; Subrama- nian, V. R. Parameter Estimation and
Capacity Fade Analysis of Lithium-Ion Batteries Using Reformulated
Models. J. Electrochem. Soc. 2011, 158, A1048.
(35) Fan, G.; Lu, D.; Trimboli, M. S.; Plett, G. L.; Zhu, C.; Zhang, X.
Nondestructive diag- nostics and quantification of battery aging under
different degradation paths. J. Power Sources 2023, 557, 232555.
(36) Li, J.; Wang, D.; Deng, L.; Cui, Z.; Lyu, C.; Wang, L.; Pecht, M.
Aging modes analysis and physical parameter identification based on a
simplified electrochemical model for lithium-ion batteries. Journal of
Energy Storage 2020, 31, 101538.
(37) Uddin, K.; Perera, S.; Widanage, W. D.; Somerville, L.; Marco,
J. Characterising Lithium-Ion Battery Degradation through the
Identification and Tracking of Electro- chemical Battery Model
Parameters. Batteries 2016, Vol. 2, Page 13 2016, 2, 13.
(38) Daigle, M.; Kulkarni, C. S. End-of-discharge and End-of-life
Prediction in Lithium-ion Batteries with Electrochemistry-based
Aging Models. AIAA Infotech@Aerospace, AIAA 2016-2132; SCI-
TECH Forum, 2016. DOI: 10.2514/6.2016-2132.
(39) Sfiligoi, I.; Bradley, D. C.; Holzman, B.; Mhashilkar, P.; Padhi,
S.; Wü rthwein, F. The Pilot Way to Grid Resources Using
glideinWMS. 2009 WRI World Congress on Computer Science and
Information Engineering, CSIE 2009; IEEE, 2009; Vol. 2, pp 428−432.
DOI: 10.1109/CSIE.2009.950.
(40) Pordes, R.; et al. The open science grid. Journal of Physics:
Conference Series 2007, 78, 012057.
(41) Bills, A.; Sripad, S.; Fredericks, L.; Guttenberg, M.; Charles, D.;
Frank, E.; Viswanathan, V. A battery dataset for electric vertical
takeoff and landing aircraft. Sci. Data 2023, 10, 344.
3584
Letter
(42) muRata. Cylindrical Type Lithium Ion Secondary Batteries.
https://www.murata.com/en-us/products/batteries/cylindrical (ac-
cessed 2023-07-17).
(43) Brosa Planella, F.; et al. A continuum of physics-based lithium-
ion battery models reviewed. Prog. Energy 2022, 4, 042003.
(44) Subramaniam, A.; Kolluri, S.; Parke, C. D.; Pathak, M.;
Santhanagopalan, S.; Sub-ramanian, V. R. Properly Lumped Lithium-
ion Battery Models: A Tanks-in-Series Approach. J. Electrochem. Soc.
2020, 167, 013534.
(45) Doyle, M.; Fuller, T. F.; Newman, J. Modeling of Galvanostatic
Charge and Discharge of the Lithium/Polymer/Insertion Cell. J.
Electrochem. Soc. 1993, 140, 1526−1533.
(46) Girolami, M.; Calderhead, B. Riemann manifold Langevin and
Hamiltonian Monte Carlo methods. Journal of the Royal Statistical
Society: Series B (Statistical Method- ology) 2011, 73, 123−214.
(47) Hoffman, M. D.; Gelman, A. The No-U-Turn Sampler:
Adaptively Setting Path Lengths in Hamiltonian Monte Carlo. J.
Mach. Learn. Res. 2014, 15, 1593−1623.
(48) Ge, H.; Xu, K.; Ghahramani, Z. Turing: a language for flexible
probabilistic inference. Proceedings of the Twenty-First International
Conference on Artificial Intelligence and Statistics; PMLR, 2018; pp
1682−1690.
(49) Bezanson, J.; Karpinski, S.; Shah, V. B.; Edelman, A. Julia: A fast
dynamic language for technical computing. arXiv Preprint (Program-
ming Languages, Computer Science), 2012. arXiv:1209.5145. https://
arxiv.org/abs/1209.5145 (accessed 17-July-2023).
(50) Edge, J. S.; O’Kane, S.; Prosser, R.; Kirkaldy, N. D.; Patel, A.
