Lithium-ion battery degradation indicators via

incremental capacity analysis

David Anseán, Manuela González, Cecilio Blanco, Víctor M. García

Juan C. Viera, Yoana Fernández Physical and Analytical Chemistry Department
Electrical Engineering Department University of Oviedo
University of Oviedo Oviedo, Spain
Gijón, Spain
anseandavid@uniovi.es

Abstract— Lithium ion battery (LIB) degradation originates battery degradation and performance [4]. Indeed, battery
from complex mechanisms, usually interacting simultaneously, degradation is a major concern in long-term, reliable
and in various degrees of intensity. Due to its complexity, to date, applications including EVs, BESS and aerospace systems,
identifying battery aging mechanisms remains challenging. To where long cycle life under demanding duty schedules is
resolve such issue, various techniques have been developed, required. Therefore, it is essential to understand and identify the
including in-situ incremental capacity (IC) and peak area (PA) LIB degradation phenomenon, which in fact is a complex
analysis. The use of these techniques has been proved to be process originated from multiple mechanisms, usually taking
valuable for identifying LIB degradation, both qualitatively and place simultaneously [4].
quantitatively. In addition, due to their in-situ and non-destructive
nature, the implementation of these techniques is feasible for on- In general, LIBs degrade by capacity and power fade.
board, battery management systems (BMS). However, the However, the underpinning phenomenon that originates LIB
understanding and direct applicability of IC and PA techniques is degradation are more complex, can be originated from multiple
not straightforward, as it requires the understanding of mechanisms taking place simultaneously. The main degradation
electrochemical and material science principles. Unfortunately, mechanisms are identified as: loss of lithium inventory (LLI),
BMS design teams rarely include battery scientists, and are mainly loss of active material (LAM), ohmic resistance increase (ORI)
composed of electrical engineers. Aiming to bridge gaps in and lithium plating [4]–[6]. From the different cell degradation
knowledge between electrical engineering and battery science,
modes, LLI is generally the primary source of cell degradation,
here we present a set of direct look-up tables generated from IC
mainly attributed to continuous growth of the solid electrolyte
analysis, that provides a simple tool for the evaluation of LIB
degradation modes. We begin with a brief overview of the basics
interface (SEI) layer [7]. The LLI is a loss of usable Li ions,
of IC and PA techniques and their relation to battery degradation caused by parasitic reactions that are originated in the NE
modes, to later present the look-up tables, and conclude with electrode/electrolyte interface. LLI is usually (but not always)
various real-life examples of cell degradation, to illustrate the use accompanied by LAM. The LAM is related to structural and
of the look-up tables. This study exemplifies the use of look-up mechanical degradation of the electrodes. In general, LAM is
tables for BMS applications, providing a simple, fast and accurate more prominent on the negative electrode (NE) than the positive
real-time estimation of LIB degradation modes. electrode (PE) [8]–[10]. Interestingly, LAM may be “silent”,
causing degradation effects not exhibited in cell capacity fade.
Keywords—lithium-ion battery; battery degradation modes; This “silent” degradation can eventually lead to sudden
incremental capacity analysis; look-up tables; appearances of capacity loss, known as second degradation
stages [5]. The ORI results from various sources of cell
I. INTRODUCTION degradation, and causes a shift of the voltage potential of the
cell, hence reducing its energy efficiency. Lastly, lithium plating
Lithium ion batteries (LIBs) have become ubiquitous in is often considered the most detrimental degradation mode; it
modern societies [1]. LIBs power electronic devices such as increases the rate of cell aging, and may also produce safety
laptops, cell phones, or tablets. Similarly, in virtue of continuous degradation, due to dendrite growth that can internally short-
improvements in battery research, LIBs have also become the circuit the battery [11].
power source of choice for sustainable transportation, e.g.,
electric and hybrid vehicles (EVs, HEVs) [2]. LIBs are also Numerous techniques - including in-situ and postmortem -,
gaining considerable attention in applications of massive energy have been developed throughout the years to evaluate cell
storage, i.e., battery energy storage systems (BESS) [3]. In view degradation [12], [13]. Among the in-situ techniques that are
of these facts, LIBs certainly play a fundamental role in feasible for BMS applications, incremental capacity (IC) and the
industrial and commercial applications worldwide. analysis of the peak area (PA) are considered some of the most
advanced, non-invasive techniques, to detect and identify the
Despite continuous advances in LIB technology, LIB evolution of LIB degradation modes [8], [14]–[16]. The results
systems still face issues to be addressed, mainly related to obtained from the IC and PA analyses provide a valuable
This work was supported in part by the Science and Innovation Ministry
and by FEDER, under the Projects DPI2013-046541-R, TIN2014-56967-R,
TEC2016-80700-R (AEI/FEDER, UE), and by the Principality of Asturias
Government under Project FC-15-GRUPIN14-073.

978-1-5386-3917-7/17/$31.00 ©2017 IEEE

approach of cell aging origins, both from a qualitative and [10], [14], [15], [19] to monitor cell degradation without the
quantitative perspective, respectively. However, using these need of complex postmortem analyses.
techniques is not straightforward, and further understanding of
the techniques needs to be acquired for an optimal evaluation The IC is the result of the ratio between an increment of
and detection of LIB degradation modes. capacity and a fixed-voltage increment (IC = ǻQ/ǻV). To
illustrate the mathematical expression in terms of cell voltage
Unfortunately, the two main disciplines (i.e., material curves, Fig. 2 is presented: in Fig. 2a we show the
science/electrochemistry and electrical/electronic engineering) charge/discharge curves under pseudo-thermodynamic
that technically contribute to the assessment of cell degradation conditions (i.e., C/25), in a commercial GIC||LFP cell, while Fig.
do not often interact. Ideally, in the design of an optimal LIB 2b shows the resulting IC curves. The resulting IC peaks are
system, it is fundamental that both scientists and engineers labeled as (ᬅǡᬆǡᬇǡᬈ and ᬉ) for charge, and (ᬚ, ᬛ, ᬜ, ᬝ
collaborate, and understand each other’s background at a certain and ᬞ) for the discharge. Each IC peak exhibits a unique shape
level. A single battery unit can be considered the connection, and intensity, as the electrochemical processes progress as the
mid-point of both disciplines. The approach behind this concept cell is charged or discharged. Each resulting IC peak is the result
is shown in Fig. 1, where we aim to illustrate the importance of of the convolution of the electrochemical reactions in the active
linking battery science and battery engineering, to design state positive and negative electrode materials. Therefore, the
of the art, reliable battery systems. resulting IC peaks contain electrochemical signatures of both
electrodes. The evolution of IC peak’s shape and position with
Herein, we present a framework to analyze cell degradation cycling yields key information on the cell degradation.
via IC and PA, using simple, direct look-up tables. The look-up
tables present the main LIB degradation indicators, with the To increase the power of the IC technique towards
advantage of avoiding extensive electrochemical analysis. We quantification of cell degradation, the PA curves are
shall provide first a brief introduction of the background of the implemented. The PA is a technique that quantifies in amp-hour
IC and PA analysis, then present the look-up tables, and the area associated with each phase transformation within a cell.
conclude with examples on real LIB experiments, to These phase transformations correspond to the formation of
demonstrate the applicability of the look-up tables. Due to space solid solutions, and are detected from the IC inflection points
constrains, in this work we analyze one particular LIB cell [8], [9]. Hence, the PA technique yields the capacity underneath
technology, i.e., graphite||lithium iron phosphate (GIC||LFP) the IC peaks from their voltage inflection points.
cells. However, the methodology provided here is valid for all
intercalation LIB materials. On account of its in-situ
characteristics and low computational cost, this framework
provides a unique tool that can be easily implemented in BMS.