N.; Hales, A.; Ghosh, A.; Ai, W.; Chen, J.; Yang, J.; et al. Lithium ion
battery degradation: what you need to know. Phys. Chem. Chem. Phys.
2021, 23, 8200−8221.
(51) Kendall, M. G. a New Measure of Rank Correlation. Biometrika
1938, 30, 81−93.
(52) Mann, H. B. Nonparametric Tests Against Trend. Econometrica
1945, 13, 245.
(53) Hussain, M. M.; Mahmud, I. pyMannKendall: a python
package for non parametric Mann Kendall family of trend tests.
Journal of Open Source Software 2019, 4, 1556.
(54) Berliner, M. D.; Jiang, B.; Cogswell, D. A.; Bazant, M. Z.;
Braatz, R. D. Novel Oper- ating Modes for the Charging of Lithium-
ion Batteries. J. Electrochem. Soc. 2022, 169, 100546.
(55) Perez, H. E.; Hu, X.; Moura, S. J. Optimal charging of batteries
via a single particle model with electrolyte and thermal dynamics.
2016 American Control Conference (ACC); IEEE, 2016; pp 4000−
4005. DOI: 10.1109/ACC.2016.7525538.
(56) Pozzi, A.; Moura, S.; Toti, D. A deep learning-based predictive
controller for the opti- mal charging of a lithium-ion cell with non-
measurable states. Comput. Chem. Eng. 2023, 173, 108222.
(57) Zou, C.; Hu, X.; Wei, Z.; Tang, X. Electrothermal dynamics-
conscious lithium-ion battery cell-level charging management via
state-monitored predictive control. Energy 2017, 141, 250−259.
(58) Gopaluni, R. B. An Algorithm for Optimal Charging of Li-Ion
Batteries Using a Single Particle Model. Proceedings of the 5th
International Symposium on Advanced Control of Industrial Processes,
2014.
(59) Choe, S.-Y.; Li, X.; Xiao, M. Fast charging method based on
estimation of ion con- centrations using a reduced order of
Electrochemical Thermal Model for lithium ion polymer battery.
2013 World Electric Vehicle Symposium and Exhibition (EVS27); IEEE,
2013; pp 1−11. DOI: 10.1109/EVS.2013.6914966.
(60) Lam, F.; Allam, A.; Joe, W. T.; Choi, Y.; Onori, S. Offline
multiobjective optimization for fast charging and reduced degradation
in lithium ion battery cells. 2021 American Control Conference (ACC);
IEEE, 2021; pp 4441−4446.
(61) Bills, A.; Salazar, M.; Zhang, D.; Viswanathan, V. A Model
Predictive Control Scheme for Fast Charging via Accurate Quadratic
Battery Models. 2022 American Control Conference (ACC); IEEE,
2022; pp 1794−1800. DOI: 10.23919/ACC53348.2022.9867614.
https://doi.org/10.1021/acsenergylett.3c01216
ACS Energy Lett. 2023, 8, 3578−3585
ACS Energy Letters http://pubs.acs.org/journal/aelccp Letter

(62) Gao, Y.; Zhang, X.; Cheng, Q.; Guo, B.; Yang, J. Classification
and review of the charging strategies for commercial lithium-ion
batteries. Ieee Access 2019, 7, 43511−43524.
(63) Sulzer, V.; Mohtat, P.; Aitio, A.; Lee, S.; Yeh, Y. T.; Steinbacher,
F.; Khan, M. U.; Lee, J. W.; Siegel, J. B.; Stefanopoulou, A. G.; et al.
The challenge and opportunity of battery lifetime prediction from
field data. Joule 2021, 5, 1934−1955.
(64) Richardson, R. R.; Osborne, M. A.; Howey, D. A. Gaussian
process regression for forecasting battery state of health. J. Power
Sources 2017, 357, 209−219.
(65) Tagade, P.; Hariharan, K. S.; Ramachandran, S.; Khandelwal,
A.; Naha, A.; Ko- lake, S. M.; Han, S. H. Deep Gaussian process
regression for lithium-ion battery health prognosis and degradation
mode diagnosis. J. Power Sources 2020, 445, 227281.