Fig. 1. Required background in the design of lithium-ion battery systems

II. THEORETICAL BACKGROUND – INCREMENTAL CAPACITY

AND PEAK AREA ANALYSIS TO IDENTIFY CELL DEGRADATION

A. Incremental Capacity (IC) and Peak Area (PA) Analysis

The IC is an electrochemical technique that detects gradual
changes in cell behavior with great sensitivity, by studying the
evolution with cycling of the resulting IC curves. The IC
analyses are based on the original work by Thompson [17] in
1979, to study materials. It was later used during the 1990s to Fig. 2. a) Charge (blue) and discharge (red) curves of a GIC||LFP cell under
characterize carbon materials [18], and more recently [5], [9], pseudo-thermodynamic conditions (C/25), and b) shows the resulting IC curves
a) B. Identification of cell degradation via IC and PA analysis
Degradation mechanisms in LIBs generally result from
various aging modes, including LLI, and LAM, ORI and lithium
plating, as previously commented. In addition, LAM is divided
into four degradation modes [5] on the negative electrode (i.e.,
LAMNE) and/or the positive electrode (i.e., LAMPE), either on
delithiated (de) or lithiated (li) state, giving a total of four aging
modes (i.e., LAMdeNE, LAMdePE, LAMliNE and LAMliPE). Each of
this aging mode affects both the IC and PA curves in a unique
manner. Hence, the analysis of each aging mode is required to
further construct the look-up tables. In this subsection, we
present an example (i.e., LLI) that shows how this aging mode
modifies the IC and PA, and what are the main signatures that
must be evaluated for its identification. A complete analysis of
b)
all the aging modes is out of the scope of this work, and can be
found in [5], [20].
1) Loss of lithium inventory (LLI): in a LIB, the LLI is
modeled as a slippage of the NE over the PE (see inset, Fig. 4)
[21]. This slippage causes a reduction of peak ᬚ (and the area
underneath), as indicated by arrow ᬚ, next to peak (Fig. 4).
Only upon further and drastical peak ᬚ reduction (i.e., all
intercalation stage ᬚ shifted outside voltage window of full
cell), peak ᬛ begins to reduce its intensity. LLI also causes a
rather slight shift of peak ᬞ upon cycling, moving it towards
high cell potentials. However, its intensity is not reduced.
Similarly, peaks 3 and 4 are barely altered by the effect of LLI.
Fig. 3. a) Discharge curve at C/25, showing the individual electrodes (positive, Finally, peak ᬚ and ᬛ voltage inflection point remains
blue, negative, black) and the resulting full cell curve (red). In b), the schematic constant, although the IC value is reduced.
representation to obtain the PA is presented
The effects of LLI on PA are the shown in Fig 5a. As
Fig. 3 presents the use of the PA technique: Fig. 3a shows observed, LLI induces a linear capacity fade of ‫׬‬ᬚ, reaching a
the discharge curve of a commercial GIC||LFP cell (red curve). point where its capacity is lost. In contrast, ‫׬‬ᬛǦᬞ evolution
This voltage potential is obtained from the subtraction of the remains unaffected, until ‫׬‬ᬚ is vanished. From that point, ‫׬‬ᬛǦ
positive electrode (blue, LFP) minus the negative (black, ᬞ begins to lose capacity linearly. In the full cell, LLI induces
graphite) electrode. The PA is calculated from the capacity a linear capacity loss throughout cycling (see Fig. 5b).
associated underneath the IC peaks (dashed area, Fig. 3b), which
correspond to various phase transformations. In brief, LLI mainly affects ‫׬‬ᬚ. Only under massive cell
degradation ‫׬‬ᬛǦᬞ is affected, whereas ᬞ can be used as a
To calculate the area of a peak, i.e., ‫׬‬ᬚ, the IC curve is succinct indicator. Hence, to identify LLI in a GIC||LFP cell, one
generated. Then, the voltage minima (i.e., inflection point, VIP) should verify peak ᬚ reduction on the IC curves, together with
between peak ᬚ and ᬛ is detected. The inflection point is
evaluated versus the cell capacity (in this particular case,
SOCPE). Subtracting the cell capacity at the detected VIP, minus
the full cell capacity yield the peak area for peaks ᬛǦᬞ, i.e.,
‫׬‬ᬛǦᬞ. The calculation of ‫׬‬ᬚ can now be directly calculated,
as is the result of the full cell capacity minus ‫׬‬ᬛǦᬞ. For better
quantification of the aging modes, it is recommended to distinct
the area underneath peak ᬚ and the area associated under peaks
ᬛǦᬞ. This is because principal aging mode (i.e., LLI) affects
mostly to peak ᬚ [5], therefore facilitating its detection. In
addition, peaks ᬛǦᬞ affect LAM on the NE, another common
degradation mode.
The PA distribution is given directly in amp-hour, or in terms
of percentage of the total cell capacity. Following the same
approach as with IC as the cell ages, the evolution of the PA
distribution changes. Hence, tracking the evolution of the PA
with cell aging allows for an in-situ evaluation of degradation Fig. 4. IC signatures of LLI evolution from beginnig (solid line) to end of
modes from a quantitative perspective (i.e., in amp-hour). cycling (dashed). Inset figure shows the NE slippage effect
a) b) TABLE I. LOOK-UP TABLE OF MAIN AGING MODES, PARTICULARIZED
FOR GIC||LFP CELL DURING DISCHARGE. NOTICE THAT ARROW ՛ INDICATES
IC PEAK REDUCTION

Incremental Capacity Peak Number

Aging mode
ᬚ ᬛ ᬜ ᬝ ᬞ ᬮ
LLI ՛ ൌ՛ ൌ ൌ ՜ Ǧ
LAMdeNE ՝՛ ՛ ՛ ՛ ՠ ൌ ‘” ՝
LAMliNE ՛ ՛ ՛ ՛ ա Ǧ
Fig. 5. a) Normalized PA evolution under LLI for peak 1 (squared) and peak
2-5 (diamond), and b) capacity fade evolution caused by the effect of LLI alone LAMdePE ൌգ ൌ՛ ൌ՛ ൌ՛ ՛ Ǧ

the linear degradation of capacity fade, linear degradation of

LAMliPE ՛ ൌ՛ ൌ ൌ ൌ Ǧ
‫׬‬ᬚ in the PA, while peaks ‫׬‬ᬛǦᬞ are unaffected. The given ORI ՚ ՚ ՚ ՚ ՚ Ǧ
analysis procedure, evaluating peak evolution for a particular
degradation mechanisms is carried out to construct the look-up increase. The horizontal arrows indicate a voltage shift of the
tables. peaks. The equal symbols indicate no changes in the peaks. The
symbols red-typed are to be applied during second degradation
III. EXPERIMENTAL stages, e.g., for LLI, that occurs when peak ᬚis vanished then
In this work, we use both computer simulations and peak ᬛ starts to decrease, or for under the effects of lithium
experimental testing results. Computer simulations were carried plating, under severe LAMdeNE occurrence. Under the effects of
out with the ‘alawa toolbox, developed at the University of lithium plating, peak ᬮmay or may not appear, depending on
Hawaii [5], [22]. The computer simulations were used to obtain its reversibility [24], [25].
the degradation patterns of the battery aging modes. The Table II presents the main features to evaluate during the PA
experimental procedures were carried out on commercial analyses. It additionally includes the effects that the aging modes
GIC||LFP batteries (2.3 Ah), using an Arbint BT-2000 battery cause on internal constructive parameters, such as loading ratio
tester. A Memmert environmental chamber was used to maintain (LR) and the offset (OFS) [5], features useful for advanced
the cells at 23ºC throughout testing. analyses. The table also presents whether the aging mode effect
Two examples of different cell degradation, based on two remains “silent” during its first degradation stage, and also
experimental cell testing design are presented in this work. One includes if the aging modes can lead to lithium plating. Aging
of the tests was carried out using a continuous current cycling, via ORI is excluded, as this aging mode does not induce capacity
whereas the second used dynamic stress cycling. For detailed fade intrinsically.
description of the testing procedures, readers shall refer to [9],
[23], [24]. TABLE II. LOOK-UP TABLE WITH MAIN FEATURES OF CELL
DEGRADATION, OBTAINED FROM THE PEAK AREA ANALYSES

IV. RESULTS AND DISCUSSION Aging Modes

Feature
In this section, we present the main signatures of each LLI LAMdeNE LAMliNE LAMdePE LAMliPE
individual aging mode in terms of IC, PA and capacity fade. As Linear/
Linear
Linear/
‫׬‬ᬚ increase/ Linear Not affected
commented, different aging modes produce a particular Depleted
Decreases
Depleted

evolution of the IC and PA signatures. In addition, some aging ‫׬‬ᬛǦᬞ

Unchanged/
Linear Linear
Unchanged/ Unchanged/
Linear Pseudo-linear Linear
modes have the same signatures for some IC peaks, which Unchanged/
Capacity Unchanged/
complicates its identification. Therefore, it is important to fade
Linear Unchanged Linear
Pseudo-linear
Linear
or linear
summarize and facilitate the IC and PA evolution for every Loading
Not affected Decreases Decreases Increases Increases
aging mode, individually, in form of look-up tables. The ratio (LR)
approach to analyze cell degradation gets therefore simplified: Offset
(OFS)
Increases
Not
affected
Increases
Reduces/
Negative
Not affected
one shall compare the experimental IC and PA results with the
“Silent” No Yes No Yes No
look-up tables, and evaluate the coincidences. Those changes
shall correspond to the acting aging mode(s). Risk of
plating
No Yes No No No