(66) Costa, N.; Sanchez, L.; Ansean, D.; Dubarry, M. Li-ion battery
degradation modes diagnosis via Convolutional Neural Networks.
Journal of Energy Storage 2022, 55, 105558.
(67) Gasper, P.; Gering, K.; Dufek, E.; Smith, K. Challenging
practices of algebraic battery life models through statistical validation
and model identification via machine-learning. J. Electrochem. Soc.
2021, 168, 020502.
(68) Udrescu, S.-M.; Tegmark, M. AI Feynman: A physics-inspired
method for symbolic regression. Sci. Adv. 2020, 6, No. eaay2631.
(69) Martinez-Laserna, E.; Gandiaga, I.; Sarasketa-Zabala, E.;
Badeda, J.; Stroe, D.-I.; Swierczynski, M.; Goikoetxea, A. Battery
second life: Hype, hope or reality? A critical review of the state of the
art. Renewable and Sustainable Energy Reviews 2018, 93, 701−718.
(70) Martinez-Laserna, E.; Sarasketa-Zabala, E.; Villarreal Sarria, I.;
Stroe, D.-I.; Swierczynski, M.; Warnecke, A.; Timmermans, J.-M.;
Goutam, S.; Omar, N.; Rodriguez, P. Technical viability of battery
second life: A study from the ageing perspective. IEEE Trans. Ind.
Appl. 2018, 54, 2703−2713.
(71) Harris, S. J.; Noack, M. M. Statistical and machine learning-
based durability-testing strategies for energy storage. Joule 2023, 7,
920−934.
(72) Schlickenmaier, H.; Anderson, P.; Holtz, E.; Kroll, A.; Roggia,
S.; Schmidt, P.; Uchida, J. Forum 360: Flight Testing in the Age of Recommended by ACS
Electric Propulsion: Lessons from the Flight Test Pioneers. AIAA
AVIATION Forum and Exposition; American Institute of Aeronatics
and Astronautics, 2023. Anomaly Detection Method for Lithium-Ion Battery Cells
(73) Sripad, S.; Bills, A.; Viswanathan, V. A review of safety Based on Time Series Decomposition and Improved
considerations for batteries in aircraft with electric propulsion. MRS Manhattan Distance Algorithm
Bull. 2021, 46, 435−442. Minghu Wu, Sheng Hu, et al.
(74) Ma, Y.; Dixit, V.; Innes, M. J.; Guo, X.; Rackauckas, C. A DECEMBER 29, 2023
comparison of automatic differentiation and continuous sensitivity ACS OMEGA READ
analysis for derivatives of differential equation solutions. 2021 IEEE
High Performance Extreme Computing Conference (HPEC), 2021; pp Data Efficient and Stability Indicated Sampling for
1−9.
Developing Reactive Machine Learning Potential to Achieve
(75) Berliner, M. D.; Cogswell, D. A.; Bazant, M. Z.; Braatz, R. D.
Ultralong Simulation in Lithium-Metal Batteries
Methods�PETLION: Open-source software for millisecond-scale
porous electrode theory-based lithium-ion battery simulations. J. Longkun Xu, Qiang Wang, et al.
Electrochem. Soc. 2021, 168, 090504. DECEMBER 13, 2023
(76) Ai, W.; Liu, Y. Improving the convergence rate of Newman’s THE JOURNAL OF PHYSICAL CHEMISTRY C READ
battery model using 2nd order finite element method. Journal of
Energy Storage 2023, 67, 107512. Active Learning Platform for Accelerating the Search for
(77) Smith, R. B.; Bazant, M. Z. Multiphase porous electrode theory. High-Voltage Cathode Materials in an Extensive Chemical
Journal of The Elec- trochemical Society 2017, 164, No. E3291. Space
(78) Chu, H. N.; Kim, S. U.; Rahimian, S. K.; Siegel, J. B.; Monroe,
C. W. Param-eterization of prismatic lithium-iron-phosphate cells Heekyu Kim, Seungchul Lee, et al.
SEPTEMBER 15, 2023
through a streamlined ther- mal/electrochemical model. J. Power
THE JOURNAL OF PHYSICAL CHEMISTRY C READ
Sources 2020, 453, 227787.

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