A. IC and PA look-up tables

Table I presents the look-up table from the IC analysis B. Use of the look-up tables in real-life experiments
during discharge, particularized for GIC||LFP cell technology. Here we present two examples to clarify the use of the look-
The table presents the degradation modes (left column), and up tables. Full discussion and analysis of the underpinning
their effect on the IC peaks. Notice that since the table is degradation modes found on the cells is out of the scope of this
manuscript. Interested readers shall refer to our previous works
constructed for IC discharge curves, the upward arrow indicates
[9], [24].
a peak reduction, whereas the downard arrow indicates a peak
Fig. 6 shows the IC and PA results obtained from a cell tested
under constant current scheme. The first thing to observe is that
all IC peaks are reduced (although not proportionally, see peak The above reasoning lead us to conclude that aging on the
ᬚ), and both PA ‫׬‬ᬚ and ‫׬‬ᬛ-ᬞ decrease linearly. From this cell is caused mainly by LLI (significant reduction of peak ᬚ),
initial observation, we can conclude that more than one aging accompanied by the effect of LAMdeNE (reduction of peaks ᬛ-
mode is acting simultaneously: checking the look-up tables, ᬞ). These results are in agreement with the literature [8], [9].
there is no single aging mode that causes uneven IC reduction,
Fig. 7 shows the IC and PA results obtained from the cell
together with linear, individual PA degradation.
tested under dynamic stress cycling. Degradation seems very
Secondly, we observe that the proportional reduction of IC complicated at first, with peaks shifting and even appearing (see
peaks ᬛǦᬞ should be only caused by LAMNE (Table I). This is peak ᬮ). However, these unique signatures facilitate the
also validated in the PA analyses (see Table II): LAMNE causes analysis: the peculiar appearance of peak ᬮ can only be derived
a linear degradation of peaks ‫׬‬ᬛǦᬞ. At this point, we by the effect of LAMdeNE (see Table II and Table II). Together
deciphered that cell degradation is caused by LAMNE with LAMdeNE, LLI is also acting on the cell: peak ᬚ reduction,
accompanied with other aging mode(s). peak ᬞ shift, together with linear peak ‫׬‬ᬛǦᬞreduction yields
these results. In fact, from this simple, straightforward analysis
Next, we shall look into the main sensor, i.e., peak ᬚ. it can be concluded that the cell is under lithium plating. These
Indeed, peak ᬚ is reduced more abruptly than the rest. By results are in agreement with detailed analyses from the
examining Table I, we observe that either LLI, LAMliNE and literature [24].
LAMliPE reduce peak intensity ᬚ. Under LAMliNE, peak ᬚ
would be reduced proportionally and hence, it would also a)
increase reduction of peaks ᬛǦᬞ. Therefore, if LAMliNE, was
primarily acting, peaks ‫׬‬ᬛǦᬞ would decrease at the same pace,
overestimating peak reduction and thus, not matching
experimental results. In the case of LAMliPE, peak ᬚ would be
reduced individually, potentially matching the experimental
results. However, LAMliPE would not produce any shift on peak
ᬞ. The case of LLI is the final match: peak ᬚ is reduced alone,
while not affecting ‫׬‬ᬛǦᬞ evolution, thus matching the
experimental results. In fact, the slight shift of peak ᬞ
counteracts the shift and reduction that LAMdeNE would produce
(see Table I). In addition, peak ᬚ reduction does not begin
abruptly, a fact that also matches with LAMdeNE signature.

a)

b)

b)

Fig. 7. Dynamic stress cycling, and its resultin a) IC and b) PA curves

V. CONCLUSION
The use of electrochemical techniques such as incremental
capacity (IC) and peak area (PA) can yield important
improvements for battery management systems (BMS) design,
to attain accurate measurements on cell degradation. However,
these techniques may seem complex to understand and to use,
particularly when the BMS designer’s background is not related
to battery science, which usually is the actual case.

Fig. 6. Constant current cycling, and its resulting a) IC and b) PA curves

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